Structure and catalytic

[Link]/journal/rsos
behaviour of CuO – CeO2
prepared by high-energy
Research ball milling
Cite this article: The Luong N, Okumura H, Yamasue
E, Ishihara KN. 2019 Structure and catalytic behaviour Nguyen The Luong†, Hideyuki Okumura, Eiji Yamasue
of CuO –CeO2 prepared by high-energy ball milling.
Downloaded from [Link] on 26 May 2022

R. Soc. open sci. 6: 181861. and Keiichi N. Ishihara

[Link] Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto
University, Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
Received: 5 November 2018
Accepted: 14 January 2019 NT, 0000-0003-3939-8266

Subject Category: The aim of this study is to prepare CuO–CeO2 composite

Chemistry by means of mechanical milling and to investigate its
characteristics as a catalyst. The structural and morphological
Subject Areas:
features of milled samples are observed by X-ray
environmental chemistry/chemical engineering/
diffractometry and scanning electron microscopy. The redox
materials science property and total OSC (oxygen storage capacity) of the milled
Keywords: sample were measured by using GC-TCD and TG-DTA, which
are important parameters to indicate the effectiveness of
CeO2, CuO, ZrO2, H2-temperature-programmed
catalysts. Interestingly, reduction of CuO is repeatedly
reduction, oxygen storage capacity
observed when milling of CuO–CeO2 powder mixture is
Author for correspondence: processed in air. The redox property of milled CuO–CeO2
Nguyen The Luong sample is investigated by H2-TPR, where three reduction
e-mail: [Link]@[Link] peaks are observed for 0 h milling and only one broad peak
for various other milling times. The total OSC of mechanically
driven CuO–CeO2 catalyst is much higher than that of the
†
Present address: The Department of Internal CeO2 –ZrO2 traditional catalyst system at low temperatures.
Combustion Engine, School of Transportation
Engineering, Hanoi University of Science and
Technology, No.1 Dai Co Viet street, Hanoi, Vietnam.

This article has been edited by the Royal Society of

1. Introduction
Chemistry, including the commissioning, peer review Nowadays, more than 95% of vehicles produced are equipped with
process and editorial aspects up to the point of a catalytic converter [1]. The three-way catalysts (TWCs), used
acceptance. for the gasoline-fuelled engine are capable of simultaneously
converting CO, hydrocarbon (HC) and NOx, with a stoichiometric
Electronic supplementary material is available online at air-to-fuel ratio (A/F ¼ 14.7), into harmless CO2, H2O and N2 [1].
[Link] Oxygen storage capacity (OSC) is one of the crucial factors for the
performance of TWCs. The CeO2 –ZrO2 composite is well known
as an excellent promoter of OSC, where CeO2 exhibits the oxygen
storage/release behaviour by redox variation of Ce ions between
Ce3þ and Ce4þ, while the introduction of ZrO2 into CeO2
improves the reduction temperature of ceria through structural
modification of the ceria lattice [2], although the OSCs at low

& 2019 The Authors. Published by the Royal Society under the terms of the Creative
Commons Attribution License [Link] which permits
unrestricted use, provided the original author and source are credited.
 temperatures are still not high [1]. Many studies on CeO2-based materials have been reported, such as 2
CeO2 –Al2O3 [3], CeO2 –SiO2 [4], CeO2 –La2O3 [3,5,6], CeO2 –TbOx [7], CeO2 –PrOx [8] and CeO2 –MOx

[Link]/journal/rsos
(M: Zr, Ti, Cu) [9,10], to improve the OSC and increase the thermal stability.
As legislation becomes tighter, it is necessary to improve the efficiency of TWCs at low temperatures
under an oxygen-rich atmosphere. The copper/copper oxides are known to exhibit oxygen storage/
release behaviour at low temperatures, although it causes fragmentation due to the large volume change
[11]. Then, various metal oxides without large volume change, such as CuMO2 (M ¼ Al, Fe, Mn, Ga),
have been investigated to reduce fragmentation [11], where the reduction of Cu2þ to Cu is studied by the
H2-TPR (temperature-programmed reduction) and the OSC is improved at lower temperatures.
It is known that CuO–CeO2 mixed oxides exhibit high levels of oxidation of carbon monoxide and
hydrocarbon [12– 15], SO2 reduction by CO [16– 18], NO reduction [19] and phenol oxidation [20 –22].
It has also been shown that the redox properties and catalytic performance strongly depend on the
preparation methods, such as sol– gel [23], hydrothermal routes [24,25], precipitation method [26],
reverse micelle [27], sonochemical [28], chemical vapour deposition [29], flux method [30], micro-wave

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

heating [31] and surfactant-assisted method [32]. The preparation condition and the mixed-oxide
composition influence the phase, morphology and distribution of copper species on ceria. The
enhanced catalytic activity results from interactions among the copper –cerium oxide phases.
Mechanical milling has long been used to prepare non-equilibrium materials, solid solutions and other
metastable phases and also to drive mechanochemical reactions. It has been shown that, because the
enhanced reaction rate can be achieved and dynamically maintained during milling as a result of
microstructural refinement and mixing processes accompanying repeated fracture, deformation and
welding of particles during collision events [33], several treatments employing milling could be applied
for various preparation stages of mixed oxides [34 –37]. Recently, the mixed oxides containing CeO2
and other dopants, such as ZrO2, TbOx and HfO2, have been prepared by mechanical milling [7,38]
with strong enhancement of the OSC properties of CeO2. In addition, Castricum et al. report that the
milling process of mixed Cu, Cu2O or CuO and ZnO in synthetic air results in oxidation of Cu
precursors, while, under vacuum, it results in reduction. They also report that the mechanochemical
reactions are promoted by mechanical milling in the presence of ZnO [39].
The OSC property of the CuO –CeO2 system for TWCs has not been previously reported, and it is
interesting to study the effect of the mechanochemical process on the OSC property of the Ce–Cu– O
systems. It is also reasonable to consider that the valence change of Ce4þ/Ce3þ and/or Cu2þ/Cuþ/Cu
may improve the OSC property at lower temperatures. Thus, the primary aim of this study is to
characterize the CeO2 –CuO mixed oxides prepared by high-energy mechanical milling and evaluate
the OSC properties, which is compared with CeO2 –ZrO2 traditional catalysts prepared under the
same experimental conditions.

