Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375

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TiO2 modification by gold (Au) for photocatalytic hydrogen

(H2) production
Bhavana Gupta a,n, Ambrose A. Melvin b,nn, Tom Matthews a, S. Dash a, A.K. Tyagi a
a
Surface and Nanoscience Division, Materials Science Group, Indira Gandhi Centre of Atomic Research, Kalpakkam, Tamil Nadu 603102, India
b
Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha, Pune 411008, India

art ic l e i nf o a b s t r a c t

Article history: TiO2 is indeed one of the widely used semiconductors employed for photocatalytic hydrogen production.
Received 28 January 2014 Most of its photocatalytic activity is achieved in its crystalline form. However, its photocatalytic activity is
Received in revised form limited to ultraviolet region. For making TiO2 visible light active; Au deposition is strongly recommended
22 November 2015
due to its surface plasmon feature. Au deposition enhances the photocatalytic activity of both crystalline
Accepted 24 December 2015
and nanocrystalline TiO2. Efficiency of photocatalytic activity is controlled by shape and size of Au
nanoparticle subsequently the synthetic methodology plays an important role.
Keywords: Herein, we furnish a brief description of TiO2–Au nanocomposite synthesis by different methods viz.
TiO2 sol–gel, photodeposition, deposition–precipitation simple reducing method and dispersion method. A
Photocatalysis
discussion on physical properties of the resultant material is also provided. Three different types of
Hydrogen generation
mechanism has been described depending on the type of irradiation and form of TiO2 (crystalline and
Nanocomposite
Gold nanoparticle nanocrytalline). A comparative hydrogen production yield is also tabulated to get an idea about the best
synthesis methodology and form of TiO2 for efficient photocatalysis.
& 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1367
2. Background of the content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1367
2.1. Photocatalytic H2 production using TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1367
2.2. Effect of metal on photocatalytic H2 production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368
2.3. Properties of Au nanoparticles (Au NPs). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1368
3. Synthesis of TiO2–Au nanocomposite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1369
3.1. Chemical reduction method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1369
3.2. Sonochemical reduction method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1369
3.3. Dispersion method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
3.4. Photochemical deposition method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
3.5. Deposition–precipitation method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1370
3.6. Sol–gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
4. Photocatalytic hydrogen production under different irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
4.1. TiO2–Au activity in visible light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
4.1.1. Electric near field effect mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1371
4.1.2. Electron transfer (Au to TiO2) mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
4.2. Activity in UV and UV–vis region . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1372
4.3. Other phenomenon during photocatalytic H2 generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1373
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374

 Corresponding author. Tel.: þ 91 44 27480500x22171.

nn
Co-corresponding author.
E-mail addresses: bgupta1206@[Link], bhavanag@[Link] (B. Gupta), ashwinmelvin08@[Link] (A.A. Melvin).

[Link]
1364-0321/& 2016 Elsevier Ltd. All rights reserved.
 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375 1367

Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1374

1. Introduction synthesized by different synthetic methodology. Also, role of Au

under different type of light irradiation and TiO2 is elaborated.
Hydrogen is one of the ideal fuels for future as it can be pro-
duced by utilizing natural and renewable sources such as water
and solar energy. The cost effectiveness of renewable H2 produc- 2. Background of the content
tion is poor in comparison to the electrolyticaly produced H2.
Moreover, major part of H2 also comes from the fossil fuel [1]. Thus As it is mentioned that TiO2 is the most preferred material for
there is a huge scope for further development in the field of H2 photocatalytic water splitting. Possible equation of water splitting is
generation using natural resources. Photovoltaics and water elec- described based on TiO2 in the following section. Subsequently the
trolysis are becoming more competitive day by day with the price effect of Au deposition with reference to other metals is also ela-
reduction and improvement in the device technology. Alternative borated for better understanding. The synthetic strategy adopted
to all the existing possibilities, photocatalytic water-splitting using for TiO2:Au nanocomposite formation is explained as it is very
TiO2 for hydrogen production offers a promising way for realizing crucial because it affects the resultant physical property as well as
clean, low-cost and environmentally friendly production of hydrogen production efficiency. Furthermore, comparative hydro-
hydrogen by use of solar energy [2]. gen production yield is mentioned with respect to the existing
Honda and Fujishima, pioneers in photocatalytic generation of mechanism and to justify its synthetic methodology. Also role of
H2, investigated photo-electrochemical H2 generation through use TiO2:Au interface under different types of irradiation and versatile
of TiO2 electrode [3]. Latter revolutionary works were carried out TiO2 nanostructures is elaborated. Finally, a conclusion is drawn
in the field of photocatalysis by various leading research groups stating the best TiO2:Au nanocomposite in photocatalytic hydrogen
[4–7]. Significant part of this endeavor is dedicated to air/water production, its current challenges and possibility to overcome.
purification [8–11]. However, small fraction of this effort was
directed towards H2 generation [12,13]. 2.1. Photocatalytic H2 production using TiO2
Initial step of both the activities is the same i.e. absorption of
light by the semiconductor, where, the charge carriers participat- Separation between conduction band (CB) and valence band
ing in the surface reaction are different [14–16]. In photocatalytic (CB) or band gap in the range of electromagnetic radiation is the
H2 generation, conduction band electron participates in the H2O key factor responsible for photocatalytic hydrogen production
reduction process, whereas valence band holes are the key com- using a semiconductor. Band gap of TiO2 is 3.2 eV which is suitable
ponent that participates in the destruction of organic and other only for UV-radiation absorption which accounts for  4% of the
surface contaminant [17–19], as shown in Fig. 1. total solar light. After irradiation of TiO2, electron from the VB gets
Various types of semiconductor materials have been tried for excited to the CB, where it participates with the reactant present
the above purpose viz. TiO2, CdS, Cu2O and Co3O4 [20–23]. These on the semiconductor surface in the adsorbed form without
catalysts possess high absorption co-efficient, but the efficiency of showing any photocorrosion, while the hole remaining in the VB
H2 generation is low due to unwanted dissipation of energy in participate in the oxidation of adsorbed species as shown in Fig. 1.
form of electron–hole (e  –h þ ) recombination that drastically Thus photocatalytic reaction either oxidation or reduction can be
reduces light utilization efficiency [24–28]. In order to achieve catalyzed more effectively by reducing the dimension of the TiO2. In
industrial acceptance, certain aspects like cost effectiveness and connection with photocatalytic H2 production, TiO2 CB level is more
negative than H2 production level (ξH2/H2O) while the VB is more
facile synthesis of TiO2 should be on top of the priority list [27–29].
positive than water oxidation level (ξO2/H2O) for efficient hydrogen
Nevertheless, to reduce the energy dissipation; excited electron
and oxygen production from water by photocatalysis [33].
lifetime is to be increased. Hence, for increasing the electron
It was found that H2 production rate is much higher in case of
lifetime certain moiety need to be incorporated with TiO2 [30,31].
water–alcohol mixture, particularly water–methanol mixture. It
Plasmonic metals are widely adopted due to its profound activity
has been reported that in the absence of alcohol photocatalysis
in visible region. This then tends to active TiO2 in visible light
based on TiO2 remains very small even after the deposition of
irradiation and increase the efficiency in UV–vis irradiation [32]. In
nobel metal. In addition to that, in the absence of alcohol, surface
this review article we are describing about TiO2:Au nanocomposite
of the noble metal does get poisoned after few cycles due to the
strong adsorption of oxygen species and finally bringing about
H2 various side reactions based on the formation of O2 by oxidation
process. In presence of alcohol, such kinds of side reaction get
-
e H2 suppressed due to alcohol reforming process in which alcohol
work as a sacrificial agent. The life time of the catalyst is conse-
TiO2 quently enhanced. The alcohol consumption takes place by two
distinct process: (1) alcohol reformation where hole combine with
+ the alcohol to give H2 and CO2 and (2) O2 scavenging leading to the
h
formation of H2O and CO2 [34]
H2O
CH3OH þ3/2O2-CO2 þ2H2O (1)
O2
Amount of O2 and CO2 evolved are constant and non-negligible
Fig. 1. Bifunctional photocatalytic property of TiO2. which gives a hypothesis that all O2 produced after water splitting
1368 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375

