Applied Catalysis A: General 480 (2014) 58–78

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Applied Catalysis A: General

journal homepage: [Link]/locate/apcata

Recent development of mixed metal oxide anodes for electrochemical

oxidation of organic pollutants in water
Weiyi Wu a,b , Zhao-Hong Huang c , Teik-Thye Lim a,b,∗
a
School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
b
Nanyang Environment & Water Research Institute (NEWRI), Nanyang Technological University, 1 Cleantech Loop, CleanTech One, Singapore 637141,
Singapore
c
Singapore Institute of Manufacturing Technology, 71 Nanyang Drive, Singapore 638075, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: Mixed metal oxides (MMOs) have been extensively employed for heterogeneous catalysis. In recent years,
Received 16 December 2013 MMOs have received an intensive interest as anode materials for electrochemical treatment of wastew-
Received in revised form 25 March 2014 aters which contain recalcitrant organics. This review article gives an overview of the classification of
Accepted 19 April 2014
MMO anodes systems, synthesis methods, characterization techniques, and recent advance of removing
Available online 26 April 2014
or alleviating various recalcitrant organic pollutants using MMO anodes, highlighting areas of consensus
and currently unresolved issues. Practical issues pertinent to modification to the catalytic activities of
Keywords:
MMO anodes are discussed, including nano- and microstructured deposits, doping and polymer com-
Mixed metal oxide (MMO)
Organic pollutants
posites. Electrogenerated reactive oxygen species (ROS) with MMO anodes and their determination by
Electrochemical oxidation various techniques have also been reviewed. In addition, this article discusses several important factors
Wastewater treatment which could affect the electrochemical oxidation of recalcitrant organics with MMO anodes, and critically
Surface modification identifies the shortcomings in current research including discrepant results and ambiguous conclusions.
Finally, the challenges and possible improvement of MMO anodes for their future application are also
proposed.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2. Metal oxide systems of MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2.1. Bulk mixed metal oxide anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2.2. Supported metal oxide anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3. Synthesis of MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4. Surface modification of MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.1. Deposits with nano- and microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.2. Doped MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.3. Polymer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5. Characterization of MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6. Active and non-active MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
7. Direct anodic and mediated anodic oxidation of organics by MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
8. Determination of reactive oxygen species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
9. Factors influencing electrochemical oxidation efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
9.1. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
9.2. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

∗ Corresponding author at: School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore.
Tel.: +65 67906933; fax: +65 67910676.
E-mail address: cttlim@[Link] (T.-T. Lim).

[Link]
0926-860X/© 2014 Elsevier B.V. All rights reserved.
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 59

9.3. Current density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

9.4. Supporting electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
10. Challenges, improvement and potential application of MMO anodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
10.1. Toxicity of byproducts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
10.2. Divided electrochemical oxidation cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
10.3. Coupling with other processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
11. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

single-component metal oxides. This could be due to an increase in

Nomenclature the surface area, an increase of active acidic or basic sites or a change
in the chemical states of the metal ions. Some important applica-
Abbreviation
tions of MMOs as heterogeneous catalyst include Al2 O3 supported
AFM atomic force microscopy
MMOs for (CH3 )2 S2 degradation [2], TiO2 -ZrO2 for nonoxida-
AOP advanced oxidation process
tive dehydrogenation of ethylcyclohexane [3], Mg-V-Al MMOs for
BDD boron doped diamond
oxidative dehydrogenation of propane [4], Fex Ce1−x O2 for N2 O
COD chemical oxygen demand
degradation [5], V-Sb-Nb MMOs for ammoxidation of propane [6],
CA carbon aerogel
LaNiO3 for ethanol reforming [7] and RuO2 -IrO2 -SnO2 for chloral-
CV cyclic voltammetry
kali process [8].
CVD chemical vapor deposition
Besides their applications as catalysts, MMOs have also been
DRS diffuse reflectance spectroscopy
studied for a wide range of other purposes, i.e. semiconductors,
DSA dimensionally stable anode
sensors, photoconductive thin films, and electrode materials for
EAOP electrochemical advanced oxidation process
lithium battery, fuel cell and environmental application [9–12].
EIS electrochemical impedance spectroscopy
Remarkable progress has been achieved in the research of MMOs’
FR fluorine resin
application as the anode material for electrochemical oxidation of
FTIR Fourier-transform infrared spectroscopy
recalcitrant pollutants in aqueous environment, since the treat-
FTO fluorine doped tin oxide
ment of water and wastewater has become a more challenging
ICE instantaneous current efficiency
issue due to the ineffective degradation of those pollutants by
MMO mixed metal oxide
conventional treatments which rely on biological process [13,14].
NT nanotube
Several reviews have described the removal or alleviation of recalci-
OEP oxygen evolution potential
trant organic pollutants in water by electrochemical oxidation, with
OER oxygen evolution reaction
regard to the various MMO anodes employed and different mech-
PED pulse electrodeposition
anisms involved [15–18]. Typically, MMO anodes are prepared
PVD physical vapor deposition
by depositing the MMOs layer on inert substrates (titanium, car-
PTFE polytetrafluoroethylene
bon, stainless steel, etc.). Indeed, increasing efforts have been put
SCE standard camel electrode
forward to evaluating the ability of MMO anodes to remove or alle-
SEM scanning electron microscopy
viate various types of recalcitrant organic pollutants including dyes,
SHE standard hydrogen electrode
pesticides and herbicides, phenolic compounds, pharmaceuticals,
TEM transmission electron microscopy
antibiotics and hormones, plasticizers, perfluorinated chemicals,
TOC total organic carbon
surfactants and derivatives, chelating agents and microcystin tox-
TGA thermalgravimetric analysis
ins.
XAS X-ray adsorption spectroscopy
Table 1 summarizes various types of recalcitrant organic pol-
XPS X-ray photoelectron spectroscopy
lutants which have been investigated for their electrochemical
XRD X-ray diffraction
oxidation with different MMO anodes. The organic pollutants can
be degraded by either direct oxidation or mediated oxidation with
Symbols
MMO anodes. In the mediated oxidation, the reactive chlorine gen-
Cd,i internal differential capacitance
erated from chlorides is the most commonly employed mediator.
Cd total differential capacitance
The reactive chlorine has the merit to treat landfill leachate [19,20]
Cdl pseudo-capacitance
and reverse osmosis (RO) concentrate from water reclamation
ϕmorph morphology factor
plant [21–24], both of which have high salinity. In general, MMO
anodes are effective to abate aqueous pollution caused by recal-
citrant organics, even for those which have extraordinary strong
1. Introduction C–F bond (490 kJ mol−1 ) [25–28]. With appropriate MMO anodes
chosen and suitable operating condition for electrochemical oxi-
dation, most recalcitrant organics can be completely removed, or
Metal oxides represent one of the most important categories
alleviated to their acceptable levels before biological treatment
of solid catalysts which are widely used either as active phases
[29].
or supports [1]. Because of their acid-base and redox properties,
In this review, several aspects of MMO anodes are discussed, i.e.
metal oxides have been extensively employed for heterogeneous
the classification of MMO anodes, their synthesis and characteri-
catalysis. Among all kinds of metal oxide catalysts, those which
zation, and the surface modification of MMO anodes, with specific
contain more than one kind of metal cations are known as mixed
emphasis on the improvement of their catalytic activity to degrade
metal oxides (MMOs). By mixing different metal oxides, new
aqueous organics pollutants by electrochemical oxidation. Several
stable compounds can be formed, and some of them exhibit sig-
factors which have important effects on the process efficiency are
nificant improvement in catalytic activity than their respective
60 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

Table 1
Summary of various types of recalcitrant organic pollutants which can be degraded by MMO anodes.

Compound MMO anode Current density Removal Current Service life (h) Reference
typea (mA cm−2 ) efficiencyc efficiency

Dyes and dye Acid Black 194 Ti/SnO2 - 30 0.57–0.88 0.014–0.024 –d [30]
effluent Sb/PbO2 -Pr [COD]
Acid Orange 7 Ti/SnO2 -Sb2 O4 20 0.88 [TOC] 0.39 – [31]
Gold yellow Ti/SnO2 - 43–86 0.40–0.74 – – [32]
X-GL Sb2 O3 /PTFE-La- [COD]
Ce-PbO2
Indigo carmine Ti/IrO2 -SnO2 - 5–20 0.99 [COD] – – [33]
Sb2 O5
Industrial dye Ti/RuO2 /IrO2 10–25 0.56–1 [COD] – – [34]
effluent
Industrial dye Ti/Ru-Ti-O 10–50 0.53–0.83 0.47–0.89 – [35]
effluent [COD]
Industrial dye SS/SnO2 -CeO2 P 0.49 [COD] – – [36]
effluent
Methyl orange Ti/SnO2 - 1 0.77 [Color] – 158 [37]
Sb/PbO2 -TiO2
Methyl orange Ti/PbO2 -Pr2 O3 40 0.89 [COD] 0.17 750 [38]
Methyl orange Ti/TiO2 - 30 0.59 [TOC] – – [39]
NTs/SnO2
Methyl orange TiO2 - P 0.16–0.27 – 116 [40]
NTs/SnO2 -Sb [Color]
Methyl orange Ti/IrO2 -SnO2 - P 0.98 [Color] – – [41]
Sb2 O5
Orange II Ti/SnO2 -Sb-Mn 10 0.46 [COD] – – [42]
Reactive Black Ti/RuO2 -IrO2 31.7 0.32 [COD] – – [43]
8
Reactive Blue Ti/TiO2 -RuO2 - 21.66 0.56 [COD] – – [44]
19 IrO2
Reactive Blue Ti/TiO2 - 100–200 0.30–0.40 0.06–0.09 75 [45]
194 NTs/SnO2 - [TOC]
Sb/PbO2
Reactive Blue Ti/IrO2 /TaO2 /RuO2 16.2 0.44 [COD] 0.04–0.065 – [46]
221
Reactive Ti/SnO2 -Sb-Pt 125 0.9–0.95 [COD] – 990 [47]
Orange 4
Reactive Red Ti/IrO2 -RuO2 15–50 0.32–0.43 0.13 – [48]
120 [COD]
Reactive Red Ti/SnO2 - 30 0.53–0.8 [TOC] 0.015–0.04 – [49]
195 Sb/PbO2
Reactive Red Ti/Ru0.3 Ti0.7 O2 5–89 0.40–0.80 – – [50]
198 [TOC]
Selected Ti/RhOx -TiO2 30 0.40 [Color] 0.1–0.2 – [51]
disperse dyes
Selected Ti/SnO2 -Sb-Pt 125 0.99 [Color] [52]
reactive dyes
Selected Ti/TiO2 -RuO2 - 72.2 0.735 [COD] – – [53]
reactive dyes IrO2
Synthetic dye Ti/Ti-Pt-Ir-O 5–14 0.55–0.86 0.045–0.314 – [54]
effluent [COD]

Pesticides and Atrazine Ti/Rux Sn1−x O2 10 0.21 [COD] – – [55]

herbicides (0.1 ≤ x ≤0.3)
Atrazine Ti/Ru0.3 Ti0.7 O2 10–120 0.04–0.46 – – [56,57]
[TOC]
Carbaryl Ti/Ru0.3 Ti0.7 O2 40 0.58 [COD] – – [58]
Cyanuric acid Ti/Ru0.3 Ti0.7 O2 5–50 0.13–0.56 – – [59]
[TOC]
Cypermethrin Ti/SnO2 -Sb 40–80 0.44–0.76 – – [60]
[COD]
Dichlorvos Ti/SnO2 -Sb2 O5 P 0.99 [COD] – – [61]
Methamidophos Ti/SnO2 -Sb 20–30 0.40 [COD] – – [62]
Glyphosate Ti/(RuO2 )0.7 (Ta2 O5 )0.350
; 0.81–0.91 0.20–0.40 – [63]
Ti/Ru0.3 X0.7 O2 [COD]
(X = Ti, Sn or
Pb);
Ti/Ir0.3 Sn0.7 O2

Phenolic Benzoic acid Ti/TiO2 - 20 0.658 [COD] 0.261 45 [64]

compounds NTs/Sb-SnO2
Phenol Ti/SnO2 - 0–50 0.72–0.84 0.15–0.2 [65]
Sb2 O3 /Nb2 O5 - [Phenol]
PbO2
Phenol Ti/SnO2 -Sb-Gd 20 0.74 [TOC] – – [66]
Phenol Ti/SnO2 -Sb2 O3 10–50 0.17–1[TOC] – – [67]
Phenol Ti/SnO2 -Sb-Eu 20 0.90 [TOC] – – [68]
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 61

Table 1 (Continued)

Compound MMO anode Current density Removal Current Service life (h) Reference
typea (mA cm−2 ) efficiencyc efficiency

Phenol Ti/SnO2 - 15 0.38–0.59 0.20–0.45 8.4–29.5 [69]

Sb2 O3 /PbO2 [COD]
Ti/SnO2 -
Sb2 O3 /MnO2
Ti/SnO2 -
Sb2 O3 /RuO2 -
PbO2
Phenol Ti/SnO2 -Sb2 O4 - 10 0.71 [COD] – 4.3 [70]
CNT
Phenol Ti/SnO2 -Sb2 O5 - 10 0.94 [COD] 0.53 59 [71]
RuO2 /␣-
PbO2 /␤-PbO2
Phenol Ti/SnO2 -Sb-La 30 0.86 [COD]; 0.406; 35.5; [72]
Ti/SnO2 -Sb-Ru 0.82 [COD] 0.386 34
Phenol Ti/TaOx - P – 0.6 – [73]
IrOx /BiOx -
TiO2 /BiOx -TiO2
Phenol Ti/TiO2 -BiOx 14.7 0.60 [Phenol] 0.67 – [74]
Pentachlorophenol Ti/SnO2 -Sb 5–40 0.9–0.99 [PCP] – – [75]
(PCP)
4- Ti/SnO2 - 20 0.81 [COD] 0.1–0.161 – [76]
Chlorophenol Sb/PbO2 -Er
4- Ti/SnO2 - 200 0.96 [COD] 0.87 141 [77]
Chlorophenol Sb2 O3 /PbO2 -
ZrO2
4- Ti/IrO2 /RuO2 39 0.9 [COD] – – [78]
Chlorophenol
4- Ti/Sn-Sb-Ni-O 3.1 0.99 [TOC] – – [79]
Chlorophenol
4-Chloro-3- Ti/SnO2 - 1–30 – 0.065–0.2 175 [80]
methyl Sb/PbO2
phenol
2,4- Ti/SnO2 -Sb 2–40 0.928 [TOC] – - [81]
Dichlorophenol
2,4- Ti/TiO2 - 20 0.89 [COD] 0.294 170 [82]
Dichlorophenoxyacetic NTs/PbO2 -FR
acid

Pharmaceuticals, Acetaminophen Ti/TiO2 /RuO2 24–180 0.90 [COD]; – – [83]

antibiotics, Ti/Ta2 O5 /IrO2 0.40 [COD]
hormones
Ketoprofen Ti/SnO2 -Sb 20 0.70 [TOC] 0.25 – [84]
Metronidazole Ti/SnO2 -Sb-Ce 4.8 0.10–0.31 – – [85,86]
[TOC]
Ofloxacin and Ti/IrO2 /Ta2 O5 20 0.30 [COD] – – [87]
Lincomycin
Paracetamol RVC/CuO/TiO2 /Al2 O3 Pb 0.80–0.99 0.32–0.68 – [88]
[TOC]
Sulfamethoxazole Ti/SnO2 - 2–40 0.46–0.91 – – [89]
Sb/PbO2 -Ce [TOC]
Tetracycline Ti/Ru0.3 Ti0.7 O2 P 0.13–0.43 – – [90]
[COD]
Various phar- Ti/Pt/SnO2 - 10–30 0.17–0.82 0.45–0.88 – [91]
maceuticals Sb2 O4 [COD]
17-␣- Ti/SnO2 -Sb 10 0.99 [TOC] 0.075–0.2 – [92]
ethylnylestradiol

Bisphenol-A Bisphenol-A Ti/SnO2 - 40 0.82 [COD] – – [93]

Sb2 O5 /PbO2
Bisphenol-A Ti/SnO2 -Sb 10–50 0.90 [TOC] – – [94]
Bisphenol-A Ti/TiO2 -RuO2 6.5–30 0.09 [COD] – – [95]

Plasticizers Diethyl Ti/IrO2 /RuO2 39 0.40 [COD] – – [96]

phthalate
Diethyl Ti/SnO2 -Sb 20–40 – 0.001–0.026 [97]
phthalate

Nitrophenol 2-Nitrophenol Ti/PbO2 -Ce 20 0.91 [COD] 0.383 895 [98]