2. Experiment
2.1. Catalyst preparation
Monoclinic CuO (Nilaco Corporation, less than 250 mm, 99.999% purity), monoclinic ZrO2 (Nilaco
Corporation, less than 200 mm, 99.8% purity) and cubic CeO2 (Kojundo Chemical, less than 180 mm,
99.99% purity) powders were used as starting materials. The molar ratio of CuO in the composite was
changed to be 0, 20, 30, 50, 80 and 100%. High-energy vibratory ball milling (Super-Misuni, Nissin
Giken Co. Ltd.) was employed, with a rotational speed of 710 r.p.m., where the milling atmosphere
was ambient. The powders and zirconia balls (f10 mm) were charged in a stainless steel vial
(f100 mm), where the ball-to-powder weight ratio was 18 : 1 (18 g balls per 1 g powder) and the
milling durations were changed from 0 to 30 h.

2.2. Characterizations
The structures, the morphological aspects and the compositions of milled samples were analysed by X-ray
diffractometry (XRD) using Cu Ka radiation (RIGAKU RINT-2100CMT), scanning electron microscopy
(SEM, JEOL, JSM-5800) and EDX (energy-dispersive X-ray). The silver powder (99.8% purity) was used
for both the 2-theta calibration of X-ray diffraction line positions and the background intensity
calibration, and the lattice parameter and the crystallite size were then calculated on the basis of FWHM
(full width at half maximum intensity) of the 220 peak of CeO2, where the Scherrer’s Equation was
used for the latter. The surface areas were estimated by the N2 adsorption method (single-point BET).
 2.3. Catalytic property measurements 3

The milled sample was subjected to measurement of total OSC according to the method by Tanabe et al. [40]

[Link]/journal/rsos
and Morikawa [41]. The weight change of the milled sample was measured with TG-DTA (RIGAKU TG-
8120) by the following procedure; the milled sample (about 20 mg) on an alumina container was
completely oxidized at 5008C in a N2-20vol%O2 mixed gas flow (dry air, 500 ml min21) for 60 min,
followed by cooling to 3008C. Then, the gas atmosphere was switched to an Ar-5vol%H2 flow
(500 ml min21) and the weight decrease due to reduction was monitored until no weight change
was observed. Afterward, the gas atmosphere was again switched to the dry air and the weight increase
due to oxidation was monitored until no weight change was observed. The procedure was repeated twice.
The dynamic reduction behaviour was measured by TPR, where the milled sample (about 50 mg)
was put in a quartz reactor and heated at 4008C for 1 h under a N2-20%O2 gas flow (30 ml min21)
and cooled to room temperature (RT). The gas was then changed to Ar-5%H2 (25 ml min21) and the
sample was heated at 15oC/min for the temperature range of 35–9008C, where the H2 consumption

R. Soc. open sci. 6: 181861

was measured by GC-TCD (Varian CP-4900). For the second run of H2-TPR, the sample (50 mg) after
Downloaded from [Link] on 26 May 2022

the first TPR was cooled to RT in Ar-5%H2 gas, re-oxidized at 4008C for 1 h under a N2-20%O2 gas
flow (30 ml min21), cooled to RT again, and finally heated under an Ar-5%H2 gas flow (25 ml min21)
at 15oC min21 up to 9008C for the repeated H2-TPR.

3. Results and discussion

3.1. Structural characterization
The XRD patterns of milled samples, having a composition of 50%mol CuO and 50%mol CeO2, are
shown in figure 1. The reflection peak intensities of the CuO phase are largely reduced with peak
broadening after 2 h milling, while no appearance of other phases is detected. Although not detected,
some CuO phases may exist in nanostructured or amorphous states. After 7 h milling, the CuO peaks
are almost eliminated and replaced instead by the appearance of the faint reflections from a Cu2O
phase and the clear peaks of fcc Cu. The coexistence of both phases lasts until the milling duration of
around 14 h. The Cu2O reflections become weaker with milling, while the Cu peaks become more
distinguished with milling, a tendency which continues up to 30 h milling. There is no change in the
observed phase of CeO2 up to 30 h milling, although the peak broadening with milling is significant,
particularly during the early milling stages regarding the change of the peak shape.
From the XRD results, the reductive valence change of CuO, i.e. Cu2þ ! Cu1þ ! Cu or Cu2þ ! Cu,
occurs during milling. This is consistent with a report that there are three ways [12,13] to reduce Cu2þ
to Cu: (i) CuO ! Cu4O3 ! Cu2O ! Cu, (ii) CuO ! Cu2O ! Cu or (iii) CuO ! Cu. The presence of Cu
is also confirmed by nuclear magnetic resonance spectroscopy in the 7 h- and 18 h-milled samples (not
shown here). When the CeO2 and CuO powder phases are forced to contact at the bounding interphase
interface during milling the cations of Ce4þ (or Ce3þ for non-stoichiometric sites especially near the
surface) could be interchanged with Cu2þ cations through the vacancy mechanism. The CeO2 powder,
in particular the surface volume, exhibits non-stoichiometric compositions with various defects [42],
which can be formed upon the introduction of metal cations with higher or lower valences into CeO2. It
is also known that the mechanical milling of powders induces the fracture and deformation through
high-energy collisions among balls, vial surface and particles [43], leading to a modification of the
crystal structure as well as large lattice strain. In this study, the Cu cations can be introduced in the
lattice of CeO2, replacing the Ce cations as well as producing the extra oxygen vacancies in the CeO2 lattice.
Figure 2 shows XRD patterns of 18 h-milled samples with various CeO2 –CuO content ratios. For pure
CuO (figure 2a), no phase change of CuO is observed after 18 h milling. But, with the 80 mol% CuO
composite (figure 2b), the coexistence of both Cu and Cu2O phases is observed replacing the CuO,
besides the existence of the cubic CeO2. With 70 mol% CuO (figure 2c), the observable Cu-related
phase after 18 h milling is an fcc Cu phase only. By further reducing the CuO content (figure 2d –f )
for each after 18 h milling, the emerged intensity of the Cu phase is gradually lowered, without a
major change in the CeO2 reflections.
The lattice parameter and the estimated crystallite size of the cubic CeO2 phase in the
(CuO)0.5(CeO2)0.5 composite are shown in figure 3, as a function of milling time. The crystallite size is
rapidly decreased during an early stage of the milling periods, less than approximately 5 h, followed
by a gradual decrease up to 30 h milling. But the lattice parameter is only gradually increased during
an early stage of milling, less than approximately 5 h, followed by a rather rapid increase with the
 4