is not scavenged by alcohol. Presence of O2 in the exhaust gas also Rh3 þ þ 3e  ⇄Rh E° ¼0.758 V—————————————————————
gives an indication of water splitting and hole consumption by (7)
water instead of alcohol that ultimately causes formation of O2
Ag þ þe  ⇄Ag E° ¼0.7996V——————————————————————
H2Oþ 2h þ -2H þ þO2 (2) (8)

Thus the overall H2 production can be represented by the fol- Pd2 þ þ 2e  ⇄Pd E° ¼0.951 V—————————————————————
lowing surface reaction: (9)

CH3OHþ H2O-CO2 þ 3H2 (3) [AuCl4]  þ3e  ⇄Auþ 4Cl  E° ¼1.002 V———————————————
(10)
It is well known that TiO2 is one of the most efficient photo-
catalyst in terms of stability and photoconversion efficiency It is generally inferred that metal with high work function
amongst various other semiconductor materials. But it has some helps in enhancing the Schottky barrier effect, which in turn
drawbacks which opens up multiple directions for research in TiO2 suppresses e  –h þ recombination. Usually metal after deposition
based photocatlysis as mentioned below: on semiconductor surface exhibits movement of Fermi level
towards more negative direction, which is a key factor for
1. Rate of recombination in case of excited charge is very high and increasing Schottky barrier or efficiency of charge-transfer [38].
is released in form of heat. After light irradiation followed by electron transfer (TiO2 to M),
2. An absorption response of TiO2 to the electromagnetic radiation Fermi level shift become more pronounced to facilitate further
is very small and is one of the key factors for the low efficiency. electron transfer as shown in Fig. 2. As we know, shift in fermi
3. The chance of backward reaction is also possible i.e. combina- level further depends on work function of a metal. Thus, a metal
tion of H2 and O2. with high work function is more suitable for photocatalytic H2
production. Work functions of Ag, Cu, Rh, Au and Pd are 4.26, 4.65,
To improve the photocatalytic property of TiO2, certain mod- 4.98, 5.1 and 5.12 eV, respectively. This ascending order is also
ifications are required to be done in electron donor or electron observed for photocatalytic activity [39]. Amongst various nano-
acceptor energy level. Electron donor falls in the category of che- metals, Au shows comparatively high photocatalytic activity under
mical additive; however, second one belongs to catalyst mod- visible light due to its distinguishing features as mentioned in the
ification. In terms of electron acceptor, modification is made by following section.
introducing a noble metal, metal ion doping, anion doping, dye
sensitization, composite semiconductors, metal ion-implantation 2.3. Properties of Au nanoparticles (Au NPs)
etc. Amongst the above mentioned techniques, noble metal load-
ing and dye sensitization are useful in photocatalytic H2 genera- Au in the bulk form is inert and does not exhibit significant
tion. There are many reports which deals with the metal i.e. Pt reactivity. In contrast Au NP shows very promising catalytic
deposition over semiconductor which forms p–n junction with the activity in specific reference to the oxidation of carbon monoxide.
semiconductor (photocatalyst) and work as an electron sink, thus Highly disperse Au NPs are very difficult to achieve. Melting point
averting recombination process. However, high cost of Pt reduces of Au (1063 °C) is considerably lower than that of Pt (1769 °C) and
the applicability of such a catalyst. Au NPs are comparatively Pd (1550 °C) [40–42]. One interesting point to note is that Au NPs
cheaper to Pt and due to the inherent plasmonic oscillation; it with a diameter of 2 nm exhibit a drastically reduced melting
absorbs in visible region as well acts as an electron trap. This point of 300 °C due to quantization effect [42,43].
process reduces the e  –h þ recombination. Here, we will discuss Free space of face centered cubic lattice of Au is composed of
about TiO2 modification by metal nanoparticle with special three low index planes i.e. (110), (100) and (111). Amongst them,
emphasis on Au. (100) and (111) have lower surface energy compared to (110),
which generally supports the stability of the system. Schematics of
2.2. Effect of metal on photocatalytic H2 production the Au (100) (110) and (111) planes are shown in Fig. 3.
Change in physical properties while going from bulk to nano-
It is reported that the photochemical reduction depends on gold is described on the basis of solid state chemistry. The
metal ion reduction potential and the location of conduction band
level of semiconductor. For a feasible reduction process, conduc-
tion level should be comparatively more negative to that of
reduction potential of the metal ion. Since the energy level of a
semiconductor depends on pH of the medium, the feasibility of
reduction of different metals becomes dependent on the pH of the
electrolyte medium [35–37]. It was reported that at pH ¼7,
reduction is feasible in case of transition metal like Ni, Cu, Ag, Au
and Pd (reduction potentials are mentioned in the following
equations). However, the H2 production is enhanced only in case
of Pt, Pd, Au and Rh along with the reduction process.