4-Nitrophenol Ti/SnO2 - 20 0.34 [TOC] 0.08–0.20 115 [99]
Sb/PbO2
4-Nitrophenol Ti/SnO2 -Sb2 O5 50 0.94 [COD] – – [100]
4-Nitrophenol Ti/TiO2 - 20 0.91 [TOC] – – [101]
NTs/SnO2 -Sb
4-Nitrophenol Ti/CeO2 -RuO2 - 20 0.86 [COD] 0.336 340 [102]
SnO2
4-Nitrophenol Ti/SnO2 -Sb2 O5 - P 0.75 [TOC] 0.468 [103]
IrO2
62 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

Table 1 (Continued)

Compound MMO anode Current density Removal Current Service life (h) Reference
typea (mA cm−2 ) efficiencyc efficiency

4-Nitrophenol, Ti/PbO2 -Bi 30 0.76–0.83 0.281–0.315 – [104,105]

3-nitrophenol [COD]
and
2-nitrophenol

Perfluorinated Perfluoro Ti/SnO2 - 10 0.87–0.92 – – [26,106]

chemicals carboxylic Sb/PbO2 -Ce [TOC]
acids
Perfluoro Ti/SnO2 -Sb-Ce 10 0.81–0.88 – – [106]
carboxylic [TOC]
acids
Perfluorooctanoate Ti/SnO2 -Sb 10 0.90 [TOC]; [27]
Ti/SnO2 - 0.91 [TOC];
Sb/PbO2 0.32 [TOC]
Ti/SnO2 -
Sb/MnO2
Perfluorooctanoate Ti/SnO2 -Sb-Bi 22 – – 0.8 [25]
Perfluorooctanoate CA/SnO2 -Sb 20 0.86 [TOC] – 6.5 [28]

Surfactants and Triton X-100 Pt-RDE/PbO2 - 5–25 – – – [107]

derivatives Co
Sodium Ti/Co/SnO2 - 38.1 0.56–0.86 0.46–0.84 – [108]
dodecyl Sb2 O3 [COD]
benzene
sulfonate
Nonylphenol Pt-RDE/PbO2 - 5–25 – – – [28,107]
Co

Chelating Ethylenediaminete- Pt/Bi/PbO2 P – – – [109]

agents traacetic acid
(EDTA)
Humic acid Ti/TiO2 -RuO2 20 0.25–0.65 – – [110]
[TOC]
Humic and Ti/RuO2 -IrO2 13.1–56.3 0.88 [COD] 0.30 [111]
fulvic acid-like
substances
Humic Ti/TiO2 -lrO2 - 100 0.56 [COD] 0.15–0.65 [112]
substances RuO2

Microcystin Microcystin RR Ti/RuO2 -IrO2 4.44–8.89 0.43–1 [MCRR]; – – [113]

toxins and 0.50–1 [MLRR]
microcystin LR
(MCRR and
MCLR)
a
MMO anode type: SS – stainless steel; FR – fluorine resin; RVC – reticulated vitreous carbon; CA – carbon aerogel; RDE – rotating disk electrode; CNT – carbon nanotubes;
b
P-Operated at potentiostatic mode.
c
Removal efficiency: determined by COD, TOC, Color and pollutant concentration.
d
Data not reported.

also systematically discussed, including pH, temperature, current decomposition [68], electrodepostion [70], chemical vapor deposi-
density and supporting electrolytes. tion (CVD) [114] and physical vapor deposition (PVD) [115] have
Overall, this review focuses on the following issues that arise: been employed to produce the bulk mixed metal oxide layer.
For each preparation, the employed precursor solution contains a
• the extent to which the electrocatalytic activities of MMO anodes mixture of metal precursors. Thus different metal oxides can be
can be improved by specific surface modifications; deposited on the substrate concurrently and homogenously. The
• the mechanisms that are responsible for the electrochemical mixed metal oxides can be binary, ternary or quaternary system
degradation of organic pollutants at MMO anodes; and so on in accordance with the number of metal cations involved.
• the determination of electrogenerated reactive oxygen species Fig. 1a shows a conceptual diagram of the surface composition in
(ROS) at MMO anodes that can be achieved by various qualitative a binary metal oxide anode system. In a bulk mixed metal oxide
and quantitative methods; system, the MMO layer with completely mixed MMO components
• the main challenges and perspectives with regard to both the provides active sites for electrocatalytic reactions. For the applica-
experimental study and the practical application of MMO anodes tion of removing or alleviating organic compounds in wastewater,
in wastewater treatments. some of the important MMO anodes based on the bulk mixed metal
oxide system include Sn-Sb binary MMO anodes, Ir-Ru binary MMO
anodes, Ir-Ta binary MMO anodes, Ti-Ru binary MMO anodes, Ti-
2. Metal oxide systems of MMO anodes Bi binary MMO anodes, Ir-Ru-Sn ternary MMO anodes, Ce-Ru-Sn
ternary MMO anodes and Ru-Ir-Sn-Ti quaternary MMO anodes.
2.1. Bulk mixed metal oxide anode Normally parameters such as roughness or porosity factors are
used to describe the surface of solid electrodes. However, it is
Bulk mixed metal oxide anodes represent one kind of MMO important to gain some insight into the distribution of the surface
anodes of which the anode surface layer comprises com- sites and internal sites since the anode surface is of much concern,
pletely mixed metal oxides. Methods including thermochemical and major reactions take place in the MMO anode surface if it is
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 63

conductivity [126] and (4) increasing the surface area and hence
the reaction rates [127]. Some supported metal oxides which are
widely employed include single metal oxides of ␣-PbO2 , RuO2 , IrO2 ,
Al2 O3 , TiO2 nanotubes (TiO2 -NTs), and binary MMOs of Ir-Ru-O,
Ir-Ta-O and Sn-Sb-O.

3. Synthesis of MMO anodes

Various synthesis methods have been attempted to fabricate

MMO anodes. In general, these methods fall into two main groups,
i.e. chemical methods (e.g. thermochemical decomposition, elec-
trodeposition, anodization, sol–gel method, spin coating, CVD), and
physical methods (e.g. magnetron sputtering, PVD). When intro-
Fig. 1. Conceptual diagram and surface oxides structures of (a) binary bulk mixed
ducing the different metal oxide components to a bulk MMO anode
metal oxide anode; and (b) supported metal oxide anode.
or supported metal oxide anode, various synthesis strategies can be
applied. For example, either thermochemical degradation or elec-
not permeable. One way to determine the ratio of internal region to trodeposition can be employed as the only synthesis technique
total surface region is by calculating the morphology factor (ϕmorph ) when introducing the homogeneous MMO film onto a bulk MMO
[116,117]. The morphology factor is analogues to the porosity fac- anode [41,128] and supported metal oxide anode [124]. However,
tors proposed by Trasatti and co-workers [14,118,119]. It can be in more common cases with supported metal oxide anodes, the
considered as a measure of the ratio of the internal and total surface metal oxide films are prepared layer by layer by different synthesis
areas, and can be estimated using Eq. (1): techniques, including thermochemical degradation of the support
Cd,i layer and electrodeposition of the active layer [26]. Such attempts
ϕmorph = (1) result in good anti-corrosion property of the inner layer and elec-
Cd
trocatalytic active outer layer. The list of recent approaches for the
where Cd,i and Cd are the internal and total differential capacitances synthesis of various MMO anodes, and their corresponding physic-
of the mixed oxides region respectively, and they represent the cor- ochemical characteristics and performances is presented in Table 2.
responding surface areas. The values of ϕmorph range from 0 to 1. Indeed, the stability of MMO anodes is critical for their indus-
In general, ϕmorph close to 0 indicates small or negligible contri- trial application, in which the cost-effectiveness of process has to
bution of the internal sites to the overall differential capacitance, be considered. In laboratory-scale studies, the stability of MMO
and the value approaching 1 indicates a large internal region of the anodes can be accessed by accelerated life test. At specific temper-
electrode. ature, the accelerated life tests are carried out in a three electrode
cell under galvanostatic conditions at 100–1000 mA cm−2 in highly
2.2. Supported metal oxide anode concentrated H2 SO4 solutions, and the service life is defined as the
duration from beginning of the test to the time at which the cell
It is always desired for MMO anodes to have improved elec- potential reaches a given value [136,141,142]. However, there is a
trocatalytic performance or prolonged service life by mixing the lack of consistency in the test conditions in previous studies, which
metal oxides in the surface layer, as what has been discussed for makes it difficult to compare the service life of MMO anodes. To
the bulk MMO system. However, sometimes such twin goals can avoid the “disguised service life”, accelerated life test must be rig-
be realized by depositing one active metal oxide film on the other orously conducted with a good protocol of quality control, and the
metal oxide support [120]. Such kind of metal oxide anodes is experimental conditions have to be well defined.
known as supported metal oxide anodes. It has been demonstrated Among all the chemical methods, thermochemical decompo-
that spontaneous dispersion of one crystalline metal oxide over sition, or pyrolysis, is the most widely applied method for the
the other metal oxide may take place by surface spreading above fabrication of SnO2 -based MMO anodes or Ir- and Ru-based MMO
the Tammann temperature (TTAM = 1/2TMP , where TMP is the melt- anodes. The main advantage of this synthesis method is its easy
ing point of metal oxide) [121,122], or at a reduced temperature operation. In a typical thermochemical decomposition procedure,
(240–400 ◦ C) [123]. Thus, a dispersion layer comprising a mixture the metal salts, of which metal chlorides are most frequently used,
of different metal oxides will be formed. For those supported metal are directly dissolved in the alcohol solvent. The alcohol solvent
oxide anodes which require a calcination process for their fabri- includes isopropanol, ethanol, butanol or their mixtures. In order
cation, the calcination temperatures usually range from 400 ◦ C to to avoid the hydrolysis of the metal salts, it is necessary to intro-
700 ◦ C, which are high enough for the occurrence of spontaneous duce acidity to the precursor solution by adding hydrochloric acid.
dispersion and formation of MMOs layer. In addition, when the It is worth noting that the calcination temperature plays a crit-
active oxide layer is prepared using facile methods like electrode- ical role in the electrocatalytic performance of MMO anodes. As
postion, such dispersion effect was also confirmed by XRD [124]. reported by Domashevskaya et al. [143], when preparing SnO2
For the purpose of this review, the supported metal oxide anodes anodes, a calcination temperature less than 450 ◦ C would lead to
are discussed as MMO anodes. the incomplete oxidation of tin precursor, resulting in the forma-
The layered structure of active oxide layer, dispersion layer and tion of SnOx (1 < x < 2) nanolayer and a reduced band gap. Feng et al.
supported oxide layer in supported metal oxide anode is illustrated [68] described Eu doped Ti/SnO2 -Sb electrodes fabricated at vari-
in Fig. 1b. Although the supported oxide layer does not directly ous temperatures ranging from 450 to 850 ◦ C, and observed well
participate in the surface reactions including organic compounds developed SnO2 crystal and better electrocatalytic performance
oxidation, oxygen evolution or oxidizing reagents generalization, for phenol degradation when the anode calcination temperature
it can enhance the performance of the MMO anode by: (1) increas- is 750 ◦ C. However, high calcination temperature may not extend
ing the electrocatalytic activity of the surface layer [45,125], (2) the service life of MMO anodes [144]. In view of above mention-
enhancing the mechanical and chemical stability of the surface, and ing reasons, the most popularly used calcination temperature for
thus prolonging the service life [71], (3) improving the electrode SnO2 is among 500–550 ◦ C to ensure both the high electrocatalytic
64 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

Table 2
MMO anodes: Synthesis, physicochemical characteristics and performances.

Synthesis techniques Anodes Physicochemical characteristics and performance Reference

Thermochemical
decomposition
Dip-coating and bake Ti/SnO2 -Sb/Ce SEM showed “mud-crack” surface morphology; XRD rutile [85]
phase of SnO2 was observed by XRD. Limited conversion of
oxidation byproducts to CO2 was found.
Ti/SnO2 -Sb-Eu Rutile type SnO2 increased with pyrolysis temperatures in [68]
(SnO2 -Sb inner layer prepared by thermal the range of 550–750 ◦ C. Eu3+ (95 pm) replaced the Sn4+
decomposition) with smaller ionic radii (71 pm), resulted in lattice
expansion. Best phenol removal efficiency (96.4%) was
achieved when the pyrolysis temperature was 750 ◦ C.
Ti/CeO2 -RuO2 -SnO2 The crystal size decreased by incorporation of Ce, which in [102]
turn increased the specific surface area of anode.
SS/CeO2 -SnO2 “Cracked-mud” morphology was distinct. The size of ‘mud’ [36]
islands of SnO2 -CeO2 coating was smaller than that of
SnO2 film.
Ti/IrO2 -SnO2 -Sb2 O5 The surface morphology was “crack-mud” type. [129]
Ti/(Ru1−x Tix )O2 XPS showed a charge transfer from the RuO2 to the TiO2 , [130]
resulted in enhanced oxygen evolution reaction.
Ti/BiOx -TiO2 Heavy doping level of Bi enabled the electrode both [73]
photoelectron-catalytic and electrocatalytic activites.
TiO2 -NTs/SnO2 -Sb Electron transfer resistance of TiO2 -NTs/SnO2 -Sb (0.59 k) [64]
(TiO2 -NTs prepared by anodization) was much less than Ti/SnO2 -Sb (3.85 k). Lattice
parameters of TiO2 -NTs/SnO2 were also smaller.
Spray pyrolysis Ti/SnO2 -Sb2 O5 Small uniform particles were predominant, and the film [131]
was polycrystalline with a tetragonal structure.
Ti/IrO2 /SnO2 –Sb2 O5 The electrode surface is low rugosity/porosity compared [125]
with Ti/IrO2 . IrO2 interlayer strongly increases the
electrode service life. 95% TOC elimination of p-CP can be
acheavied.
Sol–gel Ti/IrO2 -SnO2 -Sb2 O5 SEM showed uniformly distributed rough surface. Effective [41]
removal of methyl orange dye was acheived.
Ti/SnO2 -Sb-La; XRD studies evidenced the tetragonal rutile structure of [72]
Ti/SnO2 -Sb-Ru RuO2 ; no diffraction peak of La, Ru or Sb was found.
Ti/SnO2 -Sb-La showed lowest impedance and best
electrocatalytic activity.
Ti/SnO2 -RuO2 -IrO2 ; SEM showed a heterogeneous cracked morphology for [132]
Ti/Ta2 O5 -IrO2 ; Ti/Ta2 O5 -IrO2 and rough coating with a grain-like
Ti/RhO2 -IrO2 appearance for Ti/RhO2 -IrO2 . More than 90% phenol can be
removed.
Electrodeposition
Continious TiO2 -NTs/SnO2 -Sb XRD showed rutile phase of SnO2 and no diffraction peak [133]
electrodeposition (TiO2 -NTs prepared by anodization) of Sb. Enhanced phenol degradation activity was obtained
by TiO2 -NTs substrate.
TiO2 -NTs/SnO2 -Sb/PbO2 “Flower-like” surface is observed by SEM; XRD studies [45]
(TiO2 -NTs prepared by anodization) confirmed ␤-PbO2 on the surface. Phenols can be
completely degraded, and the electrocatalytic activity
debased as the morphology became more compact.
Ti/SnO2 -Sb2 O3 /MnO2 Compact and homogeneous MnO2 layer was produced. [27]
(SnO2 -Sb2 O3 prepared by sol–gel)
Ti/SnO2 -Sb/Ce-PbO2 Porous nanocrystalline PbO2 film was found. The anode [26]
(SnO2 -Sb2 O3 prepared by thermal showed better performances for perfluorooctanoic acid
decomposition) (PFOA) degradation.
Ti/TiO2 /PbO2 The surface of the anodized titanium electrodes is not [134]
(TiO2 prepared by anodization) homogeneous; electrodeposition of PbO2 occurred
selectively on the (0001) grains.
Ti/SnO2 -Sb2 O5 -RuO2 / The prevailing crystal structure was ␤-PbO2 in the surface; [71]
␣-PbO2 /␤-PbO2 ␣-PbO2 layer had a cauliflower structure with average size
(SnO2 -Sb2 O5 -RuO2 prepared by thermal 4 ␮m, and ␤-PbO2 had angular crystals with average size
decomposition) 6 ␮m. An increase in lifetime was obtained.
Ti/SnO2 -Sb2 O3 / Orthorhombic ␣-PbO2 and tetragonal ␤-PbO2 are found; [65]
Nb2 O5 -PbO2 improvement in electrical conductivity and hydrophilicity
(SnO2 -Sb2 O5 prepared by thermal was obtained by doping Nb.
decomposition)
Pulse TiO2 -NTs/PbO2 SEM showed PbO2 grew around TiO2 -NTs [135]
electrodeposition (TiO2 -NTs prepared by anodization)
Ti/SnO2 -Sb2 O4 -CNT SEM revealed granular surface structure. Prolonged [70,136]
lifetime and better COD removal was achieved compared
with dip coating.
Ti/TiO2 -NTs/SnO2 -Sb The electrode had high OEP (2.4 V vs SCE), high [137]
(TiO2 -NTs prepared by anodization) electrocatalytic activity with 97.4% TOC removal for
fluorobenzene. Compared with sol–gel made SnO2 , higher
crystallinity, higher order degree of atomic lattice, and less
oxygen vacancies were achieved.
CVD Ti/IrO2 /SnO2 XRD confirmed existence of high purity Ir protective layer; [138]
SEM observed dense, homogeneous surface with high
roughness.
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 65