[Link]/journal/rsos
: cubic CeO2
: monoclinic CuO
: Cu2O
diffraction intensity (arb. units)

: Cu

30 h
18 h
16 h
14 h
12 h

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

7h
2h
0h

25 30 35 40 45 50 55 60 65 70 75
2q (°)
Figure 1. XRD patterns of (CuO)0.5(CeO2)0.5 powder (CuO: monoclinic, CeO2: cubic) with milling time.

: cubic CeO2
: Cu2O
: Cu
: CuO
diffraction intensity (arb. units)

b
c
d
e
f
25 30 35 40 45 50 55 60 65 70 75
2q (°)
Figure 2. XRD patterns (CuO)x(CeO2)12x powder after 18 h milling (x¼: (a) 1, (b) 0.8, (c) 0.7, (d) 0.5, (e) 0.2, (f ) 0).

increase of the milling time up to approximately 18 h, and then the variation becomes small up to 30 h
milling. This indicates that although the change of the crystallite size is not directly related to the lattice
parameter variation, the latter is activated only after the former event. This is consistent with the idea that
the appearance of Cu and Cu2O phases is clearly observed when the milling duration is longer than 7 h,
as shown in figure 1, because atomic-order mixing of powders that is prerequisite for the phase change is
generally expected, particularly in the vicinity of the interphase interface, only after effective repeated
folding of particles during milling, the so-called kneading effect, producing fine layered structures
inside powder. It is also suggested that a steady state of the structural variation of CeO2 is attained
after approximately 18 h milling. The decrease of crystallite size and the increase of lattice parameter
of CeO2 with milling time are also reported [44 –48].
 50 5
5.4164

[Link]/journal/rsos
40 5.4160

lattice parameter (Å)

crystallite size (nm)

5.4156
30

5.4152
20
5.4148

R. Soc. open sci. 6: 181861

10
Downloaded from [Link] on 26 May 2022

5.4144

0 5.4140
0 5 10 15 20 25 30
milling time (h)
Figure 3. Crystallite size and lattice parameter of CeO2 in (CuO)0.5(CeO2)0.5 composite powder as a function of milling time.

Table 1. Lattice parameter, crystallite size, of cubic CeO2 and BET surface area for various (CuO)x(CeO2)12x samples after 18 h
milling.

lattice crystallite size (nm) SA (BET)

sample parametter (Ao) d[220] m2g21

(CuO)0.8(CeO2)0.2 5.4168(6) 11.3 17.5 – 19.7

(CuO)0.5(CeO2)0.5 5.4163(2) 12.8 18.6 – 21.9
(CuO)0.8(CeO2)0.2 5.4160(0) 13.6 19.4 – 22.3
(CuO)0.2(CeO2)0.8 5.4158(9) 14.4 21.1 – 23.7
CeO2 5.4152(4) 15.6 23.3 – 25.6

The lattice parameters and crystallite sizes of the cubic CeO2 phase and the specific surface areas
(BET) of 18 h-milled samples with various CuO contents are listed in table 1. With an increase of
mol% CuO contents, the lattice parameter of CeO2 is increased, the average crystallite size is
decreased and the BET surface area of CuO– CeO2 powder composite is decreased. Because the
smaller crystallite size may cause an elongation of the cubic lattice in the nano-sized CeO2 phase [47],
which is ascribed to the lattice strain from the formation of the Ce3þ cations and the corresponding
oxygen vacancies, the observed tendency is consistent. The slight decrease of the BET area with the
CuO ratio is probably due to formation of the soft Cu phase during 18 h milling (figure 2), which
may cause agglomeration of powders.

3.2. Morphological features

The morphological features and the compositional homogeneity are studied by SEM and EDX. Similar
morphology is observed for all the milled samples, where aggregations of packed particles from a few
hundred nanometres to micrometres in size exist, as shown in figure 4. Some reports show that the CuO
is incorporated and evenly distributed into the CeO2 structure [49,50]. As shown in figure 5, with the
use of each beam size adjusted as 10 mm, the areal average concentrations of each 18 h-milled sample
with a different overall composition (20, 50, 70 or 80 mol% CuO) exhibit high homogeneity in terms of
Ce and Cu contents, judging from the EDX analyses at 20 randomly selected squares. The magnification
of SEM is fixed at 220 times. This strongly suggests that the dimensional size of the Cu or Cu2O phase,
as observed in figure 2, is much smaller than 10 mm. Contamination from the milled media (ZrO2 balls
 (b) 6
(a)

[Link]/journal/rsos
5 µm 5 µm

Figure 4. SEM micrograph of 18 h-milled powders; (a) (CuO)0.8(CeO2)0.2 and (b) (CuO)0.2(CeO2)0.8.

100

R. Soc. open sci. 6: 181861

100
Downloaded from [Link] on 26 May 2022

(CuO)0.5(CeO2)0.5
80 80
(CuO)0.2(CeO2)0.8 Ce Cu
atomic %

60 Ce 60
Cu
40 40

20 20

0 0
0 5 10 15 20 0 5 10 15 20
100 100
(CuO)0.7(CeO2)0.3 (CuO)0.8(CeO2)0.2
80 80
atomic %

60 60 Ce
Ce Cu
Cu
40 40

20 20

0 0
0 5 10 15 20 0 5 10 15 20
test number test number
Figure 5. EDX analysis on various (CuO)x(CeO2)12x samples after 18 h milling; 15 kV.

and a steel vial) is also examined by EDX, and the maximal contamination level is less than 1 wt% for Fe
while no contamination is detectable for Cr, ZrO2, and so on, after 18 h milling.