Zn2 þ þ2e  ⇄Zn E°

¼  0.7618 V—————————————————————————————
(4)

Ni2 þ þ2e  ⇄Ni E° ¼  0.257 V————————————————————

(5)

Cu þ 2 þ2e  ⇄Cu E° ¼0.3419 V————————————————————

(6) Fig. 2. Fermi level equilibrium at TiO2–metal interface.
 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375 1369

Fig. 3. Schematic of the Au planes (100) (left), (111) (middle) and (110) (right).

reconstruction of (111) plane is only possible under ultra high 3.1. Chemical reduction method
vaccum (UHV) conditions. The structure obtained by reconstruc-
tion is composed of face-centered cubic and closed-packed hex- Reduction method is one of the simplest methods of Au NP
agonal structures, in which 23 atoms are arranged in a space that deposition/adsorption over TiO2 surface. In terms of Au nano-
is suitable for typically 22 atoms, thus surface energy of the system particle decoration, this technique is highly preferred for its
is lowered by squeezing in more atoms [44]. For a 2 nm size Au availability as well established procedures for the preparation of
particle the Au (110) planes can also be modified in UHV condition colloidal suspensions in water and other solvents. Turkevich
to form Au (111) plane in which 60% of the atoms are present over method [50] and Brust method [51] are well known methods for
the surface. Smaller particle is having comparatively higher energy the synthesis of Au nanoparticles of  5 nm size with narrow size
because of preponderance by free surface where unsaturated co- distribution. It can be done either in the presence or absence of
ordination bonds in the form of dangling bonds are present. Those solid supports like TiO2, It is usually observed that during
states are energetically ahead of bulk Au. Decrease in particle size adsorption process, Au tends to agglomerate, forming Au islands of
causes the electrons to occupy the surface of the particle in free particle size well above 50 nm. In various photocatalytic processes,
unbound form. These unbound orbital or electron plays a crucial the activity of such catalyst is diminished due to reduced surface
role in the manifestation of physical property of the particle as it area and weak interaction with support.
traverses from bulk to nanoscale. As the particle size is diminished, Naldoni et al. synthesized Au:TiO2 nanocomposite and studied
band overlapping of valence electron also diminishes thus repla- these by optical, morphological and structural characterizations.
cing it in the form of discrete energy level characteristics akin to TiO2:Au typically shows absorption at 549 nm attributed to the
molecular orbit. Outcome of this phenomenon unfolds in the form SPR effect without altering the band gap of pure TiO2 [52]. It is also
of decrease in conductivity and appearance of Mie plasmonic observed that reduction procedure of metal nanoparticle does not
resonance as observed in case of Au55 and other smaller clusters. affect the morphology of TiO2. XPS investigation on Au:TiO2
This phenomenon is not only dependent on particle size but is also nanocomposite did not reveal any spectral alteration even after
influenced by the surrounding temperature and dielectric con- sputtering with Ar þ ion for 1 h. This indicates the stability of TiO2
stant. At high temperature, metallic property is observed and vice- matrix supported Au NPs opposite to that of TiO2:Pt nanocompo-
versa [45]. site. However, the size of Au NPs is bigger than that of Pt cluster.
Incorporation of nano Au into TiO2 matrix for water splitting Chiarello et al. made Au:TiO2 composites and observed a 550 nm
reaction has been extensively studied as it enhances the efficiency SPR frequency which is about 20 nm more than that observed for
of the photocatalytic reaction and shifts the photo response pure Au nanoparticles. The alteration of electronic configuration of
towards the visible light regime due to surface plasmon resonance Au due to the interaction with TiO2 support causes such a shift
(SPR) [46,47]. Following section deals with the synthetic strategy [53,54]. Comparative experimental condition is reported in
adopted for the formation of TiO2:Au nanocompsite along with its Table 1. Chemical reduction of Au salt in TiO2 was also performed
resultant physical properties. when TiO2 is in the form of photonic crystal. The deposition of Au
is significantly responsible for tuning the photonic band gap and
subsequently hydrogen production [55].