Table 2 (Continued)

Synthesis Anodes Physicochemical characteristics and performance Reference

techniques

Ti/IrOx /SnO2 The SnO2 films were slightly textured either in the (1 1 0) [139]
or (2 0 0) direction. (1 1 0) preferential orientation is
favored at high deposition temperatures and high metal
salt concentration.
PVD Si/Irx Ru1–x O2 Highly single crystalline Irx Ru1–x O2 nanowires were [115]
formed. Eg phonon mode from pure RuO2 nanowire
linearly blue shifted with incorporating Ir contents.
Magnetron Glass/ZnO2 -SnO2 The Sn 3d5/2 peak can be resolved into two parts located at [140]
sputtering 486.7 and 486.0 eV, which corresponded to Sn4+ and Sn2+ .

activity and anode stability. One of the main drawbacks of ther- template wherein metal oxides are implanted aiming to have
mochemical degradation is the tendency to form cracks due to the improved loading capacity of Ti substrate. The mean pore diam-
high internal pressure of surface layer, and the cracks may lead to eters of the TiO2 -NTs range between 100 and 220 nm, according to
the poor stability. the different anodization condition. PbO2 is reported to be directly
Sol–gel method has been developed to produce the SnO2 based deposited into the TiO2 -NTs by pulse electrodeposition [148] and
MMO electrodes to overcome the drawbacks of direct thermo- photoelectrodeposition [149]. However the SEM images of the
chemical decomposition. First proposed by Pechini [145], the resulting anode showed the blocking of TiO2 -NTs by PbO2 , resulting
sol–gel method can achieve colloidal precursor solution by dissolv- in a limited increase of active surface area. Li et al. [135] fabricated a
ing the citric acid into a mixture of ethylene glycol and ethanol. novel TiO2 -NTs/PbO2 structure by introducing an electrochemical
After that the desired molar ratio of metal salt precursors is added reduction step and modifying parameters of pulse electrodeposi-
and the solution is treated with ultrasonication for several hours, tion, and finally the crystalline structured ␤-PbO2 nanoparticles
followed by the dip coating procedure. Modification of Pechini were successfully deposited without blocking the TiO2 -NTs. The
method has been made by Canevari et al. [146] to use organic metal real atomic percentage of Pb of the anode surface was found to be
compound (C4 H11 )2 Sn(OCOCH3 )2 as precursor, and grafting Sb(V) 11.75%, and such novel structure can effectively degrade phenol
into the SnO2 surface. with 96.6% removal efficiency and 88.7% COD removal at current
Electrodeposition can be regarded as a facile method for density of 30 mA cm−2 in NaCl electrolyte. Similar approaches have
the preparation of MMO anodes, and it has particularly exten- also been adopted to deposit SnO2 on TiO2 -NTs by thermal decom-
sive application for the preparation of PbO2 -based MMO anodes. position [64], pulse electrodepostion [137], hydrothermal method
For electrodeposited PbO2 , depositing conditions including pH, [150] and electrodeposition [133,151]. Fig. 3a illustrates the fabri-
depositing current, Pb source and depositing temperature can have cation of TiO2 -NTs with enhanced conductivity by electrochemical
significant influence on the surface morphology, adhesion property reduction of the bottom TiO2 -NTs and subsequent Cu deposition
and crystal forms of the resulting PbO2 [147]. For SnO2 -based MMO [152]. After SnO2 -Sb deposition, the anode could have a distinc-
anodes, preparation by electrodeposition gives rise to regularly tively high oxygen evolution potential (OEP) of 2.4 V vs SCE. The
dispersed surface morphology compared to the thermochemical mass loading of Ti/TiO2 -NTs/SnO2 is 1.4 times higher than that
decomposition method, as illustrated in Fig. 2. In order to improve of Ti/SnO2 , and mineralization current efficiency and first-order
the anti-corrosion property of MMO anodes, single layer or multi kinetic constant for BA degradation were also 1 and 3.5 times
interlayers may be applied to the substrate before electrodeposi- greater [127]. Moreover, the Ti/TiO2 -NTs/SnO2 can also serve as
tion of the outer layer, which is rather typical in the supported metal the support for PbO2 deposition [45] to enhance its chemical and
oxide system. physical resistance.
CVD appears to be the least attempted chemical method for The other approach is through self-assembly of surfactants in
preparing MMO anodes, due to its high operation cost and the the precursor solutions of metal oxides to form micelles, and
difficulty in introducing several metal precursors in the furnace. mesoporous MMOs layers can be formed by simply removing the
Physical methods employed to fabricate MMO anodes include mag- surfactant templates [153,154]. Fig. 3b shows the mesoporous
netron sputtering and PVD. The main difference between physical SnO2 -Sb anode fabricated by evaporation induced self-assembly
methods and chemical methods is the metal precursors used. Both (EISA) using pluronic F127 [84]. In addition, F127 could reduce
magnetron sputtering and PVD directly employ metal oxides rather the surface energy of SnO2 growth, which inhibited the aggrega-
than metal salts as their precursors, and it is reported that physi- tion of SnO2 . In other studies, Zhao and co-workers [101,155] first
cal methods contribute to better crystalline formation [115]. But so reported the assembling of 2D macroporous SnO2 to 1D TiO2 -NTs
far, few reports have been found about electrochemical oxidation by using liquid crystal soft template prepared by self-assembly
of organic compounds with MMO anodes which were prepared by block copolymer (styrene phenol polyoxyethylene ether, or SPPE).
physical methods. The SnO2 layer is about 100 nm in thickness with 2D nanoscale pore
structure in horizontal direction (diameters of macroporous pores
4. Surface modification of MMO anodes 150–400 nm). The fabricated mesoporous SnO2 /TiO2 -NTs showed
both excellent photo-catalytic and electrocatalytic oxidation per-
4.1. Deposits with nano- and microstructure formances for removing 4-nitrophenol and reducing its toxicity. In
general, their study presents concept and new insight to develop
MMO anodes with nanostructured deposits have drawn a lot of photoelectric functional materials for degradation of toxic organic
interest in the recent years. For their application in electrochemi- pollutants with high concentration.
cal oxidation/degradation of organic compounds, the main goal of Recently, carbon aerogel (CA) has attracted considerable atten-
nanostructured MMO anodes is to increase the surface area, and tion as novel porous substrate for MMO anodes, due to their
hence the reaction rates. three-dimensional network structure, good electrical conductivity
Many papers report the anodic oxidation of Ti substrate to and high surface area [28,156,157]. Fig. 4a illustrates the prepara-
get vertically aligned TiO2 -NTs. They can serve as the tubular tion process of a novel SnO2 -Sb/CA electrode. After CA fabrication,
66 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

Fig. 2. SEM of TiO2 /SnO2 -Sb electrodes prepared by the authors by (a) thermal decomposition; and (b) electrodeposition.

SnO2 -Sb was deposited on CA by thermochemical decomposition. bromide, or CTAB). The ternary MMOs have tetragonal rutile-like
However, calcination temperature is critical due to the reducibility structure (P4/mnm), with a specific surface area of ∼100 m2 g−1 .
of CA, which would reduce SnO2 to metallic Sn at high heat treat- Lee et al. [115] described deposition of highly single crystalline
ment (>700 ◦ C) [157]. The optimal calcination temperature is 600 ◦ C Irx Ru1−x O2 nanowires on Si(0 0 1) wafer by PVD of IrO2 and RuO2
at which well dispersed SnO2 -Sb nanoparticles were achieved mixtures at 700 ◦ C and under atmospheric pressure.
(Fig. 4b). In electrochemical oxidation of PFOA, SnO2 -Sb/CA showed
much better performance than SnO2 -Sb/Ti by improving the total 4.2. Doped MMO anodes
organic carbon (TOC) removal from 17% to 86% as well as doubling
the HO• generation [28]. For the past 15 years, many attempts have been put for-
It should be noticed that the above mentioned MMO anodes ward to develop doped MMO electrodes in order to obtain
are based on supported metal oxide system. Hence, no complete improved characteristics (e.g. electrocatalytic activity, photoelec-
mixture of TiO2 and other metal oxide was achieved in the anode trocatalytic activity, corrosion resistance and conductivity) or
surface. However, the advantages of a high surface area have driven desired properties (e.g. hydrophilic–hydrophobic properties). The
research efforts to modifying bulk MMO anodes. Frolova et al. doped components, or dopants, can be simply introduced to MMO
[158] reported a nanostructured Pt/SnO2 -SbOx -RuO2 via reversed anodes by including dopant ions into the precursor solution or elec-
micelles assisted by adding surfactant (cetyltrimethylammonium trodeposition bath, or by more complicated methods (e.g. grafting).

Fig. 3. Schematic illustration of (a) the formation process of TiO2 -NTs/SnO2 -Sb electrodes (modified from Chen et al. [151]) (b) growth of mesoporous SnO2 electrode by
EISA method.
Modified from Fan et al. [84].
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 67

Fig. 4. (a) Schematic illustration for fabrication novel SnO2 -Sb/CA electrode; and (b) SEM images of SnO2 -Sb/CA electrodes calcined at 600 ◦ C.
Reprinted with permission from [28].

It is not surprising that the performances of the anodes are greatly to be at their highest oxidation state. He et al. [30] reported in
enhanced after doping. However, it is worth noting that the extent the Ti/SnO2 -Sb/PbO2 -Pr anode, Pr existed in the form of Pr6 O11
of property improvement by certain dopant is really dependent which can be regarded as complex compound with four PrO2 and
on anode materials. Moreover, the level of dopants and doping one Pr2 O3 . The ionic radius of Pr4+ (90 pm) is close to that of Pb4+
conditions can result in obviously different effects on the physic- (84 pm), which influences the nucleation and crystal growth of
ochemical property and oxidation performance of MMO anode PbO2 . While Pr3+ has a larger ionic radius (101 pm) and leads to the
[98,159]. expansion of surface particles. Another typical example of coexis-
For each preparation, it is important to identify whether the tence of different oxidation states is Sb doped Ti/SnO2 electrode.
ions are incorporated into the metal oxide lattice or whether the In an earlier study by Terrier et al. [160], the lower oxidation state
anode surface film is a mixture of different metal oxides. Kong Sb3+ was found to overtake the higher oxidation state Sb5+ in Sb
et al. [76] used XRD to investigate PbO2 films doped with four rare 3d3/2 XPS peak when the Sb doping level was increased. Indeed,
earth metal elements (La, Ce, Er and Gd) of the same concentrate more studies about the effect of dopants oxidation states on the
(2.5 g L−1 ). Well defined diffraction peaks of rare earth oxides La2 O3 , MMO anodes electrocatalytic activity are needed.
CeO2 and Er2 O3 were found in La-PbO2 , Ce-PbO2 and Er-PbO2 lay- Some of the dopants used and their corresponding improve-
ers, suggesting the crystal structures of corresponding rare earth ments to different types of MMO anodes are summarized in Table 3.
oxides present in the surface film. In the case of Gd-PbO2 layer, Among them, fluoride ions are non-metallic dopants that have been
doping did not disturb the crystal structures of ␤-PbO2 but there widely used to improve the conductivity of SnO2 or improve the
was evidence of alternation of main crystal plane from ˇ(1 0 1) to adhesion and stability of PbO2 [147]. In Ti/PbO2 -Co-F MMO anode,
ˇ(3 0 1). When introducing the dopants to the surface MMO layer, the fluoride ions are found to inhibit the incorporation of Co into
the synthesis methods employed can also influence the surface the surface film [161]. Li et al. [162] described an Ti/Ni-Sb-SnO2
crystal phases, which was reported by Wang et al. [38]. In their anode with fluorine doped tin oxide (FTO) interlayer, and the ser-
study of preparing Ti/PbO2 -Pr2 O3 by cyclic voltammetry (CV) and vice lifetime of the modified MMO anode was improved by a factor
co-electrodeposition, XRD peaks of Pr2 O3 were only found for the of 6. Bi(III)-doped MMO anodes are very practical for catalyzing
electrode prepared by the former method. the oxidation of organic compounds. In addition, Bi(III) has the
Nevertheless, it is worth noting that the oxidation states of great potential to introduce photoelectrocatalytic property when
dopants may be uncertain, even though they are usually assumed they are doped with photocatalyst TiO2 [73]. Ce(IV)-doped MMO
68 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

Table 3
Doped MMO anodes and proposed roles of the dopants.

Dopant Active anode material Purpose References

Sb(V) SnO2 Improve the conductivity [160]

F(-I) SnO2 Prolong the electrode service life [162,163]
Catalyzes organic degradation [164]
F(-I) PbO2 Improves chemical and electrochemical stability [161]
Catalyzes organic degradation [165]
F(-I) IrO2 Catalyzes O2 evolution [166]
Bi(III) SnO2 Catalyzes organic degradation [25]
Bi(III) PbO2 Catalyzes organic oxidation [167,168]
Bi(III) TiO2 Enhance photoelectrocatalytic acitivity [73]
Ce(IV) PbO2 Improves stability [98]
Catalyzes HO• generation [169]
Catalyzes organic degradation [89,170]
La(III) SnO2 Catalyzes organic oxidation [72]
Ru(IV) PbO2 Catalyzes organic oxidation [72]
Zr(II) PbO2 Decrease grain size of electrode and improve life span [77]
Co(II) PbO2 Catalyzes organic degradation [107,161]
Eu(III) SnO2 Catalyzes TOC removal [68]
Pr(IV) PbO2 Catalyzes organic degradation and improves electrode stability [30,38]
Er(III) PbO2 Catalyzes organic degradation [76]