3.3. Reduction behaviour by TPR

The H2-TPR profiles of the (CuO)0.5(CeO2)0.5 samples milled for 0, 4, 7, 14 and 18 h are shown in figure 6.
For powders without milling (0 h milling), i.e. by mixing the oxide powders, the reduction of
(CuO)0.5(CeO2)0.5 is characterized by rather combined three peaks (a, b, and g) in the range of 220–
4208C and one broad f peak in the range of 700 –8808C. After 4 h milling, the former peaks (a, b and
g) merge into one large broad peak cantered around 3008C– 3208C with some skewed symmetry. The
position and the intensity of the peak are not largely changed with further milling, but the skewness
is somewhat increased, with the peak top shifting to the higher temperatures with milling time up to
18 h (figure 6). The progression of the milling process should produce a large amount of bounding
interface/interphase between CuO and CeO2, and some Cu atoms would even be penetrated into
CeO2, producing Ce12xCuxO2 solid solutions near the interface vicinity. These would facilitate the
mobility of oxygen atoms for both phases, resulting in promoted valence variation of cations and
leading to the observed large areas of H2 consumption peak. As for the latter peak, the broadness of
the peak is slightly reduced with milling time, whereas the peak top is around 8008C.
 7
0h
f

[Link]/journal/rsos
a
b 4h
g

7h
H2 consumption (mlvolt)

14 h

18 h

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

100 200 300 400 500 600 700 800 900

temperature (°C)
Figure 6. TPR of (CuO)0.5(CeO2)0.5 composite powder with milling time.

f b
b g
a
c
H2 consumption (mlvolt)

100 200 300 400 500 600 700 800 900

temperature (°C)
Figure 7. TPR of (a) CeO2, (b) CuO powder for 0 h milling and (CuO)x(CeO2)12x powder after 18 h milling (x¼ (c) 1, (d) 0.8,
(e) 0.5, (f ) 0.3, (g) 0.2, (h) 0).

Figure 7 shows the H2-TPR profiles of various (CuO)x(CeO2)12x powders (x ¼ 1, 0.8, 0.5, 0.3, 0.2, 0)
after 18 h milling, compared with pure CeO2 (a) and CuO (b) powders without milling (0 h milling). For
pure CuO (x ¼ 1), the reduction is characterized by rather combined three peaks (a, b, and g) in the range
of 200 –4708C and one broad f peak in the range of 750–8508C (figure 7b,c), regardless of milling or
without milling, strongly indicating that the powder morphology and the milling-induced defects are
not the major factors influencing the reduction behaviour. In addition, the range of reduction
temperatures is wider compared with that of the (CuO)0.5(CeO2)0.5 composite (figure 6: 0 h), indicating
multiple reduction steps are involved with possible inhomogeneous reactions. But, only two apparent
peaks are observed for lower CuO contents (figure 7d–g), and the intensity of both peaks is reduced
when CuO content is decreased, demonstrating the major contribution of CuO to the H2
 consumption. For pure CeO2 (figure 7a,h), there is no distinguished H2-TPR peak in the temperature 8
range observed, while the consumption of H2 steadily exists above 3508C up to approximately 9008C

[Link]/journal/rsos
for reducing CeO2 to Ce2O3, where the reduction first occurs near the surface defects [51,52] followed
by the formation of intermediate CeO2-x and complete transformation to Ce2O3.
It is reported by Fierro et al. [53] that the TPR characteristics could be affected by mass transfer
limitations and experimental operating variables such as the initial amount of reducible species,
the initial H2 concentration, the total gas flow rate, the heating rate, and the activation energy of the
reaction. They claim that desorption of H2 attached to the reduced Cu metal surface could exhibit
the apparent double-peak behaviour, which may be affected by water vapour produced by the
reduction process, and that the H2-TPR profile of CuO depends on the particle size and surface area,
where the peak top is higher by 2888C for particle sizes of 425 approximately 850 microns compared
with less than 100 microns [53]. A similar tendency but with a much larger peak shift (over 3738C) is
also reported by Luo et al. [49], who claim that the hydrogen spillover effect is the reason for the
difference between CO-TPR and H2-TPR.

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

Kim et al. [54] report that there is an incubation period prior to reduction, which is longer at lower
temperatures. The tendency is in agreement with the general theory of nucleation and growth, where
the number of newly formed nuclei is copious at lower temperatures, but because the growth is very
much limited at lower temperatures, the phase existence is not easily detected by x-ray diffractometry.
They claim that CuO reduction is generally easier than Cu2O reduction with H2-TPR, with the
apparent activation energy for Cu2O close to twice that of CuO, but when the H2 flow rate is not high
enough for avoiding the rate-limiting of the reduction process, a sequential reduction process such as
CuO ! (Cu4O3 !) Cu2O ! Cu may happen. Our experimental condition is: 15oC min21, 50 mg and
25 cc min21 of 5%H2 flow. This is close to the condition for the appearance of the sequential process
due to the ‘lean H2’ flow. The incubation period and the sequential/simultaneous reduction process
are also reported by Kim et al. [54], where, with the lean H2 condition, the CuO, Cu2O and Cu are
simultaneously observed after a certain incubation period according to the time-resolved XRD. This is
consistent with our thought experiments (not shown here), where the 3 phases are simultaneously
observed when the H2-TPR is stopped at 2808C and kept for 15 min, while only CuO is observed
when the sample is immediately quenched from 2808C to RT.
Consequently, the a peak for pure CuO reduction, as shown in figure 7, should be mainly attributed to
direct reduction of CuO particles into Cu in the surface vicinity, and some simultaneous reduction to
Cu2O (or Cu4O3) should be involved with our experimental operating variables, somewhat
contributing to the a peak. Because the rate of nucleation and growth of each reduced phase is
different, which involves the shape of nuclei and the nucleation sites besides the spillover effect of H2
on the metallic Cu, one rate-determining step would gradually dominate the sequential CuO reduction
to Cu2O and Cu, exhibiting the broad b peak for the slow reduction process, which is related to the
larger activation energy for Cu2O formation compared with direct Cu formation. Before the end of the
sequential reaction, some H2 molecules would be dissociated from H atoms on newly formed Cu on
the powder surface, penetrating into the Cu(/Cu2O)/CuO particles, and at certain temperature(s),
depending on the surrounding condition, the remaining CuO would be reduced to Cu either directly
or sequentially through Cu2O (or Cu4O3), exhibiting the g peak. The extended TPR peak profile as
high as 4708C or even 4808C strongly indicates the difficulty of reduction due to longer the diffusion
path for H atoms or H2 molecules as well as the escape of produced H2O molecules. It is
acknowledged that the larger the CuO particles, the thicker the reduced Cu phase; this covers the
particle and shows the bulk-like behaviour of CuO reduction. Thus, the a and b peaks are probably
caused by surface-vicinity reduction with separate locations, whereas the g peak would be due to
reduction inside the particles. At the high temperature f peak, it may cause the Cu surface to interact
with the SiO2 quartz reactor [55,56].
The apparent increase of the H2-TPR starting temperature for the a peak, as shown in figure 6,
compared with pure CuO in figure 7b,c is probably due to variation on the mass transfer limitations
affected by experimental operating variables such as the initial amount of reducible species and
effective total gas flow rate through mixing CeO2 particles with CuO particles. But, the end
temperature for the g peak, as shown in figure 6, is much decreased, compared with pure CuO
shown in figure 7b,c. This must be the mixing effect of CeO2 particles with CuO particles, in that the
contact point or the interphase interface plays an important role in the nucleation and growth of the
reduced phase such as Cu, or even Cu2O. Owing to the valence change of cations requiring high
electron mobility as well as the higher oxygen mobility near the contact point, the nucleation event is
much more active in the vicinity, and with the fast surface diffusion of Cu atoms the nucleation is
 immediately followed by growth or accumulation of the new phase, always leaving some area of fresh 9
CuO surface contacting with H2/Ar gas. In the reduction process, the diffusion paths for H atoms or