3. Synthesis of TiO2–Au nanocomposite

3.2. Sonochemical reduction method
In heterogeneous catalysis, influence of different parameters
like particle size of catalyst and the support, percentage loading Sonochemical method for reduction is carried out in an ultra-
and interaction of the catalyst with the support does play a crucial sonication bath. This method is having an advantage as it is free
role. Furthermore, influence of the Au reduction procedure affects from post synthesis treatments like washing and drying. This also
the catalytic activity of the resulting TiO2 supported Au NPs. Effect enables deposition of metal nanoparticle on the support material
of particle size on catalytic activity was first reported by Haruta [56,57]. Organic species breaks up into smaller fragments during
and his group, and it was observed that the Au NPs exhibits sonolysis process. This then works as an initiator for metal salt
photoactivity only when the particle size is below 20 nm [48,49]. reduction. Muzukoshi et al. successfully immobilized different
Several reports described linear dependence of Au NPs size on metal nanoparticles on TiO2 surface by sonochemical method in
catalytic activity. The ratio of surface versus the total number of presence of polyethylene glycol monostearate at an input power of
atoms is significantly influenced by increase in particle size. All 200 W (6 W/cm2) in 5–60 min duration. Particle size estimated by
these parameters directly deal with synthesis procedure for TEM technique is around 14.3 nm which is comparatively higher
nanocomposite. In the following sub-sections various method to than Pt (2.1 nm) and Pd (3.6 nm) synthesized in similar manner
synthesize Au–TiO2 composites are described. [58].
1370 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375

3.3. Dispersion method Deposition on TiO2

Thermal treatment &
In terms of reproducibility and scaling up of this technique chemical reduction TiO -Au
- Au Au 2
would show distinct advantages. As, it is also free from any kind of AuCl3 Au (OH)x nanocomposite
HO O OH
by-product formation. Jose et al. prepared Au:TiO2 composite by
TiO2
solvated metal dispersion method. Where Au in butadiene is
added to TiO2 dispersion at high temperature under vacuum. After Fig. 4. Schematic representation of deposition–precipitation synthesis method of
completion of metal deposition, the as-synthesized materials are TiO2- composite.
further annealed at 200 °C for the removal of butadiene [59].
Authors made a comparative study on Au particle size by varying of Au NPs is slower than that of agglomeration process because
TiO2 type (anatase, rutile and P25). Particle size is smaller in case density of Au increase by varying the wt% of Au loading from 0.5 to
of TiO2 anatase and rutile than that of P25 with λmax located at 536 2 with this an increase in particle size from 11.3 to 25.3 nm occurs
and 560 nm. However, Au incorporation normally does not affect in case of TiO-AR50 [63]. Gomathisanker et al. studied the metal
band gap of any type of TiO2. Seh et al. described the synthesis of NPs deposition over TiO2 with the aid of simultaneous H2 gen-
non centro-symmetric janus Au:TiO2 nanocomposite. Synthesis eration using light intensity of 5.0 mW/cm2. Results reveal that,
was carried out using titanium diisopropoxide bis(acet- metal ion converted to metal NPs resulting in Fermi level shift
ylacetonate) in alcoholic–aqueous medium after dispersing towards more negative direction leading to Schottky energy bar-
Au50 nm (synthesized by Brust method in toluene:water medium) rier reduction. This barrier was found to be least in case of Pd
particle at pH 9–10 and room temperature [60]. Jenus to core–shell followed by Au and Rh with the same trend of work function [37].
morphology is controlled by just varying the concentration of TiO2 Confirmation of metal nanoparticle deposition came from
precursor from one to three times to that of the added Au salt absorption spectra in form of plasmonic absorption, however the
amount. Jenus shaped nanocomposite shows comparatively higher absorption of TiO2 always shows a red shift in presence of Au and
red shift in plasmonic absorption band than core–shell morphol- Pd. A. A. Melvin et al. studied the photocatalytic hydrogen pro-
ogy when compared with pure Au50 nm in isopropyl alcohol. High duction efficiency in both vis and UV–vis irradiation and found
refractive index of TiO2 causes this blue shift in Au absorption in that electron transfer from Au to TiO2 was feasible under both
core–shell morphology as in jenus shape some of the Au nano- irradiation. Although the catalyst did show a comparatively less
particles experience the effect of isopropyl-alcohol. activity in vis light [64].