anode is another commonly used MMO anodes for oxidations, and in organic oxidation rather than oxygen evolution. In general, MMO
such reactions involve the oxidation of pharmaceuticals [85,89], anodes with deposited polymer composites are desired to have
nitrophenol [98,102] and perfluorinated chemicals [26]. hydrophobic property and they are promising material for envi-
Several papers report quantitative comparisons of the proper- ronmental application of electrochemical oxidation.
ties of doped and undoped MMO anodes. Xu et al. [72] compared the
cyclic voltammetry curves of undoped Ti/SnO2 -Sb electrode with
5. Characterization of MMO anodes
Ti/SnO2 -Sb-La and Ti/SnO2 -Sb-Ru electrodes in 0.1 M KCl solution
containing 5 mM K4 [Fe(CN)6 ] solution. The peak currents of doped
The crystal studies of metal-based catalysts, as well as quantita-
Ti/SnO2 -Sb electrodes are greatly improved from 0.37 mA cm−2 to
tive comparison of their reaction rates were significantly conducted
0.52 mA cm−2 and 0.60 mA cm−2 , suggesting higher voltammetric
in the 1970s by the introduction of several characterization tech-
charge which is attributed to an increase of the active surface
niques. However, the catalysis science of MMO experienced a
area. Liu et al. [98] investigated the impedance and electrocatalytic
much slower development than other metal-based catalysts due
efficiency of undoped Ti/PbO2 and Ti/PbO2 -Ce electrodes with dif-
to the reasons: (1) the complexity of MMO catalysts (e.g. pos-
ferent Ce doping levels (0.7–14 mM Ce in electrodeposition bath),
sible existence of different oxidation states, coexisting bulk and
and 3.5 mM was found to be the optimal doping level since the
surface phases, various surface termination functionalities) and
lowest charge-transfer resistance and highest chemical oxidation
(2) the requirement of new spectroscopic techniques to deter-
demand (COD) removal of 2-nitrophenol was obtained. Neverthe-
mine such structural details [178]. To date, various characterization
less, if Ce is doped at a high level, the Ti/PbO2 -Ce electrode even
methods have been employed to examine the physiochemi-
experiences retrogress in electrocatalytic activity comparing with
cal, electrochemical and crystallochemical properties of MMO
Ti/PbO2 . Indeed, it is of research interest to determine the optimal
anodes. These widely applied techniques include: X-Ray diffraction
doping level of the dopants in MMO anodes.
(XRD), Raman spectroscopy, X-ray adsorption spectroscopy (XAS),
thermalgravimetric analysis (TGA), scanning electron microscopy
4.3. Polymer composites and transmission electron microscopy (SEM and TEM), energy-
dispersive X-ray spectroscopy (EDS), cyclic voltammetry (CV),
Polymers are another type of material employed to introduce scanning electrochemical microscopy (SECM), electrochemical
or enhance specific properties of MMO anodes. Polypyrrole and impedance spectroscopy (EIS), UV–vis diffuse reflectance spec-
PbO2 were co-electrodeposited on Ti/SnO2 /PbO2 substrate, and troscopy (DRS), X-ray photoelectron spectroscopy (XPS), atomic
the modified electrode had hydrophobic surface, which exhib- force microscopy (AFM) and Fourier-transform infrared (FTIR)
ited a remarkable enhancement in oxidizing hydrophobic organic spectroscopy. The characterization techniques for MMO anodes
compounds due to the strong hydrophobic interaction between and the corresponding characteristics reported are summarized in
the electrode surface and organic substrates [171]. Zhou and Table 4.
co-workers [172–175] described a novel PbO2 electrode with elec- XRD can provide structural information of the MMO anodes sur-
trodeposited polytetrafluoroethylene (PTFE) layer, and it is found to face films by examining the crystal phases. Since the metal oxides
have a good resistance to corrosion and excellent electrocatalytic can be mixed or laid in different manners, the XRD patterns of
activity to degrade nitrophenol. The good performance of PTFE- MMO anodes comparing with single-component metal oxide may
deposited PbO2 anode for organics oxidation was also reported by be influenced in different ways. In most supported metal oxide sys-
Tong et al. [176] and Hong et al. [177]. The PTFE modified MMO tems, the surface layer acts as the electrocatalytic active layer and
anodes are reported to be able to exhibit complete electrochemical its XRD pattern is not influenced by the property of the inner layer,
oxidation of some organic pollutants [32,82]. It is worth mention- indicating an identical surface crystal structure [71]. However, in a
ing that the Ti/TiO2 -NTs/PbO2 -PTFE even showed a higher removal mixed metal oxide system, the mixture of metal oxides in the sur-
efficiency (98.8%) for 2,4-dichlorophenoxyacetic acid than boron face may influence the XRD pattern in the forms of (1) appearance
doped diamond (BDD) anode (79.3%) and less energy consump- of additional diffraction peaks [76] as a result of new crystal phase
tion. Ti/TiO2 -NTs/PbO2 -FR had super hydrophobic surface and it formation and (2) visible difference on the half-width and inten-
was believed that more absorbed HO• radicals is released from the sity of diffraction peaks [66,187], due to the expansion of metal
anode surface to become free HO• radicals, which could participate oxide lattice through incorporation of other elements. However, it
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 69

Table 4
Characterization techniques for MMO anodes.

Characterization Characteristics studied Findings

techniques

XRD Crystal structure analysis ␥-Al2 O3 : 18.5◦ , 37.3◦ , 42.6◦ , 46.3◦ , 67.0◦ ; SnO2 (1 1 0): 22.6◦ ; SnO2 (1 0 1): 33.9◦ ;
SnO2 (2 1 1): 51.8◦ [179].
XAS Local coordination or electronic structure A small amount of Ti atoms are incorporated into crystalline RuO2 and occupy Ru sites
analysis in octahedral RuO6 [180].
TGA Evaporation of solvent and decomposition Evaporation of free water molecules and solvent: 0–200 ◦ C; decomposition of metal
points of metal precursors chlorides: 200–400 ◦ C; stable coating layer: 400 ◦ C and above [181].
SEM/EDS Surface morphology and elemental Uniformly distributed particles of IrO2 -SnO2 -Sb2 O5 (1–5 ␮m in height) give rise to an
compositions thickness of coating layer about 2 ␮m) in Ti/IrO2 -SnO2 -Sb2 O5 electrode [41].
TEM Size of dopants particles Pt nanoparticles are well dispersed in the support surface of TiO2 -RuO2 and in the
particle size of 4–8 nm [182].
CV Onset potential of OER TiO2 -NTs/SnO2 prepared by electrodeposition has higher OEP than that of
TiO2 -NTs/SnO2 prepared by thermal decomposition.
SECM Electrocatalytic activity of MMO anodes Electrocatalytic OER activity of the mixed (Ru0.76 :Ti0.24 )O2 coating is 13% higher
compared to the RuO2 coating [130].
EIS Electrochemical systems analysis Charge transfer resistance: Ti/SnO2 -Sb2 O5 (492.70  cm−2 ) > Ti/SnO2 -Sb2 O5 IrO2
(8.94  cm−2 ) > Ti/SnO2 –Sb2 O5 -RuO2 (4.44  cm−2 ) [183].
Raman Stoichiometry and crystalline quality analysis Eg mode of pure RuO2 linearly blue shifts with incorporating Ir amounts in Irx Ru1−x O2
of MMO mixed oxide systems [115].
UV–vis Valance state analysis of metallic elements in One less intense band of Ru(III) (341 nm) is found when mixed Ru(IV) and Sn(II) using
DRS precursor solution aqueous HCl as solvent [184].
XPS Elemental surface chemistry analysis Mn: Mn(IV) is verified by Mn 2p3/2 and Mn 2p1/2 at 642.2 eV and 653.8 eV; Sn: Sn(IV) is
verified by Sn 3d5/2 and Sn 3d3/2 at 486.7 eV and 495.3 eV [179].
AFM High-resolution surface image of MMO coating The roughness of Ti/TiO2 -RuO2 -IrO2 increases by increasing the amount of IrO2 in the
layer coating layer [185].
FTIR Analysis of organic deposits on MMO anodes Organic species do not exist in the TiO2 -AgO film after annealing at 500 ◦ C [186].

should be pointed out that sometimes the introduction of dopants several milli Hertz is used. EIS has been used to study the system
into MMO films does not cause any noticeable changes in the XRD resistance and deactivation mechanism of MMO anodes. For exam-
patterns [36,72,133]. In such cases, the presence of dopants with ple, Lassali et al. [188] found that the oxidation of Ti substrate,
small doping level is usually verified by other techniques including which resulted in poorly doped TiO2 , lead to the deactivation of
XPS, XAS and Raman Spectroscopy. Ti/Ir0.3 Ti(0.7−x) Snx O2 anodes by analyzing their system equivalent
XPS is employed to determine the quantitative atomic composi- circuit of EIS under accelerated conditions. Adams et al. [183] cor-
tion, and also the oxidation states of surface elements. This property roborated chronopotentiometry (CP) and EIS findings and observed
makes it particularly useful to study the doped MMO anodes. the lowest charge-transfer resistance for oxygen evolution in
In MMO anodes, the binding energy peaks of O 1s include two Ti/SnO2 -Sb2 O5 -RuO2 electrode, comparing with Ti/SnO2 -Sb2 O5 -
parts: the main peak with lower binding energy value (∼530 eV) is IrO2 , Ti/SnO2 -Sb2 O5 -PtOx and Ti/SnO2 -Sb2 O5 electrodes. In another
attributed to the lattice oxygen, while the peak with high binding study, the Ti/SnO2 -Sb2 O5 electrode without interlayer showed an
energy value (531–532 eV) is believed to be the adsorbed oxygen. increase in charge-transfer resistance of oxide/solution interface
The O 1s peak was found to be lower in Gd doped Ti/SnO2 -Sb anode faradaic process from 28 to 3200  cm−2 after 45 min lifetime test,
than that of sample lacking Gd, suggesting more lattice oxygen however this number only increased from 26 to 35  cm−2 after
present in Gd doped Ti/SnO2 -Sb [66]. Its higher lattice oxygen con- 60 min lifetime test when FTO interlayer is applied [162].
tent increased the activity of the adsorbed hydroxyl radicals, hence Different from those characterization techniques which focus on
improved the anode performance. However, it should be noticed the surfaces characteristics of MMO anodes, TGA gives an insight
that the XPS spectra of Sb 3d5/2 and O 1s are overlapped, so it is into the physical and chemical changes of the precursor solutions
necessary to fit the XPS spectra into three peaks to identify the during pyrolysis. Makgae et al. [181] conducted TGA in a flow of air
presence of Sb. For MMO anodes, dopants are usually in their high- (100–700 ◦ C) at the rate of 10 ◦ C/min for their coating containing
est oxidation states, but there are exceptions if the MMO anodes hydrated SnCl2 , RuCl3 and IrCl3 precursors separately and a mixture
are calcined at low temperatures or the dopants are at high dop- of them, after evaporation at 100 ◦ C. For the precursors contain-
ing level. Cui et al. [187] described rare earth elements doped with ing single metal chloride, initial mass losses took place between
Ti/SnO2 -Sb anodes, which was prepared by thermal decomposi- 0 and 200 ◦ C, followed by sharp mass losses at 400 ◦ C. They were
tion with the presence of both Ce3+ and Ce4+ , and the presence of attributed to the evaporation of solvent and decomposition of chlo-
Ce3+ might have negative effect on the electrocatalytic activity of ride ions respectively. A thermal curve obtained for the three mixed
Ti/SnO2 -Sb due to the increased oxygen vacancies. However, in Ce metal chlorides showed a similar behavioral pattern to that of single
doped Ti/SnO2 -Sb and Ti/PbO2 electrodes where Ce presents in the metal chloride, indicating that polymerization occurred between
form of highest oxidation states, improved electrocatalytic activity the three mixed metals. However, a previous study by Kim et al.
for organic oxidation was observed [76,98,169]. [189] reported higher temperature (600 ◦ C) for sufficient conver-
EIS is a technique for the characterization of electrochemical sion of IrCl3 to IrO2 , and the conclusion was also supported by the
systems. Electrochemical impedance is usually measured by apply- corresponding XRD analysis.
ing a small AC amplitude sinusoidal potential to the system and
measuring the response current. The response current will be a 6. Active and non-active MMO anodes
sine wave at the same frequency but its phase shifted. Therefore
by varying the frequency of signal, the impedance of the system During electrochemical oxidation of organic pollutants at high
can be determined as a function of frequency. Typically for elec- potentials, secondary reactions (e.g. oxygen evolution reaction or
trochemistry characterization, a frequency range of 100 kHz to OER) will take place inevitably and decrease the current efficiency
70 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

for the desired reactions. Furthermore, the nature of anode mate- presence of Br− [200], I− [201] or natural organic materials (NOMs)
rial, including the adsorptive ability and electrocatalytic activity, [202–204] also gives rise to the release of soluble Pb (II) into solu-
plays an essential role in both the selectivity and efficiency of the tions. Besides Pb (II) ions, soluble Pb (IV) can be also present in
process by influencing the rate-limiting steps [62,190,191]. In order solution and act as a strong oxidant during electrochemical oxida-
to interpret the observations, a comprehensive model has been tion of organics [205]. The above-mentioned factors have restricted
described by Comnimellis et al. [192], including the anodic oxida- application of PbO2 as anodic material in wastewater treatment,
tion of organics and simultaneous oxygen evolution. Based on the where the Pb contamination of the treated water must be avoided.
different oxidation pathways proposed by the model, the anodes
can be divided into two classes: active anode and non-active anode.
Active anodes present low OEP, and only partial oxidation of organ- 7. Direct anodic and mediated anodic oxidation of organics
ics can be achieved by the chemisorbed HO• in the anode surface. In by MMO anodes
contrast, non-active anodes present high OEP and the physisorbed
HO• gives complete oxidation to the organic compounds. As an The electrochemical oxidation of organic pollutants can take
extension of Comnimellis’s work, Scialdone developed a theoret- place in two ways. The pollutants can be oxidized at the anode sur-
ical model involving both direct anodic oxidation and mediated face by direct electron transfer or by physisorbed or chemisorbed
oxidation routes by means of physisorbed and chemisorbed HO• HO• generated from OER, and this process is called direct anodic
[193], and by means of reactive chlorine species [194]. In the oxidation. Or, the pollutants can be degraded by mediated anodic
theoretical model, several assumptions were defined and relation- oxidation, which takes place in the bulk solution by oxidizing
ships between instantaneous current efficiency (ICE) and operating reagents electrogenerated at the anode surface. Fig. 5 shows the
parameters were presented with regard to mass transfer con- schematic illustration of the direct and mediated anodic oxida-
trol, oxidation control and mixed kinetic regimes. The theoretical tion mechanisms. Both of the two oxidation mechanisms have been
predictions matched well with experimental observations for elec- studied using MMO anodes.
trochemical oxidation of carboxylic acids at IrO2 -Ta2 O5 anode The studies investing phenolic compounds degradation have
[195,196]. shown that aromatic ring intermediate compounds were produced,
In order to comprehend the performances of various MMO including catechol, hydroquinone and benzoquinone. Benzo-
anodes, OEP (in H2 SO4 or Na2 SO4 ) of some commonly investigated quinone was subsequently oxidized to aliphatic carboxylic acids
MMO anode materials are given in Table 5. All the values are cal- resulting from aromatic ring cleavage, including maleic acid, mal-
culated compared to the standard hydrogen electrode (SHE). In onic acid, formic acid and acetic acid [64,75,80]. Fig. 6a shows the
general, MMO anodes which contain IrO2 and RuO2 especially in degradation pathway of phenol on MMO anodes [132]. Compared
bulk MMO have low values of OEP. It indicates that only partial with other anodes, MMO anodes have the merit of fully alleviat-
oxidation of pollutants can be achieved. However, those IrO2 and ing the intermediates of phenolic compounds oxidation. Otherwise
RuO2 based MMO anodes, i.e. dimensionally stable anodes (DSAs), they will accumulate and form polymeric compounds [94,206].
have received wide application in wastewater treatment because In other studies, several groups have reported electrochemical
of their good resistance to corrosion. One way to improve the elec- treatment of perfluorinated chemicals including perfluorocar-
trochemical oxidation efficiency of these anodes is by applying low boxylic acid (PFCA) and perfluorooctanoic acid (PFOA) at MMO
current densities, at which OER is not favored. anodes [25–27]. The mechanistic investigation of PFOA degrada-
In contrast, SnO2 - and PbO2 -based MMO anodes show high OEP, tion (Fig. 6b) has shown that the whole process was initialized
and they are ideal electrodes for complete oxidation of organics in by direct electron transfer at anode surface, and followed by
wastewater treatment. Chen et al. [151] reported that the TiO2 - two different reaction pathways: (1) perfluoroheptyl radical F-
NTs/SnO2 electrode prepared by electrodeposition has higher OEP (CF2 )6−n -CF2 combined with HO• to produce thermally unstable
than that of TiO2 -NTs/SnO2 prepared by thermochemical decompo- alcohol F-(CF2 )7−n -OH, and (2) perfluoroheptyl radical F-(CF2 )6−n -
sition, which is desirable for electrochemical oxidation of organics. CF2 reacted with oxygen to produce perfluoroheptylperoxy radical
When extra electrodepostion times were applied, the OEP also F-(CF2 )7−n -OO• , and then combined with another perfluorohep-
increased. PbO2 is another typical material with high OEP, but the tylperoxy radical to form perfluoroalkoxy radical F-(CF2 )7−n -O• .
presence of interlayers like RuO2 -TiO2 and IrO2 -Ta2 O5 will decrease Intermediates of the two degradation pathways later underwent
the OEP, resulting from the richer crystalline orientations of PbO2 CF2 unzipping cycle steps, and PFOA can be finally decomposed to
when it was deposited on interlayers [126]. CO2 and HF by repeating the cycle steps.
Although SnO2 - and PbO2 -based MMO anodes are attractive Direct anodic oxidation is attractive because it does not need
materials for electrochemical oxidation of recalcitrant organics, chemical additives which may cause secondary pollution. How-
their industrial application may be restricted by their specific fea- ever, efficient oxidation of organic compounds can only be achieved
tures. For SnO2 -based MMO anodes, the main problem is their with non-active MMO anodes which employed SnO2 or PbO2 as the
short service life, which is attributed to the formation of a certain active layer, and this phenomenon is observed by many compara-
degree of nonstoichiometry SnO(2−x) during OER [141]. This modi- tive studies [24,27,207]. Mao et al. [208] investigated the oxidation
fication of the anode gives rise to the internal stress of the oxidized of azo dye at Ti/SnO2 -Sb and Ti/SnO2 -Sb/PbO2 MMO anodes, and
layer, and finally its detachment from the electrode. The service the former electrode showed better electrocatalytic activity than
life of SnO2 -based MMO anodes can be improved by increasing the latter. However, no noticeable differences between SnO2 -Sb
the electrode mass loading [141], applying isomorphous interlayer and PbO2 electrode is reported in treating landfill leachate [19]. The
[151], modifying the conditions of thermochemical decomposi- main problem during direct anodic oxidation is the deactivation of
tion [198] or doping with platinum [47]. However, the value of the anode surface, due to the formation of polymer on the anode
service life still remains low for practical application. While for surface [206]. The extent of deactivation depends on the adsorption
PbO2 -based MMO anodes, the main issue is the presence of toxic properties of anode surface and the nature and concentration of
Pb ions in treated water. Pb ions were found to be released at the target organics [15]. In practical application, sometimes strong
ppm levels (5–15 mg L−1 ) during electrochemical oxidation of phe- anodic current are required intermittently to oxidize the polymer
nol with Ti/IrO2 -Ta2 O5 /PbO2 electrodes. Nevertheless, the values in the anode.
were significantly influenced by the electrodeposition conditions of For the electrochemical oxidation of pollutants through
PbO2 [199]. Reductive dissolution of PbO2 in acidic solution in the the mediated oxidation at MMO anodes, the electrochemically
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 71

Table 5
Oxygen evolution potential of various MMO anodes.