[Link]/journal/rsos
H2 molecules as well as the escape path of the produced H2O molecules are established, and the
reduction is continued until all the CuO is consumed.
There are many reports on the CuO–CeO2 powder systems and the reduction study. Many researchers
report that ceria in the CuO– CeO2 powder promotes surface species reduction of highly dispersed copper
oxide [57 –64] and the CuO particles with smaller sizes are easier to reduce [65]. According to Liu et al. [58],
the reduction peak at lower temperature is attributed to copper oxide clusters strongly interacting with
ceria, whereas the peak at higher temperature is attributed to larger CuO particles, not associated with
ceria. A similar tendency in the H2-TPR profile is also reported by Luo et al. [60] and Xiaoyuan et al.
[61]. Furthermore, Tang et al. [66] report that the lower temperature peak is assigned to reduction of
amorphous CuO clusters closely interacting with the CeO2, while Luo et al. [48] claim that with
increasing CuO content three peaks appear, with the lowest temperature deriving from reduction of
finely dispersed CuO, the intermediate temperature associated with reduction of Cu2þ ions in

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

CuxCe12xO22d solid solutions, and the additional highest one due to reduction of bulk CuO.
As observed in figure 6, with increasing milling time on (CuO)0.5(CeO2)0.5 composite samples, the
skewness of H2-TPR profile is somewhat increased with the peak top shifting to the higher
temperatures. Also, in figure 7, as the CuO content is decreased in various 18 h-milled
(CuO)x(CeO2)12x powders, the H2 absorption at lower temperatures involved with the a peak is
gradually diminished, with the peak tops of the main H2-TPR profiles around 310–3308C, which is
similar to that shown in figure 6. Wang et al. claim that [49] Cu atoms embedded in ceria have an
oxidation state higher than those of the cations in Cu2O or CuO, where (i) Cu in the doped sample is
only partially reduced to metallic Cu, especially at low temperatures as CuO ! Cu2O ! Cu, because
Cu embedded in ceria is difficult to reduce, (ii) The lattice of the Ce12xCuxO2 systems (fluorite-type)
is highly distorted with local order defects and multiple cation-oxygen distances, and (iii) Doping
CeO2 with Cu introduces large strain and O vacancies.
This is consistent with our results in that, at the early stage of milling such as before 7 h milling, the
ultrafine mixture of CuO/CeO2 is more effective for H2-TPR profile, which corresponds to the rapid
crystallite size reduction before 4 h milling, as shown in figure 3. Here, the large area of CuO/CeO2
interphase interface is extremely efficient for producing the path for H2 diffusion and H2O escape,
besides the effective valence change of cations, where the x-ray diffractometry in figure 1 identifies
only CuO and CeO2 phases. But, the longer the milling time, the more intense the formation of
Ce12xCuxO2 solid solution systems, where the higher peak temperature for the H2-TPR profile should
be observed due to Cu embedded in ceria as milling proceeds. The results are also consistent with
our x-ray results shown in figure 1, where atomic-order mixing is achieved at least near the interface
vicinity of CuO/CeO2, producing Cu and Cu2O after 7 h milling, and that the clear increase in the
lattice parameter is observed (figure 3) after approximately 7 h milling.
It is thus quite reasonable to consider that, at the early stage of milling, the major H2-TPR peaks
caused by milling of CuO/CeO2 are attributed to reduction of Cu2þ ions in the interfacial vicinity of
CeO2, which exist in the ultrafine mixture of CuO/CeO2 or some Cu2O/CeO2. The CuO particles are
highly dispersed, producing many active sites for Cu2þ reduction on the interphase interface with
CeO2. With the increase of milling time, some Cu atoms are even incorporated into CeO2, causing
formation of Ce12xCuxO2 solid solutions. The large intensity and the broad profile of the H2-TPR
peaks would be observed due to the dual effect.
Figure 8 shows the repeated H2-TPR cycles of milled (CuO)0.5(CeO2)0.5 composites (50 mol% CuO
milled for 0, 4, 7, 14 and 18 h) in figure 6, each after the first TPR. The peak intensity for the 0 h
milled sample is largely decreased, when compared with the first run, with high temperature peak(s)
remaining, suggesting agglomeration/recrystallization of CuO particles that produce bulk-like CuO
after heating to 9008C. When increasing the milling time, the CeO2 particles are finely distributed into
the CuO particles, or some Ce–Cu –O solid solutions are produced, which prevents agglomeration/
recrystallization of CuO, leading to the slow decrease observed in the peak intensity. The
temperatures of the reduction start as well as the peak top of the H2 consumption are lowered
compared with the first run. On considering that the pure CuO is reduced in the wide range of
temperatures (200–4708C, figure 7b,c) regardless of milling or without milling under this particular
experimental condition, some CuO is heterogeneously reduced (lean H2-TPR) at low temperatures
(200–2508C) to produce Cu and CuxO simultaneously. But, because the (CuO)0.5(CeO2)0.5 composite
powders are finely mixed with milling, even after the H2-TPR to 9008C, the elemental mixture is
maintained, and the CuO reduction is activated by surface contact with CeO2.
 0h 10