3.4. Photochemical deposition method 3.5. Deposition–precipitation method

Besides adsorption of preformed Au colloids on to TiO2, an Deposition–precipitation method for the synthesis of Au:TiO2
alternative that has been widely used to prepare titania supported nanocomposite, has proven to be the most feasible method
Au NPs has been estabilized through photodeposition method. adapted to heterogeneous catalysis. This is because it retains very
This methodology is valid when the support is a semiconductor small Au nanoparticles with an average particle size of about 5 nm.
such as TiO2. Irradiation of the semiconductor with light of The size is very suitable as the catalytic activity is most pro-
appropriate wavelength produces the photogenerated electrons nounced [65,66]. This methodology starts with the aqueous solu-
and holes. These electrons can be used to reduce Au salt to Au tion of HAuCl4, brought to the required pH level and followed by
metal that will be simultaneously adsorbed on to the surface of the addition of TiO2 to this solution. Finally the resultant suspension is
semiconductor. A hole scavenger such as an alcohol need to be stirred continuously for a relatively longer time of 24 h at a con-
present as such to avoid accumulation of positive charge during stant pH. The resultant solid is collected by proper washing to
the photodeposition process. Deposition condition adopted by remove traces of Cl  ions. The crucial parameters involved in the
various research group is mentioned in Table 2. Chen et al. con- deposition–precipitation process which control the particle size of
solidated the synthesis of Au:TiO2 nanocomposite by photo- Au NP is the pH value of the deposition step [67–69]. The
chemical methods at 4.5 pH in 0.2 N salt solutions of Na2CO3. In deposition–precipitation method is a highly desirable technique
presence of TiO2, Au particle size does reduces from 20 nm to due to the reproducibility of the quality of product. Synthesis
3 nm. However, the corresponding SPR falls at 563 nm with red procedure for nanocomposite fabrication is shown in Fig. 4.
shift of 30 nm as compared to pure Au NPs [33]. Gartner et al. Catalysts made by this method are considered as “reference
synthesized Au NPs in TiO2 matrix using different metal salts. High catalysts” type A and is considered for commercialization by World
deposition is achieved by using NaAuCl4 (0.97 wt%) followed by Gold Council. In order to achieve high photocatalytic activity and
AuCl3 (0.96 wt%), AuCl (0.65 wt%) and [Au(PPh3)]Cl (almost 0). observe the influence of surface hydroxyl group, the acidic pH
Although the average particle size remain almost same (3–12 nm) state is highly favorable. Such a processing condition is amenable
in all these cases, in case of AuCl it was noted that there is some to size regulation of NPs through reducing surface titanol group.
dilution observed on TiO2 surface in terms of Au concentration Silva et al. synthesized TiO2 supported Au NPs by deposition pre-
[61]. A comparative photodeposition process was carried out by cipitation technique by varying pH (4.5, 6 and 9) and temperature
Bamwenda et al. in alcoholic–aqueous solution of Au and Pt salts. (200 and 400 °C). Particle size can easily be controlled by adjusting
Smaller particle size (1–8 nm) with narrow size distribution could the pH of the medium and heat treatment. Higher pH and tem-
be achieved in case of Pt as compared to Au (1–10 nm) [62]. perature causes agglomeration due to the sintering occurring at Au
Yuzawa et al. incorporated Au nanoparticle into TiO2 matrix by and TiO2 interface. Smallest particle is formed by heating the
photochemical reduction process using different grades of TiO2. composite at 200 °C with pH around 9. Agglomeration at higher
With 0.5 wt% of Au loading, NP size of 11.5 nm could be obtained. temperature is supported by absorption spectrum which reveals
This exhibited nearly similar absorption spectra in all the cases red shifting in the plasmonic absorption [70]. Rosseler et al. syn-
indicating the same shape and size of the NPs. In case of TiO2-R3, thesized TiO2 by sol–gel method using different porogen like
there is a peak splitting at 2 wt% Au loading and is explained as Polyethylene glycol (PEG), Polyoxyethylene (10) cetyl ether (Brij
due to the formation of rod shaped particles. Hence, from different 56), Polyvinyl alcohol (PVA) and (10) cetyl ether (Brij 56) and
findings, the author has concluded that the growth of Au NPs take hexadecyltrimethylammonium bromide (CTAB). Au loading was
place faster on TiO2 of low surface area. Furthermore, growth rate carried out by an ion exchange procedure using HAuCl4. Ammonia
 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375 1371

H2O different temperature. Heating was carried out to get different

degree of crytallinity to investigate hydrogen production rate but
- also excited photo-electron lifetime [74].
H2 e
Au 4. Photocatalytic hydrogen production under different
TiO 2 irradiation
Visible light