Anode Oxygen evolution potential (V) vs SHE Condition Reference

TiO2 -NTs/SnO2 1.84–2.19 0.5 M H2 SO4 [151]

Ti/SnO2 -Sb 2.05 0.1 M Na2 SO4 [197]
Ti/SnO2 -Sb2 O3 -Nb2 O5 /PbO2 2.04 0.05 M Na2 SO4 [65]
TiO2 -NTs/SnO2 1.80 0.1 M Na2 SO4 [127]
TiO2 -NTs/Sb-SnO2 /PbO2 1.74 0.5 M Na2 SO4 [45]
Ti/SnO2 -Sb2 O5 /PbO2 1.74 0.1 M Na2 SO4 [93]
Ti/IrO2 -Ta2 O5 1.53 0.5 M H2 SO4 [23]
Ti/IrO2 -SnO2 -Sb2 O5 1.52 0.05 M Na2 SO4 [41]
Ti/IrO2 -RuO2 1.50 0.5 M H2 SO4 [23]
Ti/RuO2 -IrO2 -SnO2 -TiO2 1.44 0.5 M Na2 SO4 [128]

Fig. 5. Mechanistic schemes for (a) direct and (b) mediated electrolytic treatment of pollutants.

generated oxidizing reagents include ozone, chlorine, peroxide, compared to other species. The reactive chlorine usually presents
hypochlorite, peroxodisulfate, and Fenton’s reagent [209]. Among in the form of Cl2 , HClO and ClO– , with the following reactions:
these, reactive chlorine generated from chlorides is probably the
Cl2 + 2e−  2Cl− , E 0 = 1.36 V (2)
most commonly produced mediators, due to their effective activity
+ − 0
and ubiquitous presence in wastewaters at elevated concentration 2HClO + 2H + 2e  Cl2 + 2H2 O, E = 1.63 V (3)

Fig. 6. (a) Schematic diagram of the electrochemical degradation mechanism of PFOA. Reprinted with permission from [27]; (b) reaction pathway for the phenol electrocat-
alytic oxidation on MMO anodes.
Reprinted with permission from [132].
72 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

ClO– + H2 O + 2e−  Cl− + 2OH− , E 0 = 0.90 V (4) discharge to generate HO• . Furthermore, by coupling with ultra-
sonic irradiation, the concentration of HO• could have a maximum
the oxidizing power of the active chlorine are dependent on solu- 54% increase, leading the TOC removal from 33% to 86% [28].
tion pH, which makes the mediated oxidation more effective in
acidic condition [210]. In most cases, the organic pollutants can be
9. Factors influencing electrochemical oxidation efficiency
eliminated at the suitable chloride concentration [16]. However,
the variation of reactive chlorine species is strongly influenced by
There are several operating variables that can influence the elec-
electrolysis conditions such as time, temperature and electrode
trochemical oxidation of organic pollutants by MMO anodes, as
material [211]. Metallic mediators have also found their applica-
outlined and discussed in the following review.
tion in mediated oxidation at MMO anodes. In this case, stable,
low-valence metal ions are oxidized to reactive, high-valence medi- 9.1. pH
ators. Some of the important redox couples of metallic mediators
include Ag(I)/Ag(II), Co(II)/Co(III), Fe(II)/Fe(III) and Ce(III)/Ce(IV) Solution pH is an important factor for electrochemical oxida-
[103,212–214]. However, employing metallic mediators may have tion of organic pollutants using MMO anodes. The effect of pH on
a risk of introducing high toxicity in the effluent and an addition anodic oxidation has been well reported in literature. The find-
step to recover the metallic species is required before discharging ings are diverse and sometimes even contradictory, depending on
the effluents [16]. the types of target pollutants, types of supporting electrolytes and
types of MMO anodes. In general, many published literature report
8. Determination of reactive oxygen species that the removal efficiency of organic pollutants by electrochemi-
cal oxidation tends to increase in the lower pH range, with a few
The determination of ROS, mainly generated from OER in the exemptions. Such trend can be explained from the viewpoint of
anode, has become an important approach to understand the mech- thermodynamics, taking into account that the oxidative power
anism of oxidation of organic pollutants at MMO anodes. Although of solution oxidative species varies with pH. In the direct anodic
ROS can also be generated from oxygen reduction reaction (ORR) oxidation where inert supporting electrolytes are employed, the
in the cathode, it is considered a slow process due to the extraordi- first reaction is the HO• generation from the oxidation of water
nary strong O O bond (498 kJ mol−1 ). Among the ROS, HO• , H2 O2 , molecules:
O2 •− and HO2 • (hydroperoxyl radical) are of special research inter-
est because of their strong oxidative abilities, especially in acidic H2 O → HO• + H+ + e− (8)
solution [215].The rate of ROS formation provides a mechanistic In standard condition (T = 298 K, [HO• ] = 1 M), the redox poten-
parameter to investigate the feasibility of these oxidative species tial for HOaq • /H2 O couple at pH 0 is 2.59 V. According to Nernst
generated by anodic oxidation, and hence the catalytic activity of relationship, the redox potential for HOaq • /H2 O couple at different
the anode material can be evaluated. However, the above men- pH can be given by:
tioned ROS are highly reactive and unstable in solution, with
considerably short life span. In addition, in high pH condition they E 0 (HOaq • /H2 O) = 2.59–0.059 pH (9)
will convert to the anion forms, which exhibit much lower oxidative Thus, a value of 2.18 V for E0 (HOaq • /H2 O)
at pH 7 and 1.77 V for
abilities: E0 (HOaq • /OH– ) at pH 14 can be obtained. The pKa of HO• is 11.9,
HO• + OH−  • O− + H2 O, pKb = 2.1 (5) which results in E0 (• O– aq /OH– ) = 1.64 V at pH 14 [231]. Since the
HO• exhibits higher oxidative potential in the lower pH range, it is
H2 O2 + OH  HO2 – + H2 O,
−
pKb = 2.4 (6) not surprising that better removal efficiency for organic pollutants
is achieved. Moreover, the OER caused by HO• radicals or water
HO2 • + OH−  O2 • – + H2 O, pKb = 9.2 (7)
oxidation is inhibited at the acidic condition (Eqs. (10) and (11)):
Since the ROS in solution are difficult to be determined by
2HO• → O2 + 2H+ + 2e− (10)
direct measurements, reagents known as chemical probes or ROS
+ −
scavengers have been employed to react with them to form sta- 2H2 O → 2O2 + 4H + 4e (11)
ble products. These products can be qualitatively or quantitatively
Thus, the oxidation of organic pollutant is favored at acidic
analyzed by various techniques, including high performance liq-
pH range. For electrochemical oxidation of real wastewater which
uid chromatography (HPLC), fluorescence spectroscopy, UV–visible
contains various anions, acidic condition also reduces the con-
spectroscopy (UV–vis), photoluminescence (PL), amperometric
centration of HCO3 − and CO3 2− which are strong HO• scavengers
detection and electron spin resonance (ESR). Table 6 summarized
[232,233].
the various reported analysis techniques and corresponding scav-
Many studies have reported the influence of pH on mediated
engers for detection of electrogenerated ROS in some studies.
anodic oxidation of organics in chlorine solution with MMO anodes.
Moreover, those ROS scavengers were also added to the bulk solu-
In most cases, the degradation of organic pollutants is attained by
tions as effective quenchers of selective ROS, since it is interesting
anodically generated reactive chlorine species at suitable pH ranges
to investigate the role of individual ROS in organics removal by
[27,196,197,234,235]. The solution pH can affect the form of reac-
advanced oxidation processes (AOPs) by inhibiting their aquatic
tive chlorine species and their oxidation potentials [236]. However,
presence [216]. However, to the best of authors’ knowledge, related
chlorine molecule (E0 (Cl2 /Cl− ) = 1.36 V) only exists in neutral or
study has not been reported for electrochemical oxidation at MMO
acidic solution. When the proton and chloride concentrations are
anodes.
not high enough, chlorine molecule will dissolve in the water by
Comparing with Pt and Ti anodes, the HO• production on
disproportionation to form hypochlorous acid and chloride:
Ti/RuO2 -TiO2 anode is much larger [222]. One way to increase
the HO• production is by surface modification. The HO• produc- Cl2 + H2 O → HClO + Cl− + H+ (12)
tion on mesoporous SnO2 -Sb (61.7 ␮mol L−1 ) is twice that of the − +
HClO → ClO + H (13)
conventional one (30.3 ␮mol L−1 ). Moreover, the yield of HO• on
SnO2 -RuO2 was found to be significantly enhanced by doping with The pKa of hypochlorous acid is 7.54. In the lower pH
Ce, which could act as active centers on Ce-Ru-SnO2 and increase range, the dominant form of active chlorine is hypochlor-
the active sites [102]. More water molecules were adsorbed and ous acid (E0 (HClO/Cl2 ) = 1.63 V or E0 (HClO/Cl− ) = 1.48 V), which
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 73

Table 6
Analysis technics employing ROS scavengers for determination of electrogenerated ROS.

ROS type Analysis ROS scavengers Determination Remark Reference

technics accuracy

HO• ESR 5,5-Dimethyl-1-pyrroline-N- Quantitative DMPO-HO• was generated with [78,217,218]

oxide hyperfine constants ˛N = ˛H = 14.0 G
(DMPO) and g-value = 2.0065.
HPLC Benzoic acid; dimethyl Quantitative HO• scavengers reacted with HO• and [84,219–221]
sulfoxide (DMSO); salicylic acid the concentration of final products are
analyzed by HPLC.
UV–vis p-Nitrosodimethylaniline Quantitative RNO was bleached by HO• , with [191,222]
(RNO) maximum absorbance at 440 nm and
350 nm reported.
PL Terephthalic acid Qualitative Highly fluorescent product was [223–225]
generated with corresponding PL
signal at 425 nm.
Fluorescence Aminophenyl fluorescamine Quantitative Excitation and emission wavelengths [226]
were set to 490 nm and 520 nm
respectively.

HO2 • /O2 • − ESR 5,5-Dimethyl-1-pyrroline-N- Quantitative DMPO-O2 • − and nitroxide-like radicals [227]
oxide were generated, with hyperfine
(DMPO) constants ˛N = 14.1 G, ˛H ␤ = 10.8 G and
˛H ␥ = 1.4 G for DMPO-O2 • − and
˛N = 1.4 G for nitroxide-like radical.
Fluorescence Luminol Quantitative 3-Aminophthalate of excited state was [228]
generated and emitted light at
wavelength 425 nm.
HPLC Hydroethidine Quantitative 2-Hydroxyethidium was generated [229]
and its concentration was analyzed by
HPLC.

H2 O2 UV–vis 2,9-Dimethyl-1,10- Quantitative Maximum absorbance wavelength [230]

phenanthroline obtained at 454 nm.
(DMP)

has considerably higher oxidation potential than hypochlorite to determine. In other study, Rajkumar et al. [241] investigated the
(E0 (ClO− /Cl− ) = 0.89 V) in alkaline media. Thus, the organic pollu- electrochemical oxidation of phenol at initial pH from 3 to 10 using
tants are removed more efficiently in acidic media. However, when Ti/TiO2 -RuO2 -IrO2 anode, and they found the final pH always in
treating paper mill wastewater using Ti/Co/SnO2 -Sb2 O5 anode, the range 8–8.5. The authors explained such observation from the
much better COD removal and decolorization rate was obtained viewpoint of bicarbonate buffering effect. In addition, some litera-
at pH 11 than pH 3 [234]. ture did not report clearly whether the pH was initial or final pH,
In addition, pH may influence the process efficiency through and whether solution pH was maintained during the electrochem-
electromigration mass transfer. It is reported that the solubility or ical oxidation process.
ionization degree of cationic dyes can be improved at lower pH
condition [237], which could enhances the dispersion of dye and 9.2. Temperature
decreases the resistance to mass transfer. In other study, the degra-
dation of PFOA by Ti/SnO2 -Sb-based MMO anodes was found to be A change in temperature will change both the reaction rates of
more favorable in acidic solution [27]. However, under strongly organic degradation in bulk and capacity of HO• adsorption in the
acidic condition (pH 3), the removal efficiency of PFOA by the MMO anode surface. The effect of temperature on the anodic oxi-
anodes decreased again because of the weak dissociation ability of dation of organic compounds has been investigated with respect to
PFOA at low pH, which limited the electromigration mass transfer. different MMO anodes. Some published literature report increased
Similar result was observed in pentachlorophenol (PCP) degrada- organics removal with solution temperature. For example, the
tion by Ti/SnO2 -Sb anode. The anion form of PCP at higher pH can be first-order kinetic rate constant (k) of lignin oxidation by Ti/TiO2 -
much more easily adsorbed on the anode surface, resulting in the NTs/PbO2 electrode was found to increase from 0.0018 min−1 at
enhanced PCP degradation at pH 11. Nevertheless, some organic 20 ◦ C to 0.0043 min−1 at 60 ◦ C [149]. In other study, the rate was
compounds may experience polymerization at higher pH, including even 2.7-fold higher at 65 ◦ C than at 23 ◦ C for electrochemical oxi-
dye [238] and phenol [239,240]. The polymer films have low perme- dation of 4-chorophenol with quaternary Ti/Sn-Sb-Mn-Pt-O anode
ability and show strong adhesion to the MMO anodes, which lead [242]. By plotting ln k vs 1/T through Arrhenius equation, the acti-
to the anode fouling problems. Though in most cases acidic con- vation energy (Ea ) can be derived:
dition favors the organic pollutants degradation by MMO anodes,
the decrease of electrode service life and leaching of toxic metal Ea
ln k = − + ln A (14)
ions in acidic media should also be taken into consider in practical RT
application of wastewater treatment. where A refers to the frequency factor which is a constant, and R
Several reasons may give rise to the discrepancies on the refers to the universal gas constant.
reported pH influences on electrochemical oxidation of organic Many studies found the influence of temperature on removal
pollutants by MMO anodes. One important reason is that the solu- rates of target pollutants was in good accordance with this equa-
tion pH is not constant throughout the electrochemical oxidation tion [149,243,244]. Ea can be regarded as the energy barrier
process, since OER in the anode and hydrogen evolution reaction for electrochemical oxidation reaction to occur, which provides
(HER) in the cathode involve drastic hydrogen ions generation and a thermodynamic view of the electrocatalytic activity of MMO
consumption. However, their influences on solution pH are difficult anodes. For example, the Ea of lignin oxidation by Ti/TiO2 -NTs/PbO2
74 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