[Link]/journal/rsos
4h

7h
H2 consumption (mlvolt)

14 h

18 h

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

100 200 300 400 500 600 700 800 900

temperature (°C)
Figure 8. TPR of (CuO)0.5(CeO2)0.5 powder with milling time after the first TPR cycle.

3000 2862 2906

2753
2604
2500
OSC (µmol-O2/g-catalyst)

2000
1806

1500
1158

1000

500

0
0h 4h 7h 14 h 18 h 30 h
Figure 9. Total OSC at 3008C of (CuO)0.5(CeO2)0.5 powder with milling time.

Figure 9 shows the total OSC at 3008C of various milled samples (50 mol% of CuO) after 0, 4, 7, 14, 18
and 30 h milling. The total OSC is increased with milling time, with the rapid increase from 0 to 7 h
milling followed by the gradual increase from 7 h to 30 h. This is consistent with figure 1 (x-ray
results) and figure 3 in that the rapid atomic-order mixing is effective during the early stage milling of
7 h, evidenced by both solid state reactions and crystallite size variations. It is also noted that, because
the lattice parameters are largely varied after 7 h milling, the CuO/CeO2 interphase interface creation
and the corresponding atomic contact would be more important for the effective OSC than formation
of the Ce–Cu –O solid solution, although both contribute to the OSC promotion. That is, the activated
valence change of Cu2þ/Cuþ/Cu assisted by neighbouring Ce-O bonds is extremely important, and
the oxygen transport path is also critical for the OSC. The enhanced oxygen storage/transport would
 8000 11

7094

[Link]/journal/rsos
powder milled for 18 h
6000 aged powder (1000°C, 5 h)
OSC (µmol-O2/g-catalyst)

after 18 h milling

4000 3919

2862

2000 1870

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

1242 1418
979
637
234 330
0
0
CeO2 (CuO)0.2(CeO2)0.8 (CuO)0.3(CeO2)0.7 (CuO)0.5(CeO2)0.5 (CuO)0.8(CeO2)0.2 CuO

Figure 10. Total OSC at 3008C of milled samples for 18 h and after ageing at 10008C for 5 h.

8000
7094

6000
OSC (µmol-O2/g-catalyst)

4000

2862

2000

185 258
0
(CuO)0.8(CeO2)0.2 (CeO2)0.8(ZrO2)0.2 (CuO)0.5(CeO2)0.5 (CeO2)0.5(ZrO2)0.5

Figure 11. Comparison of total OSC at 3008C of CuO – CeO2 and CeO2 – ZrO2-milled powder.

thus be realized through easy valence change of Cu2þ/Cuþ/Cu neighboured by Ce-O bonds and the
large surface area with the large number of the available oxygen vacancies.
The total OSC at 3008C for the samples milled for 18 h is increased, as shown in figure 10, from 0 to
7094 mmol-O2/g-catalyst with increased CuO content from 0 to 80 mol%, but is decreased to 3919 mmol-
O2/g-catalyst for pure CuO (BET surface area of 15 –16 m2 g21). After ambient ageing at 10008C for 5 h,
however, the total OSCs at 3008C are significantly reduced (figure 10), probably ascribed to the
agglomeration/recrystallization of fine particles.
As shown in figure 11, the total OSCs of the CeO2-20 at %ZrO2 and the CeO2-50 at %ZrO2 at 3008C
are 185 and 258 mmol-O2/g-catalysts, respectively, while those of the CuO–CeO2 catalyst system
prepared with the same condition are at least one order greater. It clearly shows that the mechanically
driven CuO/CeO2 system exhibits the high OSC property, and this should contribute to improving
the performance of TWCs at lower temperatures.
 4. Conclusion 12

[Link]/journal/rsos
Mechanical milling was applied to the CuO –CeO2 powder system to produce mixed-oxide catalysts. The
milled sample was characterized by the use of XRD, SEM, TG-DTA, GC-TCD and BET analyses. Milling
of powder mixtures of CuO and CeO2 showed the reduction of CuO when milling was processed in air.
The crystallite size of ceria was rapidly decreased at the early stage of milling, followed by an increase of
the lattice parameter, indicating formation of Ce12xCuxO2 solid solutions after the rapid crystallite size
reduction. The redox property of milled CuO–CeO2 samples was investigated by H2-TPR. Three
reduction peaks were observed for 0 h milling and only one broad peak for various milling times,
where the valence change of Cu ions enhanced the redox activity. The higher OSC for the CuO– CeO2
system was observed with increased milling time. The total OSC of the CuO –CeO2 catalyst was much
higher than that of the CeO2 –ZrO2 traditional catalyst system at low temperature.
Data accessibility. The datasets supporting this article have been uploaded as part of the electronic supplementary
material.

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

Authors’ contributions. Nguyen The Luong carried out the catalyst preparation, experiment tests and drafted the
manuscript. Hideyuki Okumura, Eiji Yamasue and Keiichi N. Ishihara participated in the design of the study and
helped to modify the manuscript. All authors approved the final version of the manuscript.
Competing interests. The authors declare no competing interests.
Funding. This work was supported by Global Center of Excellence (GCOE) Program and the Monbukagakusho
Scholarship, Japan.
Acknowledgments. The authors thank Prof. K. Yoshimura and Prof. C. Michioka for their help on NMR measurements.