TiO2:Au based nanocomposite is opportune for photocatalytic
activity in both UV–vis as well as visible light irradiation. Under
+ different irradiation; site of excitation and redox reaction does
h +
varies. Following sub-section is formed according to the type of
A
irradiation i.e. visible and UV–visible.
A
Fig. 5. Induced electronic filed (green arrow) effect at TiO2:Au interface useful for
4.1. TiO2–Au activity in visible light
charge separation at TiO2 surface for water splitting. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of Two possible mechanism is described in the literature based on
this article.) Au:TiO2 composite activity in visible region. In the first mechanism
e  –h þ is separated at TiO2, however, second one deal with the
(35 vol%) was used for washing followed by calcinations at 300 °C electron transfer from Au to TiO2 due to the plasmonic effect of Au
for 4 h. Amongst all TiO2, TiO2 (Brij 56) posses highest surface area nanoparticle. The following subsection explains both mechanism
and least rutile phase content [34]. By changing wt% from 0.3 to based on the reports of various research group.
2 wt%, the particle size was found to increase form 3 nm to 8 nm in
all types of TiO2. Effect of Au on TiO2 is also maximum in case of 4.1.1. Electric near field effect mechanism
TiO2 (Brij 56) in terms of its band gap. In XPS studies, no change in Interaction between Au and Ag with a semiconductor leads to
Ti peak position could be detected even the deposition of Au NPs. the formation of e  /h þ pairs in the semiconductor as shown in
However, the peak related to oxygen in Ti-OH gets shifted towards Fig. 5. Charge carrier generation is created by coupling between
higher binding energy side amounting to  1 eV because of strong electromagnetic radiation and oscillation of electron in Au and Ag
interaction with Au. This happened due to strong ion-exchange of nanoparticle which causes strong-field enhancement more than
[Au (OH)4]  with TiOH. incident light. Thus a resonance happened wavelength of incident
light matches with the SPR band of Au or Ag in form of extra
3.6. Sol–gel method electron magnetic field to add up the light effect. Such enhanced
field is nonhomogeneous and found to be highest at the place in
This widely used technique adequately promotes chemical semiconductor where metal nanoparticle presence is nearest.
interaction between Au and TiO2. Oxy and hydroxyl bridges are Probability of e  /h þ pairs recombination is very less when its
formed between Au and TiO2 during the process of hydrolysis
resulting form biphasic gel structure. Cihler et al. adopted sol gel
H2
technique for the dispersion of Au in TiO2. Hydrolysis was carried
out using NH4OH followed by metal salt addition. A suspension of
TiO2 precursor and metal salt was reduced by the addition of D- H2O e- e- e-
glucose. This process involves post-synthesis calcinations at 600 °C
for 6 h. Due to mild reducing capability of D-glucose, the particle e- e- e- e-
size of NPs is very small in case of Pt (1.8 nm), Pd (2.1 nm) and Au
Visible light
(3.3 nm). Presence of metal nanoparticle favors the formation of irradiation >400 nm
anatase phase of TiO2 during calcinations with consequent +
reduction in surface area. This effect is most pronounced in case of h
Pt which has least effect in case of Au [71]. Fang et al. made Au:
TiO2 composite by using AuCl3 and TiCl4 in gelation, where the
gelating agent is a copolymer (pluoronic P123). Presence of
copolymer enhances the surface area of TiO2 twice to that of pure A
TiO2. Moreover, the deposition of Au reduces the active surface
area of TiO2 catalyst. Plasmonic absorption of TiO2–Au (590 nm) is
comparatively red shifted to that of pure Au (520–530 nm) [72]. +
A
XPS also supports interaction between TiO2 and Au by showing
some shift in Au binding energy towards higher value. Murdoch Fig. 6. Electron transfer from Au to TiO2 in Au:TiO2 nanocomposite.
et al. reported synthesis of TiO2–Au nanocomposite and studied its
effect of particle loading and size on the photocatalytic process Table 1
[73]. Particle size increases to 3–12 nm from 1–4 nm by varying Comparative salt reduction methods adopted for the synthesis of TiO2/Au nano-
the wt% of Au loading. Growth of smaller particles are more fea- composite by simple reduction method.
sible on high surface area anatase phase. Author also describes the
Precursor Medium Temp and Size of Au/ Ref.
effect of particle size on metal work function. Work function of Au time wt%
is highest in case of smallest NP with size  3 nm. An Au:TiO2
nanocomposite configuration with 3 nm size exhibit highest cat- TiO2(oxygen flowed) and Water Room temp, 3.6 nm/ [52]
alytic activity towards CO-CO2. Synthesis of TiO2–Au composite HAuCl4 þ NaBH4 10 min 1 wt%
P25 and HAuCl4 þNaBH4 (1:4) Water Room temp 3–8 nm/ [53]
in presence of SiO2 template is also used for making yolk–shell 1 wt%
morphology by etching of SiO2 by NaOH followed by annealing at
1372 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375