anode (16 kJ mol−1 ) was slightly smaller than that by Ti/RuO2 -IrO2 Regarding MMO anodes, the choice of upper limit of applied
(20 kJ mol−1 ), indicating better electrocatalytic activity of Ti/TiO2 - current density should be more discreet compared with other
NTs/PbO2 which lowered the energy barrier. anodes such as BDD and Pt. The crystalline structures and chemical
However, several studies reported that the electrochemical states of MMO compounds in the surface layer are likely to change
oxidation of target organic pollutants remained unaffected by irreversibly under high current density, resulting in anode deacti-
change of temperature. Examples are electrochemical oxidation of vation. Besides, semiempirical study also reported that the optimal
maleic acid at Ti/IrO2 -Ta2 O5 anode [195] and p-methoxyphenol at current densities were far from the diffusion-limiting current den-
Ti/SnO2 -Sb anode [244]. Both of the organics have strong C C bond sity [248].
(614 kJ mol−1 ). It was unclear whether this strong bond gave rise to
the temperature-independent electrochemical oxidation process. 9.4. Supporting electrolyte
In mediated oxidation process, it is generally acknowledged
that the increase of temperature favors the electrogeneration of Various types of supporting electrolyte have been employed for
oxidative reagents like reactive chlorine, peroxodisulfate and ROS, electrochemical oxidation of organic pollutants at MMO anodes,
thus improve the process efficiency [245]. However, a contradic- with the primary goal of increasing the solution conductivity.
tory observation was made by Neodo et al. [211], who investigated Intense research interest has been devoted to investigating the
the electrolysis of dilute chloride solutions at Ti/RuO2 -SnO2 and influence of types and concentrations of supporting electrolytes
found that the detected concentration of active chlorine species on the electrochemical oxidation of organic pollutants. In general,
was reduced when increasing the temperature from 10 ◦ C to 65 ◦ C. supporting electrolytes were prepared by salts including neutral
The observation may result from the drastic active chlorine con- salts (NaClO4 , Na2 SO4 , NaCl and NaNO3 ) and reducing salts (NaSO3
sumption reactions at high temperature. Indeed, more studies are and NaNO2 ) [75]. Among them, NaClO4 and NaNO3 are highly sta-
needed to illustrate the mechanism of temperature influence on ble compounds which can avoid producing any oxidizing species
both mediated anodic oxidation and mediated oxidation at MMO liable to react with organic compounds [57,233], making them
anodes. suitable for studying direct anodic oxidation at the MMO anodes.
Considering the additional cost that operation at high temper- Many studies have shown the superiority of NaCl over Na2 SO4
ature may bring, electrochemical oxidation of organic pollutants and other electrolytes, especially for the treatment of solutions
is usually conducted at ambient temperature. Nevertheless, there containing dyestuff [44,249,250]. However, the addition of chlo-
is also argument that high temperature is on applicable scale for ride ions enhanced mainly the decolorization efficiency but not
electrochemical oxidation at MMO anodes. Since electrochemical the TOC reduction [45], indicating more effective attack to the
oxidation is an exothermic process and heat can also be gener- chromophoric groups of the dyestuff molecule by active chlorine.
ated by the solution resistance, high operating temperatures may Promotion factor (f) was proposed by Zhou et al. [251] to assess the
be maintained without much additional cost. In addition, there is role of mediated oxidation by presence of additional NaCl, which
study confirmed that MMO anodes are more stable at high temper- can be given by:
ature than other anodes like BDD, meanwhile they exhibit more Kobs2
significant improvement in the pollutants removal efficiency with f = −1 (15)
Kobs1
increasing temperature [195]. All of these reasons make it attractive
for operation at appropriate high temperature. where Kobs2 and Kobs1 are the apparent rate constant for pseudo
first order reactions with and without NaCl. In their study, f can be
as large as 73.3 for electrochemical oxidation of methyl orange at
9.3. Current density RuO2 - based MMO anode.
Compared with BDD anode and non-active MMO anodes, elec-
Current density is considered as an important operating param- trochemical oxidation by active anodes have a greater influence
eter for electrochemical oxidation of organics at MMO anodes, by the presence of Cl− , due to their inefficiency to produce HO•
for the purpose of both mechanistic study and cost-effectiveness radicals [21]. The main drawback of employing NaCl as supporting
analysis. In electrochemical oxidation, the capability of electron electrolyte is its possible formation of organochlorine compounds
transfer and generation of oxidizing agents (HO• , HO2 • , ozone or (RCl), which can be present as persistent compounds and even more
active chlorine) rely on the applied current density [75]. Perez toxic than their parent compounds. However, studies have shown
et al. [246] found that the generation of ClO3 − and free chlorine that RCl could be quickly consumed before the end of electrolysis
were significantly enhanced by increasing the current density from [252].
50 mA cm−2 to 100 mA cm−2 . Rapid oxidation was also confirmed
by Neodo et al. [211], and such effect was far more dinstinctive on 10. Challenges, improvement and potential application of
Ti/RuO2 -SnO2 anode than Pt anode. Although high current densities MMO anodes
favor the electrochemical oxidation of many pollutants, obvious
enhancement of the energy efficiency is observed when the applied 10.1. Toxicity of byproducts
current densities are at a low level.
In industrial application, high current density is seldom For practical application of electrochemical oxidation treat-
employed for the electrochemical oxidation of organics due to (1) ment, one of the important considerations is the change of toxicity
the enhancement of removal rate by increasing current density is of treated wastewater, due to the nature of diverse compounds in
relatively low when it is already at a high level, (2) side reaction real industrial wastewaters. Though many studies have confirmed
such as OER consumed the HO• and competes with the electro- the improvement of biodegradability in treating specific biorefrac-
chemical oxidation of contaminants [192,247] and (3) extra energy tory aqueous pollutants, it may be a whole different scene when
are consumed since the temperature of the solution is significantly dealing with wastewaters containing halogenated compounds,
increase at high current density. From the process kinetic point such as RO concentrate [253] and olive mill wastewater [254]. The
of view, the oxidation of pollutants may be mass transfer limiting transformation of organic compounds to their halogenated deriva-
reaction when the current density is high, and a better COD removal tives involving –Cl and –Br substituents in the organic molecule
can be achieved by simply increasing the flow rate of supporting are expected to augment significantly the toxicological properties.
electrolyte [33,194]. The byproducts formed can be very problematic and the toxicity
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 75

can increase by a factor of even 40–60 times [24], which repre-

sent an insurmountable barrier to the environmental application of
MMO anodes. However, it is worth noting that such observations
were usually reported in active MMO anodes, of which the oxi-
dation power was not sufficient to fully degrade the halogenated
byproducts. Therefore, with MMO anodes, careful design of elec-
trochemical operation is crucial to the success of its application.

10.2. Divided electrochemical oxidation cell Fig. 7. Schematic diagram of the MMO anodes coupled with nanofiltration mem-
brane in the membrane cell.
Reprinted with permission from Ref. [262].
Apart from the anode material, cell design is another important
factor that could influence the efficiency of anodic oxidation pro-
cess. To date, only a few well-documented studies have reported
the electrochemical oxidation of pollutants with MMO anodes in strongly dependent on the preparation conditions, including dop-
divided cell, of which the anodic chamber and cathodic chamber ing levels of dopants and annealing temperature. Future study
are separated by ion exchange membrane [34,80,255]. Undivided should also be carried out to better distinguish the organics removal
cells are widely applied because the cell resistance is only caused by photocatalytic oxidation and by photolysis through UV irradia-
by the ohmic drop of the solution, which is much less than that of tion.
the divided cell. However, there are several drawbacks of using Electrochemical oxidation combined with pressure-driven
an undivided cell: (1) the oxidation products at the anode will membrance process has been gaining attention in recent years,
inevitably become the competitive species for reduction reaction although the electrochemical oxidation of RO concentrates has
at the cathode, which reduces the overall process efficiency; and been investigated much earlier. Fig. 7 gives the schematic dia-
(2) the reactions involved in above mentioned process will fal- gram of the MMO anodes coupled with nanofiltration membrane
sify the primary electrochemical reactions, which is not favored in the membrane cell [262]. The application of electrochemi-
in determining the reaction mechanism. Therefore the divided cell cal oxidation showed substantial improvements in nanofiltration
is a promising design to achieve better process efficiency as well as by reducing concentration polarization and reducing membrane
more precise determination of mechanism. fouling [197,262]. Indeed, future works aimed at modeling the elec-
trochemical oxidation coupled with nanofiltration are worthwhile
10.3. Coupling with other processes to better understand the synergism of the coupling process.

Electrochemical oxidation has attracted a great deal of attention

for non-biodegradable wastewater treatment, however the energy 11. Conclusions
consumption is high (>10 kWh m−3 ) for complete degradation of
organic pollutants [256]. It is much higher than that of the con- MMO anodes, prepared by depositing MMO layer on inert sub-
ventional biological treatment of biodegradable pollutants, which strates, provide technical merit in treating wastewaters containing
requires only 0.3–0.5 kWh m−3 energy consumption. Pretreatment recalcitrant organic pollutants by electrochemical oxidation. Com-
wastewaters containing non-biodegradable compounds by elec- pared with single-component mixed metal oxide anode, they
trochemical oxidation at MMO anodes has become a promising exhibit better electrocatalytic activity resulting from the increase
process before biological treatment, because the biorecalcitrance of active sites and a change in the oxidation states of the metal
of the treated wastewater significantly decreased [257]. The degra- ions. Intense research efforts have been devoted to the surface
dation of orange II by combined electrochemical-biological method modification of MMO anodes, aiming to increase the surface
with Ti/SnO2 -Sb-Mn anode has been demonstrated by Yao et al. area or introducing expected properties to the MMO layer. Such
[42], and the energy consumption was about 6 kWh m−3 , remark- approaches include nano- and microstructure deposits, element
ably lower than electrochemical oxidation. In another study, doping and polymer composites. In addition, electrochemical oxi-
electrochemical oxidation with MMO anodes was also utilized dation at MMO anodes has the advantage of coupling direct and
as post-treatment of landfill leachates treated with membrane mediated oxidation processes, making it an attractive technique
bioreactor (MBR), and such combination resulted in an efficient for treating various types of polluted water. In general, MMOs
reduction of COD and color of the permeate from MBR [258]. How- exhibit better process efficiency of electrochemical oxidation in
ever, such combination method is not suitable for wastewaters acidic media and at high temperature, but the optimal operating
with low salinity, of which the conductivity is not high enough to conditions on application scale still remain arguable.
maintain effective electrochemical oxidation process. As yet the links between the surface structure of MMO anodes
Ultrasonic irradiation of aqueous solution is well known for and their electrocatalytic performance is still not clearly estab-
yielding cavitation. The cavitation phenomenon has the merit to (1) lished in literature, as well as the role of ROS in pollutants removal
clean the anode surface; (2) improve mass transport of target pollu- or alleviation. Hence, more such information is required by careful
tants; and (3) produce active substances such as free HO• [259,260]. characterization with state-of-art analysis techniques. In addition,
Such combination system was found to enhance TOC removal of MMO anodes have several drawbacks such as limited life span and
PFOA from 33% to 86% [28]. toxic cation leaching in strong acidic solution, which may limit
From the nature of materials, metal oxide compounds involved scale-up of them for electrochemical oxidation of organic pollu-
in MMO anodes such as SnO2 and TiO2 are n-type semiconduc- tants.
tors, which make them retain photoelectrocatalytic activity as In order to achieve full-scale application of MMO anodes for
well. MMO anodes including Ti/SnO2 -SbO4 [261], Ti/BiOx -TiO2 [73], electrochemical oxidation of recalcitrant organic pollutants, addi-
Ti/(TiO2 )0.7 (RuO2 )0.3 [110] and Ti/TiO2 /SnO2 [64,101] are stud- tional studies are required to (1) better understand the role of
ied for their photoelectrochemical oxidation of organic pollutants. ROS and the degradation pathway of pollutants; (2) develop cost-
Photoelectrochemical process can improve the efficiency of pure effective method to produce MMO anodes with good chemical
electrochemical oxidation by synergistic effect, as well as avoid the and physical stability and (3) couple with other technologies as
suspensions of photocatalyst. However, the anode performance is to improve the process efficiency and reduce cost.
76 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

Acknowledgments [48] T. Panakoulias, P. Kalatzis, D. Kalderis, A. Katsaounis, J. Appl. Electrochem. 40