References
1. Kaspar J, Fornasero P, Hickey N. 2003 M. Shelef. J. Mater. Res. 11, 1960. (doi:10.1557/ 16. Tschope A, Liu W, Flytzani-Stephanopoulos M,
Automotive catalytic converters: current status JMR.1996.0247) Ying JY. 1995 Redox activity of
and some perspectives. Catal. Today 77, 9. Uzunoglu A, Zhang H, Andreescu S, Stanciu LA. nonstoichiometric cerium oxide-based
419–449. (doi:10.1016/S0920- 2015 CeO2 – MOx (M: Zr, Ti, Cu) mixed metal nanocrystalline catalysts. J. Catal. 157, 42.
5861(02)00384-X) oxides with enhanced oxygen storage capacity. (doi:10.1006/jcat.1995.1266)
2. Masui T, Ozaki T, Machida K-I, Adachi G-Y. 2000 J. Mater. Sci. 50, 3750 –3762. (doi:10.1007/ 17. Zhu T, Kudakovic L, Dreher A, Flytzani-
Preparation of ceria –zirconia sub-catalysts for s10853-015-8939-7) Stephanopoulos M. 1999 Redox chemistry over
automotive exhaust cleaning. J. Alloys Compd. 10. Uzunoglu A, Kose DA, Stanciu LA. 2017 CeO2-based catalysts: SO2 reduction by CO or
303 –304, 1 – 538. (doi:10.1016/S0925- Synthesis of CeO2-based core/shell nanoparticles CH4. Catal. Today 50, 381. (doi:10.1016/S0920-
8388(00)00603-4) with high oxygen storage capacity. Int. Nano 5861(98)00517-3)
3. Usmen RK, Graham GW, Watkins WLH, McCabe Lett. 7, 187–193. (doi:10.1007/s40089-017- 18. Fernandez-Garcia M, Gomez Rebollo E, Guerrero
RW. 1995 Incorporation of La3þ into a Pt/ 0213-3) Ruiz A, Conesa JC, Soria J. 1997 Influence of
CeO2/Al2O3 catalyst. Catal. Lett. 30, 53. (doi:10. 11. Kato S, Fujimaki R, Ogasawara M, Wakabayashi ceria on the dispersion and reduction/oxidation
1007/BF00813672) T, Nakahara Y, Nakata S. 2009 Oxygen storage behaviour of alumina-supported copper
4. Bensalem A, Bozon-Verduraz F, Delamar M, capacity of CuMO2 (M¼Al, Fe, Mn, Ga) with a catalysts. J. Catal. 172, 146. (doi:10.1006/jcat.
Bugli G. 1995 Preparation and characterization delafossite-type structure. Appl. Catal. B 89, 1997.1842)
of highly dispersed silica-supported ceria. Appl. 183–188. (doi:10.1016/[Link].2008.11.033) 19. Bera P, Aruna ST, Patil KC, Hegde MS. 1999
Catal. A 121, 81. (doi:10.1016/0926- 12. Liu W, Stephanopoulos F. 1995 Total oxidation of Studies on Cu/CeO2: a new NO reduction
860X(95)85012-0) carbon monoxide and methane over transition catalyst. J. Catal. 186, 36. (doi:10.1006/jcat.
5. Ozawa M, Kimura M, Sobukawa H, Yokota K. metal fluorite oxide composite catalysts: I. Catalyst 1999.2532)
1992 Highly thermal-resistant three-way composition and activity. J. Catal. 153, 304–316. 20. Hocevar S, Batista J, Levec J. 1999 Wet
catalyst. Toyota Tech. Rev. 27, 43. (doi:10. (doi:10.1006/jcat.1995.1132) oxidation of phenol on Ce12xCuxO22d catalyst.
11351/jsaeronbun.39.6_107) 13. Luo M, Zhong F, Yuan YJ, Zheng X. 1997 TPR J. Catal. 184, 39. (doi:10.1006/jcat.1999.2422)
6. Matsumoto S, Miyoshi N, Kanazawa T, Kimura and TPD studies of CuOCeO2 catalysts for low 21. Hocevar S, Opara Krasovec U, Orel B, Arico AS,
M, Ozawa M. 1991 The application of Ce-Zr temperature CO oxidation. Appl. Catal. A 162, Kim H. 2000 CWO of phenol on two differently
oxide solid solution to oxygen storage 121–131. (doi:10.1006/jcat.1995.1132) prepared CuO –CeO2 catalysts. Appl. Catal. B 28,
promoters in automotive catalysts. Catal. Sci. 14. Luo J, Meng Y, Yao M, Li S, Zha XG, Wang YQ, 113. (doi:10.1016/S0926-3373(00)00167-3)
Technol. 1, 335. (doi:10.1016/0925- Zhang X. 2009 One-step synthesis of 22. Robert CL, Long JW, Lucas EM, Pettigrew KA,
8388(93)90314-D) nanostructured Pd-doped mixed oxides Stroud RM, Doescher MS, Rolison DR. 2006
7. Zamar F, Trovarelli A, de Leitenburg C, Dolcetti MOx-CeO2 (M ¼ Mn, Fe, Co, Ni, Cu) for Sol2gel-derived ceria nanoarchitectures:
G. 1996 The direct room-temperature synthesis efficient CO and C3H8 total oxidation. Catal. B: synthesis, characterization, and electrical
of CeO2-based solid solutions: a novel route Environ. 87, 92– 103. (doi:10.1016/[Link]. properties. Chem. Mater. 18, 50– 58. (doi:10.
to catalysts with a high oxygen storage/ 2008.08.017) 1021/cm051385t)
transport capacity. Stud. Surf. Sci. Catal. 15. Liu W, Sarofim AF, Flytzani-Stephanopoulos M. 23. Mai HX, Sun LD, Zhang YW, Si R, Feng W,
101, 1283. (doi:10.1016/S0167- 1994 Total oxidation of carbon-monoxide and Zhang HP, Liu HC, Yan CH. 2005 Shape-selective
2991(96)80340-5) methane over transition metal fluorite oxide synthesis and oxygen storage behavior of ceria
8. Sinev MY, Graham GW, Haach LP. 1996 Kinetic composite catalysts: II. Catalyst characterization nanopolyhedra, nanorods, and nanocubes.
and structural studies of oxygen availability of and reaction-kinetics. Appl. Catal. B 4, 167. J. Physchem. B 109, 24380. (doi:10.1021/
the mixed oxides Pr1 –xMxOy (M ¼ Ce, Zr), (doi:10.1006/jcat.1995.1133) jp055584b)
 24. Zhou KB, Yang ZQ, Yang S. 2007 Highly 39. Castricum HL, Bakker H, Poels EK. 2001 Oxidation 54. Kim JY, Rodriguez JA, Hanson JC, Frenkel AI, Lee 13
reducible CeO2 nanotubes. Chem. Mater. 19, and reduction in copper/zinc oxides by mechanical PL. 2003 Reduction of CuO and Cu2O with H2: H
1215. (doi:10.1021/cm062886x) milling. Mater. Sci. Eng. A 304–306, 418–423. embedding and kinetic effects in the formation