Table 2
Comparative photochemical methods adopted for the synthesis of TiO2/Au nanocomposite.

Precursor Medium Power and time Shape and size of Au Ref.

P25 þ HAuCl4 Na2CO3 aq. solution 100 W (Hg lamp)/1 h 3 nm [33]

TiO (A50, A300, R100, AR50, R3) HAuCl4 solution Water 300 W (Xenon lamp), 3 h 11.5 nm (lowest TiO-AR500 0.5 wt%) [37]
P25 þ NaAuCl4  2H2O, AuCl3 and AuCl MeOH/H2O (1:1) 2.4 W, t¼ 30 min 3–12 nm [60]
TiO2 þ HAuCI4  4H2O MeOH/H2O (1:1) 125 W (Hg lamp, 0.5–1 h) 1–10 nm [62]
TiO2 þ HAuCI4  4H2O MeOH/H2O (1:4) 400 W (medium pressure – [64]
Hg-vapour lamp), 30 min

H2 supporting the mechanism. Resulting hole on Au NP is trapped by

water and causes O2 evolution as confirmed from cyclic voltam-
1
metry which reveals a peak at  1.14 V that is comparatively lower
H 2O H2O
2
- - -
e e e e e e
- - - than 1.21 V (thermodynamic oxidation potential for O2 evolution).
Visible light CB Yzawa et al. made comparison between different TiO2 (A50, AR50,
irradiation >400 nm A300, R3, R100)–Au nanocomposites for photocatalytic H2 gen-
H2
eration. Some of the TiO2 show initial induction time due to
Enhancement in the requirement of initial reduction process prior to onset of photo-
absorption of TiO2 catalysis. All the categories of TiO2 show the effect of Au loading on
UV light
H2 evolution rate. In all the cases, it decreases with increase in Au
+ + + + loading. However R3 shows opposite trend due to the formation of
h h h h rod shaped Au NP. In terms of amount of H2 generation or rate of
VB
+ H2 evolution A50 is more efficient catalyst with same Au loading of
A 0.25 wt%. Thus it can be inferred that plasmonic absorption or
A absorbity is the main factor affecting H2 generation rate. H2 gen-
Fig. 7. Electron transfer from TiO2 to Au (1) and Au to TiO2 (2) in Au:TiO2
eration follow a similar trend to that of increasing anatase content
nanocomposite. as A504 AR50 4A300 4R3 4R100. A50 TiO2 although have the
least surface area, shows high activity due to larger particle size.
formation takes place at the surface of the semiconductor rather Certainly, reduction in the recombination rate is the reason [63].
than in the bulk. Apart from that the path length of charge carrier Melvin et al. studied the photocatalytic hydrogen production
is also small to participate in the photocatalytic transformations efficiency in both Vis and UV–vis irradiation and found that cat-
[72,75]. Seh et al. made a comparative study of jenus and core– alyst active (comparatively less) in Vis light [64] which support
shell morphology of TiO2–Au nanocomposite in photocatalytic H2 electron transfer from Au to TiO2.
generation process. Janus shaped morphology is more efficient for
H2 generation due to larger near field enhancement at TiO2:Au 4.2. Activity in UV and UV–vis region
interface, with larger particle size (70 nm) than smaller one
(30 nm) [59]. Best finding of the author is the efficient applicability In UV only one side electron transfer (from TiO2 to Au) is
of amorphous TiO2 with Au nanoparticle because of the availability possible, however, in case of UV–vis a two side (from TiO2 to Au
of discrete energy levels in the mobility gap which helps in the and Au to TiO2) electron transfer can occur [32] as shown in Fig. 7.
enhancement of plasmonic near field effect on TiO2 and reduces Researchers explain mechanism of nanocomposite activity by
the recombination rate drastically. either/or and both of the electron transfer pathway. Murdoch et al.
reports the effect of anatase and rutile phase on photocatalytic H2
4.1.2. Electron transfer (Au to TiO2) mechanism generation. In case of anatase phase, H2 generation increase with
Electron transfer from Au to TiO2 under light irradiation is also the increase in Au loading from 1–4 wt% (3–12 nm). However,
an important phenomenon. As it effectively utilizes sun light due beyond that i.e. at 8 wt% it decreases due to much larger size of Au
to strong plasmonic absorption of Au nanoparticle. However, there (26 nm) NP. Author suggested a mechanism based on ethoxide
is the formation of Schottky barrier at the metal–semiconductor formation on TiO2 followed by consumption of hole and formation
interface which does creates hindrances in electron movement, of OH species along with acetaldehyde. OH species consumes
thus becoming unfavorable for charge separation [76–78]. Recent electron and generates H2 in comparatively higher rate than that
report describes such electron transfer process by multiple observed for Pt and Pd at same loading [73]. Cihalar et al. com-
experimental evidences. It was found that Au nanoparticle work as pared Ti oxide–hydroxide and TiO2 nanocomposite with metal
a photo-sensitizer similarly like a dye molecule in dye sensitized nanoparticles for H2 generation and reported that TiO2 nano-
solar cell thus support the possibility of Au to TiO2 electron composite is more efficient for this purpose due to proper degra-
transfer [79] as shown in Fig. 6. Silva et al. made TiO2–Au nano- dation of organic species and OH groups from the surface during
composite at low and high pH condition and calcined these at 200 heat treatment process at 600 °C. Amongst, Pt, Pd and Au, Pt based
and 400 °C temperatures, respectively. In case of 200 °C annealed nanocomposite catalyst showed highest activity under UV–vis
TiO2–Au composite, catalytic activity is successively enhanced by irradiation. Further photocatalytic activity is enhanced by
increasing the pH. However, in case of 400 °C annealed material, increasing the light intensity. However, under visible light, its
results are in contrast. Thus, not only the particle size but also activity is comparatively poor [71]. Chen et al. confirmed in their
some other factor control the catalytic activity. In terms of stability, experiment that Au NP not only works as an electron sink during
400 °C annealed nanocomposite is photocatalytically more active photocatalysis but also provides active surface site for the reaction.
than the one calcined at 200 °C [70]. Photochemical O2 evolution Thus the effect of SPR is not much responsible for enhanced H2
also takes place on the same catalyst in the presence of Ag salt production vide UV–vis irradiation. Effect of different shape on
which works as an electron scavenging agent (transferred from Au photocatalytic activity is further justified by simulation studies
to TiO2) and is reduced on TiO2 surface under visible light, thus which state that half embedded nanoparticle is more efficient in
 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375 1373

Table 3
Comparative photocatlytic H2 production yield using TiO2/Au photocatalyst under different experimental condition.

Catalyst Radiation H2 evolved Photocatalytic medium Ref.

TiO2/Au (1 wt%)- 25 mg UV (2.4 W Xenon lamp) 8.4 μmol/mg h Water:methanol (1:1)-10 ml [33]
TiO2/Au (2 wt%) Vis (150 W metal halide lamp) 120 μmol/min Water:methanol (99:1)-100 ml [34]
TiO2/AuCl4  (0.25 wt%)- 20 mg UV (LED lamp) 4 μmol/h g 40 ml (16 wt% glucose) [37]
TiO2/Au (2 wt%)-10-25mg Sun light (0.3–0.4 mW/cm2) 400 mmol/h g Water:ethanol (120:1)-60 ml [55]
TiO2 /Au (1 wt%)- 255 mg Vis (450 W Hg Lamp) 6.9 μmol/h Water:methanol (18:1)-340 ml [58]
TiO2/Au (70 nm)-45 mg Vis (Hg lamp) 56.6 ml/h Water:isopropanol (4:1)- ml [59]
TiO2/Au (1 wt%)- 1.7 g/dm3 UV–vis (500 W Hg lamp) 0.207 μmol/h Water:methanol (0.4:1)-10 ml [60]
TiO2/Au (0.1 wt%)- 500 mg Vis (300 W xenon lamp) 20 μmol/ m2 g Water:ethanol (7:3)-100 ml [62]
TiO2/Au (1 wt%)-20 mg 300 W power UV–vis (100 mW cm  2) Vis (92 mW cm  2) 307 mmol/h g 66 mmol/h g Water:methanol (3:1)-40 ml [64]
TiO2/Au (1.5 wt%)-45 mg Vis (xenon doped Hg lamp) 0.96 ml/h Water:methanol (3:1)-100 ml [68]
TiO2/Au (2 wt%)- 10 mg UV–vis (300 W arc lamp) 195/h.g Water:methanol (8:2)-120 ml [69]
TiO2/Au (2 wt%)- 10 mg Vis (300 W xenon lamp) 7 μmol/h g 10 ml (0.1 mM-ascorbic acid) [70]
TiO2/Au (4 wt%)- 6–20 mg UV (90 W lamp) 1 μmol/m2 min Water:ethanol (7:3)-100 ml [71]