(2010) 1759–1765.
[49] S. Song, J. Fan, Z. He, L. Zhan, Z. Liu, J. Chen, X. Xu, Electrochim. Acta 55 (2010)
Weiyi Wu would like to gratefully acknowledge Nanyang 3606–3613.
Technological University (NTU) for the award of a PhD research [50] M. Catanho, G.R.P., Malpass, A.J. Motheo, Appl. Catal. B: Environ. 62 (2006)
scholarship. Singapore Institute of Manufacturing Technology 193-200.
[51] L. Szpyrkowicz, R. Cherbanski, G.H. Kelsall, Ind. Eng. Chem. Res. 44 (2005)
(SIMTech) is thanked for the generous provision of experimental 2058–2068.
facilities. [52] M. Sala, A.I. Del Río, J. Molina, F. Cases, M.C. Gutiérrez-Bouzán, Int. J. Elec-
trochem. Sci. 7 (2012) 12470–12488.
[53] D. Rajkumar, J.G. Kim, J. Hazard. Mater. 136 (2006) 203–212.
References [54] E. Chatzisymeon, N.P. Xekoukoulotakis, A. Coz, N. Kalogerakis, D. Mantzavi-
nos, J. Hazard. Mater. 137 (2006) 998–1007.
[1] M.B. Gawande, R.K. Pandey, R.V. Jayaram, Catal. Sci. Technol. 2 (2012) 1113. [55] G.R. Malpass, D.W. Miwa, S.A. Machado, A.J. Motheo, J. Hazard. Mater. 180
[2] C.H. Wang, H.S. Weng, Ind. Eng. Chem. Res. 36 (1997) 2537–2542. (2010) 145–151.
[3] J.C. Wu, C.S. Chung, C.L. Ay, I. Wang, J. Catal. 87 (1984) 98–107. [56] G.R. Malpass, D.W. Miwa, S.A. Machado, P. Olivi, A.J. Motheo, J. Hazard. Mater.
[4] S. Blanco, S.R.G. Carrazan, V. Rives, Appl. Catal. A: Gen. 342 (2008) 93–98. 137 (2006) 565–572.
[5] F.J. Perez-Alonso, I. Melian-Cabrera, M.L. Granados, F. Kapteijn, J.L.G. Fierro, J. [57] G.R.P. Malpass, D.W. Miwa, A.C.P. Miwa, S.A.S. Machado, A.J. Motheo, Environ.
Catal. 239 (2006) 340–346. Sci. Technol. 41 (2007) 7120–7125.
[6] M.O. Guerrero-Perez, M.V. Martinez-Huerta, J.L.G. Fierro, M.A. Banares, Appl. [58] G.R.P. Malpass, G.R. Salazar-Banda, D.W. Miwa, S.A.S. Machado, A.J. Motheo,
Catal. A: Gen. 298 (2006) 1–7. Environ. Technol. 34 (2013) 1043–1051.
[7] K.H. Lin, C.B. Wang, S.H. Chien, Int. J. Hydrogen Energy 38 (2013) 3226–3232. [59] G.R.P. Malpass, D.W. Miwa, A.C.P. Miwa, S.A.S. Machado, A.J. Motheo, J. Hazard.
[8] L. Vazquez-Gomez, S. Ferro, A. De Battisti, Appl. Catal. B: Environ. 67 (2006) Mater. 167 (2009) 224–229.
34–40. [60] H. Bouya, M. Errami, R. Salghi, L. Bazzi, A. Zarrouk, S.S. Al-Deyab, B. Hammouti,
[9] M.M. Arafat, B. Dinan, S.A. Akbar, A.S.M.A. Haseeb, Sensors 12 (2012) L. Bazzi, A. Chakir, Int. J. Electrochem. Sci. 7 (2012) 3453–3465.
7207–7258. [61] R. Vargas, S. Díaz, L., Viele, O. Núñez, C. Borrás, J., Mostany, B.R. Scharifker,
[10] M.C. Tucker, J. Power Sources 195 (2010) 4570–4582. Appl. Catal. B: Environ. 144 (2013) 107-111.
[11] M. Hua, S. Zhang, B. Pan, W. Zhang, L. Lv, Q. Zhang, J. Hazard. Mater. 211–212 [62] C.A. Martinez-Huitle, A. De Battisti, S. Ferro, S. Reyna, M. Cerro-Lopez, M.A.
(2012) 317–331. Quiro, Environ. Sci. Technol. 42 (2008) 6929–6935.
[12] J. Desilvestro, O. Haas, J. Electrochem. Soc. 137 (1990) 5C–22C. [63] S.A. Neto, A.R. De Andrade, J. Appl. Electrochem. 39 (2009) 1863–1870.
[13] R. Andreozzi, R. Marotta, N. Paxeus, Chemosphere 50 (2003) 1319–1330. [64] P.Q. Li, G.H. Zhao, X. Cui, Y.G. Zhang, Y.T. Tang, J. Phys. Chem. C 113 (2009)
[14] S. Seker, H. Beyenal, B. Salih, A. Tanyolac, Appl. Microbiol. Biotechnol. 47 2375–2383.
(1997) 610–614. [65] X. Yang, R. Zou, F. Huo, D. Cai, D. Xiao, J. Hazard. Mater. 164 (2009) 367–373.
[15] M. Panizza, G. Cerisola, Chem. Rev. 109 (2009) 6541–6569. [66] Y.J. Feng, Y.H. Cui, B. Logan, Z.Q. Liu, Chemosphere 70 (2008) 1629–1636.
[16] C.A. Martinez-Huitle, S. Ferro, Chem. Soc. Rev. 35 (2006) 1324–1340. [67] K. Zhu, W. Zhang, H. Wang, Z. Xiao, Clean Soil Air Water 36 (2008) 97–102.
[17] C.A. Martinez-Huitle, L.S. Andrade, Quim. Nova 34 (2011) 850–858. [68] Y. Feng, Y.H. Cui, J. Liu, B.E. Logan, J. Hazard. Mater. 178 (2010) 29–34.
[18] A. Anglada, A. Urtiaga, I. Ortiz, J. Chem. Technol. Biotechnol. 84 (2009) [69] Y.Q. Wang, B. Gu, W.L. Xu, J. Hazard. Mater. 162 (2009) 1159–1164.
1747–1755. [70] F.P. Hu, X.W. Cui, W.X. Chen, Electrochem. Solid-State Lett. 13 (2010)
[19] R. Cossu, A.M. Polcaro, M.C. Lavagnolo, M. Mascia, S. Palmas, F. Renoldi, Envi- F20–F23.
ron. Sci. Technol. 32 (1998) 3570–3573. [71] Y. Zheng, W. Su, S. Chen, X. Wu, X. Chen, Chem. Eng. J. 174 (2011) 304–309.
[20] E. Tauchert, S. Schneider, J.L. de Morais, P. Peralta-Zamora, Chemosphere 64 [72] H. Xu, A.-P. Li, Q. Qi, W. Jiang, Y.-M. Sun, Korean J. Chem. Eng. 29 (2012)
(2006) 1458–1463. 1178–1186.
[21] A.Y. Bagastyo, D.J. Batstone, K. Rabaey, J. Radjenovic, Water Res. 47 (2013) [73] H. Park, A. Bak, Y.Y. Ahn, J. Choi, M.R. Hoffmannn, J. Hazard. Mater. 211 (2012)
242–250. 47–54.
[22] A.Y. Bagastyo, J. Radjenovic, Y. Mu, R.A. Rozendal, D.J. Batstone, K. Rabaey, [74] H. Park, C.D. Vecitis, M.R. Hoffmann, J. Phys. Chem. C 113 (2009) 7935–7945.
Water Res. 45 (2011) 4951–4959. [75] J. Niu, Y. Bao, Y. Li, Z. Chai, Chemosphere 92 (2013) 1571–1577.
[23] M.H. Zhou, L. Liu, Y.L. Jiao, Q. Wang, Q.Q. Tan, Desalination 277 (2011) [76] J.T. Kong, S.Y. Shi, L.C. Kong, X.P. Zhu, J.R. Ni, Electrochim. Acta 53 (2007)
201–206. 2048–2054.
[24] J. Radjenovic, B.I. Escher, K. Rabaey, Water Res. 45 (2011) 3205–3214. [77] Y.W. Yao, C.M. Zhao, J. Zhu, Electrochim. Acta 69 (2012) 146–151.
[25] Q.F. Zhuo, S.B. Deng, B. Yang, J. Huang, G. Yu, Environ. Sci. Technol. 45 (2011) [78] H. Wang, J.L. Wang, J. Hazard. Mater. 154 (2008) 44–50.
2973–2979. [79] Y.H. Wang, K.Y. Chan, X.Y. Li, S.K. So, Chemosphere 65 (2006) 1087–1093.
[26] J. Niu, H. Lin, J. Xu, H. Wu, Y. Li, Environ. Sci. Technol. 46 (2012) 10191–10198. [80] S. Song, L.Y. Zhan, Z.Q. He, L.L. Lin, J.J. Tu, Z.H. Zhang, J.M. Chen, L.J. Xu, J. Hazard.
[27] H. Lin, J. Niu, S. Ding, L. Zhang, Water Res. 46 (2012) 2281–2289. Mater. 175 (2010) 614–621.
[28] H. Zhao, J. Gao, G. Zhao, J. Fan, Y. Wang, Y. Wang, Appl. Catal. B: Environ. [81] J. Niu, D. Maharana, J. Xu, Z. Chai, Y. Bao, J. Environ. Sci. 25 (2013) 1424–1430.
136–137 (2013) 278–286. [82] G.H. Zhao, Y.G. Zhang, Y.Z. Lei, B.Y. Lv, J.X. Gao, Y.A. Zhang, D.M. Li, Environ.
[29] Y.J. Feng, J.F. Liu, L.M. Zhu, J.Z. Wei, Water Sci. Technol. 68 (2013) 257–260. Sci. Technol. 44 (2010) 1754–1759.
[30] Z.Q. He, C.X. Huang, Q. Wang, Z. Jiang, J.M. Chen, S. Song, Int. J. Electrochem. [83] M.C.Q. de Oliveira, A.A. Tanaka, M.R.D. los Lanza, M.D.T. Sotomayor, Electro-
Sci. 6 (2011) 4341–4354. analysis 23 (2011) 2616–2621.
[31] L. Ciriaco, D. Santos, M.J. Pacheco, A. Lopes, J. Appl. Electrochem. 41 (2011) [84] J. Fan, G. Zhao, H. Zhao, S. Chai, T. Cao, Electrochim. Acta 94 (2013) 21–29.
577–587. [85] W. Cheng, M. Yang, Y. Xie, B. Liang, Z. Fang, E.P. Tsang, Chem. Eng. J. 220 (2013)
[32] Q. Dai, H. Shen, Y. Xia, F. Chen, J. Wang, J. Chen, Sep. Purif. Technol. 104 (2013) 214–220.
9–16. [86] W. Cheng, M. Yang, Y. Xie, Z. Fang, J. Nan, P.E. Tsang, Environ. Technol. (2013)
[33] F.A. Rodríguez, M.N. Mateo, J.M. Aceves, E.P. Rivero, I. González, Environ. 1–11.
Technol. 34 (2013) 573–583. [87] C. Carlesi Jara, D. Fino, V. Specchia, G. Saracco, P. Spinelli, Appl. Catal. B:
[34] S. Raghu, C.W. Lee, S. Chellammal, S. Palanichamy, C.A. Basha, J. Hazard. Mater. Environ. 70 (2007) 479–487.
171 (2009) 748–754. [88] H.C.A. Valdez, G.G. Jimenez, S.G. Granados, C.P. de Leon, Chemosphere 89
[35] C.A. Basha, J. Sendhil, K.V. Selvakumar, P.K.A. Muniswaran, C.W. Lee, Desali- (2012) 1195–1201.
nation 285 (2012) 188–197. [89] H. Lin, J. Niu, J. Xu, Y. Li, Y. Pan, Electrochim. Acta 97 (2013) 167–174.
[36] J.G. Zhang, Y.P. Wei, G.J. Jin, G. Wei, J. Mater. Sci. Technol. 26 (2010) 187–192. [90] G.T. Li, J.X. Yan, J. Chen, M.Y. Zhu, L.F. Zhu, X.W. Zhang, International Confer-
[37] H. Xu, Q. Zhang, W. Yan, W. Chu, L.F. Zhang, Int. J. Electrochem. Sci. 8 (2013) ence on Energy and Environment Technology, Vol. 3, Proceedings, 2009, pp.
5382–5395. 253–256.
[38] F. Wang, S. Li, M. Xu, Y. Wang, W. Fang, X. Yan, J. Electrochem. Soc. 160 (2012) [91] D. Santos, M.J. Pacheco, A. Gomes, A. Lopes, L. Ciriaco, J. Appl. Electrochem. 43
D53–D59. (2013) 407–416.
[39] K. Zhao, G. Zhao, P. Li, J. Gao, B. Lv, D. Li, Chemosphere 80 (2010) 410–415. [92] Y. Feng, C. Wang, J. Liu, Z. Zhang, J. Environ. Monit. 12 (2010) 404–408.
[40] H. Xu, Q. Zhang, W. Yan, W. Chu, Int. J. Electrochem. Sci. 6 (2011) 6639–6652. [93] B. Xue, Y. Zhang, J.Y. Wang, Proc. Environ. Sci. 10 (2011) 647–652.
[41] R. Chaiyont, C. Badoe, C.P. de León, J.L. Nava, F.J. Recio, I. Sirés, P. Herrasti, F.C. [94] Y.H. Cui, X.Y. Li, G.H. Chen, Water Res. 43 (2009) 1968–1976.
Walsh, Chem. Eng. Technol. 36 (2013) 123–129. [95] G.F. Pereira, R.C. Rocha-Filho, N. Bocchi, S.R. Biaggio, Chem. Eng. J. 198–199
[42] P. Yao, X. Chen, Z. Shen, Desalination Water Treat. (2013) 1–7. (2012) 282–288.
[43] J. Wu, F. Liu, H. Zhang, J.H. Zhang, L. Li, Desalination Water Treat. 44 (2012) [96] H. Wang, D.Z. Sun, Z.Y. Bian, J. Hazard. Mater. 180 (2010) 710–715.
36–43. [97] L. Vazquez-Gomez, A. de Battisti, S. Ferro, M. Cerro, S. Reyna, C.A. Martinez-
[44] D. Rajkumar, B.J. Song, J.G. Kim, Dyes Pigments 72 (2007) 1–7. Huitle, M.A. Quiroz, Clean Soil Air Water 40 (2012) 408–415.
[45] H. An, H. Cui, W. Zhang, J. Zhai, Y. Qian, X. Xie, Q. Li, Chem. Eng. J. 209 (2012) [98] Y. Liu, H. Liu, J. Ma, J. Li, Electrochim. Acta 56 (2011) 1352–1360.
86–93. [99] X.P. Zhu, M.P. Tong, S.Y. Shi, H.Z. Zhao, J.R. Ni, Environ. Sci. Technol. 42 (2008)
[46] M.T. Karuppiah, G.B. Raju, Ind. Eng. Chem. Res. 48 (2009) 2149–2156. 4914–4920.
[47] A.I. del Río, J. Fernández, J. Molina, J. Bonastre, F. Cases, Electrochim. Acta 55 [100] X.B. Liu, H.Y. Lu, W.M. Huang, H.S. Kong, X.B. Ren, H.B. Lin, Curr. Org. Chem.
(2010) 7282–7289. 16 (2012) 1967–1971.
 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78 77

[101] S. Chai, G. Zhao, P. Li, Y. Lei, Y.-N. Zhang, D. Li, J. Phys. Chem. C 115 (2011) [155] P.Q. Li, G.H. Zhao, M.F. Li, T.C. Cao, X. Cui, D.M. Li, Appl. Catal. B: Environ. 111
18261–18269. (2012) 578–585.
[102] Y. Liu, H.L. Liu, J. Ma, J.J. Li, J. Hazard. Mater. 213 (2012) 222–229. [156] Y.B. Wang, Y.N. Zhang, G.H. Zhao, H.Y. Tian, H.J. Shi, T.C. Zhou, ACS Appl. Mater.
[103] Y.Y. Chu, Y. Qian, W.J. Wang, X.L. Deng, J. Hazard. Mater. 199 (2012) 179–185. Interfaces 4 (2012) 3965–3972.
[104] Y. Liu, H.L. Liu, Electrochim. Acta 53 (2008) 5077–5083. [157] M.F. Wu, Y.N. Jin, G.H. Zhao, M.F. Li, D.M. Li, Environ. Sci. Technol. 44 (2010)
[105] H.L. Liu, Y. Liu, C. Zhang, R.S. Shen, J. Appl. Electrochem. 38 (2008) 101–108. 1780–1785.
[106] H. Lin, J. Niu, J. Xu, H. Huang, D. Li, Z. Yue, C. Feng, Environ. Sci. Technol. 47 [158] L. Frolova, N. Lyskov, Y. Dobrovolsky, Solid State Ionics 225 (2012) 92–98.
(2013) 13039–13046. [159] M.K. Datta, K. Kadakia, O.I. Velikokhatnyi, P.H. Jampani, S.J. Chung, J.A. Poston,
[107] J. Kim, G.V. Korshin, A.B. Velichenko, Water Res. 39 (2005) 2527–2534. A. Manivannan, P.N. Kumta, J. Mater. Chem. A 1 (2013) 4026–4037.
[108] W. Kong, B. Wang, H. Ma, L. Gu, J. Hazard. Mater. 137 (2006) 1532–1537. [160] C. Terrier, J.P. Chatelon, R. Berjoan, J.A. Roger, Thin Solid Films 263 (1995)
[109] I.H. Yeo, Y.S. Lee, S.I. Mho, D.C. Johnson, J. Electrochem. Soc. 139 (1992) 37–41.
L49–L50. [161] L.S. Andrade, R.C. Rocha-Filho, N. Bocchi, S.R. Biaggio, J. Iniesta, V. Garcia-
[110] L. Pinhedo, R. Pelegrini, R. Bertazzoli, A.J. Motheo, Appl. Catal. B: Environ. 57 Garcia, V. Montiel, J. Hazard. Mater. 153 (2008) 252–260.
(2005) 75–81. [162] G. Li, Y.-H. Wang, Q.-Y. Chen, J. Solid State Electrochem. 17 (2013) 1303–1309.
[111] X.Y. Li, C.W. Wang, Y. Qian, Y.J. Wang, L.W. Zhang, Sep. Purif. Technol. 107 [163] C.C.P. Cid, E.R. Spada, M.L. Sartorelli, Appl. Surf. Sci. 273 (2013) 603–606.
(2013) 281–288. [164] F. Armijo, I. Torres, R. Tapia, L. Molero, M. Antilen, R. del Rio, M.A. del Valle, G.
[112] L. Shao, P. He, J. Xue, G. Li, Water Sci. Technol. 53 (2006) 143–150. Ramirez, Electroanalysis 22 (2010) 2269–2276.
[113] H.X. Shi, J.H. Qu, A.M. Wang, J.T. Ge, Chemosphere 60 (2005) 326–333. [165] Y. Wang, Z.Y. Shen, Y. Li, J.F. Niu, Chemosphere 79 (2010) 987–996.
[114] N.V. Gelfond, N.B. Morozova, I.K. Igumenov, E.S. Filatov, S.A. Gromilov, Y.V. [166] K. Kadakia, M.K. Datta, P.H. Jampani, S.K. Park, P.N. Kumta, J. Power Sources
Shubin, R.I. Kvon, V.S. Danilovich, J. Struct. Chem. 51 (2010) 82–91. 222 (2013) 313–317.
[115] Y. Lee, H.-Y. Shin, S.H. Chun, J. Lee, W.J. Park, J.M. Baik, S. Yoon, M.H. Kim, J. [167] Y. Liu, H.L. Liu, J. Ma, X. Wang, Appl. Catal. B: Environ. 91 (2009) 284–299.
Phys. Chem. C 116 (2012) 16300–16304. [168] C. Borras, T. Laredo, B.R. Scharifker, Electrochim. Acta 48 (2003) 2775–2780.
[116] L.M. Da Silva, L.A. De Faria, J.F.C. Boodts, Electrochim. Acta 47 (2001) 395–403. [169] Q. Li, Q. Zhang, H. Cui, L. Ding, Z. Wei, J. Zhai, Chem. Eng. J. 228 (2013)
[117] G.R.P. Malpass, R.S. Neves, A.J. Motheo, Electrochim. Acta 52 (2006) 936–944. 806–814.
[118] C.P. Depauli, S. Trasatti, J. Electroanal. Chem. 396 (1995) 161–168. [170] S.-Y. Al, J.-Q. Li, L.-P. Li, H.-Q. Peng, Y. Yang, L.-T. Jin, Chin. J. Chem. 23 (2005)
[119] S. Ardizzone, G. Fregonara, S. Trasatti, Electrochim. Acta 35 (1990) 263–267. 71–75.
[120] Y.Q. Wang, B. Gu, W.L. Xu, L.D. Lu, Rare Metal Mater. Eng. 36 (2007) 874–878. [171] B.J. Hwang, K.L. Lee, J. Appl. Electrochem. 26 (1996) 153–159.
[121] Y. Chen, L. Dong, Y.S. Jin, B. Xu, W.J. Ji, Stud. Surf. Sci. Catal. 101 (1996) [172] M.H. Zhou, Q.Z. Dai, L.C. Lei, Z.C. Wu, C.A. Ma, D.H. Wang, Acta Phys. Chim. Sin.
1293–1302. 20 (2004) 871–876.
[122] J. Haber, T. Machej, E.M. Serwicka, I.E. Wachs, Catal. Lett. 32 (1995) 101–114. [173] M.H. Zhou, Q.Z. Dai, L.C. Lei, Proc. Int. Conf. Env. Sci. (2005) A1704–A1709.
[123] C. Deng, Front. Chem. China 3 (2008) 391–399. [174] M.H. Zhou, Q.Z. Dai, L.C. Lei, C. Ma, D.H. Wang, Environ. Sci. Technol. 39 (2005)
[124] H. An, Q. Li, D. Tao, H. Cui, X. Xu, L. Ding, L. Sun, J. Zhai, Appl. Surf. Sci. 258 363–370.
(2011) 218–224. [175] M.H. Zhou, Z.C. Wu, J. Zhu, Q. Ye, J. Fu, Chin. J. Catal. 23 (2002) 376–380.
[125] C.L.P.S. Zanta, P.A. Michaud, C. Comninellis, A.R. De Andrade, J.F.C. Boodts, J. [176] S.P. Tong, C.A. Ma, H. Feng, Electrochim. Acta 53 (2008) 3002–3006.
Appl. Electrochem. 33 (2003) 1211–1215. [177] X.P. Hong, R. Zhang, S.P. Tong, C.A. Ma, Chin. J. Chem. Eng. 19 (2011)
[126] H.S. Kong, H.Y. Lu, W.L. Zhang, H.B. Lin, W.M. Huang, J. Mater. Sci. 47 (2012) 1033–1038.
6709–6715. [178] I.E. Wachs, Catal. Today 100 (2005) 79–94.
[127] G.H. Zhao, X. Cui, M.C. Liu, P.Q. Li, Y.G. Zhang, T.C. Cao, H.X. Li, Y.Z. Lei, L. Liu, [179] F. Chen, S. Yu, X. Dong, S. Zhang, J. Hazard. Mater. 227–228 (2012) 474–479.
D.M. Li, Environ. Sci. Technol. 43 (2009) 1480–1486. [180] I.L. Chen, T.Y. Chen, C.C. Hu, C.H. Lee, J. Mater. Chem. A 1 (2013) 2039–2049.
[128] S. Chellammal, P. Kalaiselvi, P. Ganapathy, G. Subramanian, Arabian J. Chem. [181] M.E. Makgae, C.C. Theron, W.J. Przybylowicz, A.M. Crouch, Mater. Chem. Phys.
(2012) (in press). 92 (2005) 559–564.
[129] M. Tian, L. Bakovic, A. Chen, Electrochim. Acta 52 (2007) 6517–6524. [182] C.-P. Lo, G. Wang, A. Kumar, V. Ramani, Appl. Catal. B: Environ. 140–141 (2013)
[130] L.-Å. Näslund, C.M. Sánchez-Sánchez, Á.S. Ingason, J. Bäckström, E. Herrero, J. 133–140.
Rosen, S. Holmin, J. Phys. Chem. C 117 (2013) 6126–6135. [183] B. Adams, M. Tian, A. Chen, Electrochim. Acta 54 (2009) 1491–1498.
[131] P. Yao, Desalination 267 (2011) 170–174. [184] R.D. Coteiro, F.S. Teruel, J. Ribeiro, A.R. de Andrade, J. Braz. Chem. Soc. 17
[132] M.E. Makgae, M.J. Klink, A.M. Crouch, Appl. Catal. B: Environ. 84 (2008) (2006) 771–779.
659–666. [185] M. Yousefpour, A. shokuhy, Superlattices Microstruct. 51 (2012) 842–853.
[133] Q. Wang, T. Jin, Z. Hu, L. Zhou, M. Zhou, Sep. Purif. Technol. 102 (2013) [186] M.R. Mohammadi, D.J. Fray, Metall. Mater. Trans. A 42A (2011) 2481–2492.
180–186. [187] Y.-H. Cui, Y.-J. Feng, Z.-Q. Liu, Electrochim. Acta 54 (2009) 4903–4909.
[134] D. Devilliers, D. Mahé, Electrochim. Acta 55 (2010) 8207–8214. [188] T.A.F. Lassali, J.F.C. Boodts, L.O.S. Bulhoes, J. Appl. Electrochem. 30 (2000)
[135] S. Li, F. Wang, M. Xu, Y. Wang, W. Fang, Y. Hu, J. Electrochem. Soc. 160 (2013) 625–634.
E44–E48. [189] K.W. Kim, E.H. Lee, J.S. Kim, K.H. Shin, B.I. Jung, Electrochim. Acta 47 (2002)
[136] F.P. Hu, Z.Q. Dong, X.W. Cui, W.X. Chen, Electrochim. Acta 56 (2011) 2525–2531.
1576–1580. [190] C.A. Martinez-Huitle, S. Ferro, A. De Battisti, Electrochim. Acta 49 (2004)
[137] T. Wu, G.H. Zhao, Y.Z. Lei, P.Q. Li, J. Phys. Chem. C 115 (2011) 3888–3898. 4027–4034.
[138] S. Klamklang, H. Vergnes, F. Senocq, K. Pruksathorn, P. Duverneuil, S. Dam- [191] C.A. Martinez-Huitle, M.A. Quiroz, C. Comninellis, S. Ferro, A. De Battisti, Elec-
ronglerd, J. Appl. Electrochem. 40 (2009) 997–1004. trochim. Acta 50 (2004) 949–956.
[139] P. Duverneuil, F. Maury, N. Pebere, F. Senocq, H. Vergnes, Surf. Coat. Technol. [192] C. Comninellis, Electrochim. Acta 39 (1994) 1857–1862.
151 (2002) 9–13. [193] O. Scialdone, Electrochim. Acta 54 (2009) 6140–6147.
[140] C.H. Wang, S.W. Chen, J.M. Wu, C.N. Wei, H.Y. Bor, Electrochem. Solid-State [194] O. Scialdone, S. Randazzo, A. Galia, G. Silvestri, Water Res. 43 (2009)
Lett. 14 (2011) P5–P8. 2260–2272.
[141] B. CorreaLozano, C. Comninellis, A. DeBattisti, J. Appl. Electrochem. 27 (1997) [195] O. Scialdone, A. Galia, S. Randazzo, Chem. Eng. J. 174 (2011) 266–274.
970–974. [196] O. Scialdone, S. Randazzo, A. Galia, G. Filardo, Electrochim. Acta 54 (2009)
[142] X.M. Chen, F.R. Gao, G.H. Chen, J. Appl. Electrochem. 35 (2005) 185–191. 1210–1217.
[143] E.P. Domashevskaya, O.A. Chuvenkova, S.V. Ryabtsev, Y.A. Yurakov, V.M. [197] L. Xu, Z. Guo, L. Du, J. He, Electrochim. Acta 97 (2013) 150–159.
Kashkarov, A.V. Shchukarev, S.Y. Turishchev, Thin Solid Films 537 (2013) [198] C. Carlesi Jara, G.R. Salazar-Banda, R.S. Arratia, J.S. Campino, M.I. Aguilera,
137–144. Chem. Eng. J. 171 (2011) 1253–1262.
[144] R.J. Watts, M.S. Wyeth, D.D. Finn, A.L. Teel, J. Appl. Electrochem. 38 (2008) [199] N.B. Tahar, A. Savall, J. New Mater. Electrochem. Syst. 2 (1999) 19–26.
31–37. [200] Y.P. Lin, R.L. Valentine, Environ. Sci. Technol. 44 (2010) 3895–3900.
[145] M. Pechini, US Patent, 3.330.697 (1967). [201] Y.P. Lin, M.P. Washburn, R.L. Valentine, Environ. Sci. Technol. 42 (2008)
[146] T.C. Canevari, R.C.G. Vinhas, R. Landers, Y. Gushikem, Biosens. Bioelectron. 26 2919–2924.
(2011) 2402–2406. [202] D.J. Dryer, G.V. Korshin, Environ. Sci. Technol. 41 (2007) 5510–5514.
[147] X.H. Li, D. Pletcher, F.C. Walsh, Chem. Soc. Rev. 40 (2011) 3879–3894. [203] Y.P. Lin, R.L. Valentine, Environ. Sci. Technol. 42 (2008) 760–765.
[148] C. Tan, B. Xiang, Y. Li, J. Fang, M. Huang, Chem. Eng. J. 166 (2011) 15–21. [204] Z. Shi, A.T. Stone, Environ. Sci. Technol. 43 (2009) 3604–3611.
[149] K. Pan, M. Tian, Z.-H. Jiang, B. Kjartanson, A. Chen, Electrochim. Acta 60 (2012) [205] C. Bock, B. MacDougall, J. Electrochem. Soc. 146 (1999) 2925–2932.
147–153. [206] X.Y. Li, Y.H. Cui, Y.J. Feng, Z.M. Xie, J.D. Gu, Water Res. 39 (2005) 1972–1981.
[150] X.Q. Meng, J.Y. Yao, F.L. Liu, H.C. He, M. Zhou, P. Xiao, Y.H. Zhang, J. Alloys [207] R.L. Pelegrino, R.A. Di Iglia, C.G. Sanches, L.A. Avaca, R. Bertazzoli, J. Braz. Chem.
Compd. 552 (2013) 392–397. Soc. 13 (2002) 60–65.
[151] Y. Chen, L. Hong, H.M. Xue, W.Q. Han, L.J. Wang, X.Y. Sun, J.S. Li, J. Electroanal. [208] X.H. Mao, F. Tian, F.X. Gan, A. Lin, X.J. Zhang, Russ. J. Electrochem. 44 (2008)
Chem. 648 (2010) 119–127. 802–811.
[152] J.M. Macak, B.G. Gong, M. Hueppe, P. Schmuki, Adv. Mater. 19 (2007) [209] K. Juttner, U. Galla, H. Schmieder, Electrochim. Acta 45 (2000) 2575–2594.
3027. [210] L. Szpyrkowicz, C. Juzzolino, S.N. Kaul, S. Daniele, M.D. De Faveri, Ind. Eng.
[153] J.H. Pan, S.Y. Chai, C. Lee, S.E. Park, W.I. Lee, J. Phys. Chem. C 111 (2007) Chem. Res. 39 (2000) 3241–3248.
5582–5587. [211] S. Neodo, D. Rosestolato, S. Ferro, A. De Battisti, Electrochim. Acta 80 (2012)
[154] Y.D. Wang, T. Brezesinski, M. Antonietti, B. Smarsly, ACS Nano 3 (2009) 282–291.
1373–1378. [212] T. Raju, S.J. Chung, I.S. Moon, Korean J. Chem. Eng. 26 (2010) 1053–1057.
78 W. Wu et al. / Applied Catalysis A: General 480 (2014) 58–78

[213] J.C. Farmer, F.T. Wang, P.R. Lewis, L.J. Summers, J. Electrochem. Soc. 139 (1992) [239] N.B. Tahar, R. Abdelhedi, A. Savall, J. Appl. Electrochem. 39 (2009) 663–669.
3025–3029. [240] N.B. Tahar, A. Savall, Electrochim. Acta 54 (2009) 4809–4816.
[214] T.S. Chen, K.L. Huang, Y.C. Pan, Int. J. Electrochem. Sci. 7 (2012) 11191–11205. [241] D. Rajkumar, J.G. Kim, K. Palanivelu, Chem. Eng. Technol. 28 (2005) 98–105.
[215] P. Wardman, J. Phys. Chem. Ref. Data 18 (1989) 1637–1755. [242] K.L. Meaney, S. Omanovic, Mater. Chem. Phys. 105 (2007) 143–147.
[216] X.P. Wang, T.T. Lim, Appl. Catal. A: Gen. 399 (2011) 233–241. [243] R. Tolba, M. Tian, J.L. Wen, Z.H. Jiang, A.C. Chen, J. Electroanal. Chem. 649
[217] S.A. Cheng, W.K. Fung, K.Y. Chan, P.K. Shen, Chemosphere 52 (2003) (2010) 9–15.
1797–1805. [244] C. Borras, C. Berzoy, J. Mostany, J.C. Herrera, B.R. Scharifker, Appl. Catal. B:
[218] X.J. Yu, H. Wang, D.Z. Sun, L.W. Song, L. Wu, J. Environ. Sci. China 18 (2006) Environ. 72 (2007) 98–104.
33–39. [245] P. Canizares, R. Paz, J. Lobato, C. Saez, M.A. Rodrigo, J. Hazard. Mater. 138
[219] C. Tai, J.F. Peng, J.F. Liu, G.B. Jiang, H. Zou, Anal. Chim. Acta 527 (2004) 73–80. (2006) 173–181.
[220] J.X. Gao, G.H. Zhao, M.C. Liu, D.M. Li, J. Phys. Chem. A 113 (2009) 10466–10473. [246] G. Perez, A.R. Fernandez-Alba, A.M. Urtiaga, I. Ortiz, Water Res. 44 (2010)
[221] D. Wu, M. Liu, D.M. Dong, X.L. Zhou, Microchem J. 85 (2007) 250–256. 2763–2772.
[222] C. Feng, N. Sugiura, S. Shimada, T. Maekawa, J. Hazard. Mater. 103 (2003) [247] B. Marselli, J. Garcia-Gomez, P.A. Michaud, M.A. Rodrigo, C. Comninellis, J.
65–78. Electrochem. Soc. 150 (2003) D79–D83.
[223] K. Ishibashi, A. Fujishima, T. Watanabe, K. Hashimoto, J. Photochem. Photobiol. [248] C.C. Jara, D. Fino, Chem. Eng. J. 160 (2010) 497–502.
A 134 (2000) 139–142. [249] H.S. Awad, N.A. Galwa, Chemosphere 61 (2005) 1327–1335.
[224] K. Ishibashi, A. Fujishima, T. Watanabe, K. Hashimoto, Electrochem. Commun. [250] A. Sakalis, K. Mpoulmpasakos, U. Nickel, K. Fytianos, A. Voulgaropoulos, Chem.
2 (2000) 207–210. Eng. J. 111 (2005) 63–70.
[225] J. Yu, Y. Wang, W. Xiao, J. Mater. Chem. A 1 (2013) 10727. [251] M.H. Zhou, H. Sarkka, M. Sillanpaa, Sep. Purif. Technol. 78 (2011) 290–297.
[226] C.A. Cohn, S.R. Simon, M.A.A. Schoonen, Part Fibre Toxicol. 5 (2008). [252] C. Comninellis, A. Nerini, J. Appl. Electrochem. 25 (1995) 23–28.
[227] C.E. Diaz-Uribe, M.C. Daza, F. Martinez, E.A. Paez-Mozo, C.L.B. Guedes, E. Di [253] J. Radjenouic, A. Bagastyo, R.A. Rozendal, Y. Mu, J. Keller, K. Rabaey, Water
Mauro, J. Photochem. Photobiol. A 215 (2010) 172–178. Res. 45 (2011) 1579–1586.
[228] Y. Nosaka, M. Nakamura, T. Hirakawa, Phys. Chem. Chem. Phys. 4 (2002) [254] M. Gotsi, N. Kalogerakis, E. Psillakis, P. Samaras, D. Mantzavinos, Water Res.
1088–1092. 39 (2005) 4177–4187.
[229] C.D. Georgiou, I. Papapostolou, K. Grintzalis, Nat. Protoc. 3 (2008) 1679–1692. [255] D. Vasudevan, S.S. Vaghela, G. Ramachandraiah, J. Appl. Electrochem. 30
[230] K. Kosaka, H. Yamada, S. Matsui, S. Echigo, K. Shishida, Environ. Sci. Technol. (2000) 1299–1302.
32 (1998) 3821–3824. [256] X. Chen, G. Chen, P.L. Yue, Chem. Eng. Sci. 58 (2003) 995–1001.
[231] W.H. Koppenol, J.F. Liebman, J. Phys. Chem.: US 88 (1984) 99–101. [257] Y. Chu, D. Zhang, L. Liu, Y. Qian, L. Li, J. Hazard. Mater. 252–253C (2013)
[232] X.M. Li, M. Wang, Z.K. Jiao, Z.Y. Chen, Zhongguo Jishui Paishui/China Water 306–312.
Wastewater 17 (2001) 14. [258] F. Feki, F. Aloui, M. Feki, S. Sayadi, Chemosphere 75 (2009) 256–260.
[233] E. Turro, A. Giannis, R. Cossu, E. Gidarakos, D. Mantzavinos, A. Katsaounis, J. [259] Y.G. Adewuyi, Environ. Sci. Technol. 39 (2005) 3409–3420.
Hazard. Mater. 190 (2011) 460–465. [260] M.A. Oturan, I. Sires, N. Oturan, S. Perocheau, J.L. Laborde, S. Trevin, J. Elec-
[234] B. Wang, W. Kong, H. Ma, J. Hazard. Mater. 146 (2007) 295–301. troanal. Chem. 624 (2008) 329–332.
[235] P. Asaithambi, L. Garlanka, N. Anantharaman, M. Matheswaran, Sep. Sci. Tech- [261] C.M. Fan, B. Hua, Y. Wang, Z.H. Liang, X.G. Hao, S.B. Liu, Y.P. Sun, Desalination
nol. 47 (2012) 470–481. 249 (2009) 736–741.
[236] M. Panizza, G. Cerisola, Environ. Sci. Technol. 38 (2004) 5470–5475. [262] L. Xu, L.C. Zhang, L.S. Du, S.X. Zhang, J. Membr. Sci. 452 (2014) 1–10.
[237] Y. Shiraishi, R. Miyarnoto, T. Hirai, Langmuir 24 (2008) 4273–4279.
[238] Y. Samet, S.C. Elaoud, S. Ammar, R. Abdelhedi, J. Hazard. Mater. 138 (2006)
614–619.