making the effect of plasmonic induced enhancement on absorp- control experiment to justify the existence of two mechanism i.e.
tion by TiO2 [33]. Bamwenda et al. first compared Pt and Au electron transfer from TiO2 to Au and vice versa. To see the effect of
composite followed by different technique used for the synthesis electron transfer from Au to TiO2 a comparison between TiO2–Au
of TiO2–Au nanocomposite and showed that Pt is more efficient and TiO2–Pt was made and found that photocatalytic activity is high
than Au in terms of H2/CO2 ratio. However, CO2/CH4 is higher in in case of TiO2–Au in comparison to TiO2–Pt under visible light
case of Au composites and amongst different technique of synthesis irradiation. Amongst TiO2, TiO2 derived from P123 and P25, Au
(photodeposition, deposition precipitation, imprementation and nanocomposite with P123 was more affected by plasmonic effect
simple mixing) photodeposition yield's highest H2 evolution rate. In due to sublevel present just below the conduction band due to
deposition–precipitation technique, the temperature used for defect. To justify the electron transfer from Au to TiO2 author stu-
reduction plays a crucial role in photocatalysis. Low temperature died the wavelength effect on photocatalytic activity and it was
synthesized materials are more active than high temperature syn- found that of 550 nm, H2 generation was less than that at 500 nm
thesized materials due to more amount of anatase phase [62]. irradiation. This is because maximum absorption distribution
Mizukoshi et al. describes photocatalytic H2 generation using TiO2– occurs at 500 nm. Rosseler et al. synthesized TiO2 by sol–gel
MNP (Pt, Pd and Au) nanocomposite with the same loading method using different porogen like Polyethylene glycol (PEG),
amounts and it was found that H2 generation is highest in case of Pt Polyoxyethylene (10) cety ether (Brij 56), Polyvinyl alcohol (PVA)
based nanocomposite followed by Pd and Au [58]. This difference and (10) cetyl ether (Brij 56) and hexadecyltrimethylammonium
could be due to difference in work function value and size of the bromide (CTAB). Au loading was carried out by an ion exchange
metal nanoparticle. Moreover the authors conclude that ultrasonic procedure using HAuCl4. Ammonia (35 vol%) was used for washing
method for metal deposition is better in terms of photocatalysis followed by calcinations at 300 °C for 4 h. Amongst all TiO2, TiO2
than simple impregnation method due to uniform dispersity and (Brij 56) possess highest surface area and least rutile phase content
strong metal support interaction obtained. Naldoni et al. described [34]. By changing wt% from 0.3 to 2 wt%, the particle size was found
the effect of Au and Pt loading on TiO2 on H2 and CO2 generations to increase form 3 nm to 8 nm in all types of TiO2. Effect of Au on
and it was reported that both of the products formed in higher TiO2 is also maximum in case of TiO2 (Brij 56) in terms of its band
amounts in case of Pt nanocomposite for Au. In all these studies, gap. In XPS studies, no change in Ti peak position could be detected
TiO2 treated with NaBH4 was considered as a reference. The effi- even the deposition of Au NPs. However, the peak related to oxygen
ciency of different catalysts is further proved by ESR technique by in Ti-OH gets shifted towards higher binding energy side amounting
monitoring the signal of O  and O2 formed by hole and electron to  1 eV because of strong interaction with Au. This happened due
trapping by O2 and O2: . Signal of O  is highest in case of Pt than Au to strong ion-exchange of [Au(OH)4]- with TiOH. Gomathisankar
nanocomposite due to smaller size. However O2 signal is weak in et al. found positive effect of glucose concentration in the medium
Pt under either vacuum or O2 saturated solution with UV–vis irra- both in the case of Pd (comparatively more) and Au for H2 evolution
diation. O2 signal also does not get enhanced in typical visible light rate. However, by increasing metal salt concentration, H2 evolution
irradiation condition which indicates that SPR absorption does not rate decreases due to light filteration by NPs. Also the blockage is
contribute to its activation in case of TiO2–Au nanocomposites [52]. increased by particle over TiO2 surface. Increase activity from
Effect of metal loading in case of Au is varied from 1–2 wt%. How- TiO2 oTiO2–AuoTiO2–Pd is due to decreasing band gap trend [37].
ever in case of Pt it is in the range of 0.3–1 wt%. There is no effect of Mechanism is based on the hole consumption by glucose. However,
surface area on the photocatalytic activity as seen in the case of Pt. electron gets consumed by water molecule to form CO2 and H2.
This is opposite to the case of Au, where changing Au wt% changes
size of Au nanoparticle drastically. Comparative hydrogen produc- 4.3. Other phenomenon during photocatalytic H2 generation
tion (reported by different research group) along with reaction
parameter is given in Table 3. Photocatalysis is more active in the Chiarello et al. studied the evolution rate of different compo-
pH range 4–7 and least in the case of basic media. Gartner et al. nents during photocatalytic process and fitted it for three
described the effect of different metal salt of Au and sacrificial mechanism i.e. direct path (hole consumption by methanol),
agents on photocatalytic activity towards H2 generation. It was indirect path (hole consumption by OH) and lastly water assisted
found that NaAuCl4  2H2O and methanol combination is most effi- path (hole-methanol interaction in bulk water medium) for Pt
cient amongst AuCl3, AuCl, and Au[(PPh3)]Cl as salts, whereas, gly- (0.5)/TiO2 and Au (1)/TiO2 nanocomposite. In both the composites,
cerin, iprOH, glucose and methanol as sacrificial agents [61]. Further formic acid and formaldehyde first increased and then decreased
isotopic studies reveals that methanol reforming is not a rate with the increase in methanol content in the mixture. However,
determining step, the water reduction process is affected by deu- CO2 concentration continuously decreased [53]. This states that
teration of methanol (–CH3) hydrogen. Fang et al. carried out several high methanol concentration mechanistically supports indirect
1374 B. Gupta et al. / Renewable and Sustainable Energy Reviews 58 (2016) 1366–1375

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