[Link]/journal/rsos
25. Chang HY, Chen HI. 2005 Morphological (doi:10.1016/S0921-5093(00)01485-4) of suboxides. J. Am. Chem. Soc. 125,
evolution for CeO2 nanoparticles synthesized by 40. Tanabe T, Suda A, Desorme C, Duprez D, 10 684–10 692. (doi:10.1021/ja0301673)
precipitation technique. J. Cryst. Growth 283, Shinjyoh H, Sugiura M. 2001 Surface mobility 55. Yan X, Chang YA. 2000 A thermodynamic
457–468. (doi:10.1016/[Link].2005.06.002) and redox properties: study of Pt/CeO2-ZrO2 analysis of the Cu –Si system. J. Alloys Compd.
26. Scholes FH, Hughes AE, Hardin SG, Lynch P, catalysts. Stud. Sci. Catal. 138, 135. (doi:10. 308, 221– 229. (doi:10.1016/S0925-
Miller PR. 2007 Influence of hydrogen peroxide 1016/S0167-2991(01)80023-9) 8388(00)00983-X)
in the preparation of nanocrystalline ceria. 41. Morikawa A, Suzuki T, Kanazawa T, Kikuta K, 56. Espino’s JP, Morales J, Barranco A, Caballero A,
Chem. Mater. 19, 2321 – 2328. (doi:10.1021/ Suda A, Shinjo H. 2008 A new concept in high Holgado JP, González-Elipe AR. 2002 Interface
cm063024z) performance ceria – zirconia oxygen storage effects for Cu, CuO, and Cu2O deposited on SiO2
27. Gu FB, Wang ZH, Han DM, Shi C, Guo GS. 2007 capacity material with Al2O3 as a diffusion and ZrO2. XPS determination of the valence
Reverse micelles directed synthesis of barrier. Appl. Catal. B 78, 210– 221. (doi:10. state of copper in Cu/SiO2 and Cu/ZrO2 catalysts.
mesoporous ceria nanostructures. Mater. Sci. Eng. 1016/[Link].2007.09.013) J. Phys. Chem. B 106, 6921 –6929. (doi:10.
B 139, 62–68. (doi:10.1016/[Link].2007.01.051) 42. Cho BK. 1991 Chemical modification of catalyst 1021/jp014618m)
28. Zhang DS, Fu HX, Shi LY, Pan CS, Li Q, Chu YL, support for enhancement of transient catalytic 57. Li Y, Fu Q, Flytzani-Stephanopoulos M. 2000

R. Soc. open sci. 6: 181861

Downloaded from [Link] on 26 May 2022

Yu WJ. 2007 Synthesis of CeO2 nanorods via activity: nitric oxide reduction by carbon Low-temperature water-gas shift reaction over
ultrasonication assisted by polyethylene glycol. monoxide over rhodium. J. Catal. 131, 74– 87. Cu- and Ni-loaded cerium oxide catalysts. Appl.
Inorg. Chem. 46, 2446 –2451. (doi:10.1021/ (doi:10.1016/0021-9517(91)90324-W) Catal. B Environ. 27, 179– 191. (doi:10.1016/
ic061697d) 43. Koch CC, Whiittenberger JD. 1996 Mechanical S0926-3373(00)00147-8)
29. Barreca D, Gasparotto A, Maccato C, Maragno C, milling and alloying. Intermetallics 4, 339. 58. Liu W, Flytzani-Stephanopoulos M. 1996
Tondello E. 2007 First example of ZnO2TiO2 (doi:10.1002/9783527603978.mst0177)) Transition metal-promoted oxidation catalysis by
nanocomposites by chemical vapor deposition: 44. Yadav TP, Srivastava ON. 2012 Synthesis of fluorite oxides: a study of CO oxidation over
structure, morphology, composition, and gas nanocrystalline cerium oxide by high energy CuO-CeO2. Chem. Eng. J. Biochem. Eng. J. 64,
sensing performances. Nanotechnology 18, ball milling. Ceram. Int. 38, 5783 –5789. 283–294. (doi:10.1016/S0923-0467(96)03135-1)
5642 –5649. (doi:10.1021/cm701990f ) (doi:10.1016/[Link].2012.04.025) 59. Kundakovic L, Flytzani-Stephanopoulos M. 1998
30. Bondioli F, Bonamartini Corradi A, Leonelli C, 45. Zec S, Boskovic S, Kaluderovic B, Bogdanov Z, Reduction characteristics of copper oxide in
Manfredini T. 1999 Nanosized CeO2 powders Popovic N. 2009 Chemical reduction of cerium and zirconium oxide systems. Appl.
obtained by flux method. Mater. Res. Bull. 34, nanocrystalline CeO2. Ceram. Int. 35, 195 –198. Catal. A Gen. 171, 13. (doi:10.1016/S0926-
14– 15. (doi:10.1016/S0025-5408(00)00154-9) (doi:10.1016/[Link].2007.10.031) 860X(98)00056-8)
31. Yang HM, Huang CH, Tang AD, Zhang XC, Yang 46. Zec S, Boskovic S. 2004 Cerium silicates 60. Luo M, Zhong Y, Yuan X, Zheng X. 1997TPR and
WC. 2005 Microwave-assisted synthesis of ceria formation from mechanically activated oxide TPD studies of catalysts for low temperature CO
nanoparticles. Mater. Res. Bull. 40, 1690 –1695. mixtures. J. Mater. Sci. 39, 5283 –5286. (doi:10. oxidation. Appl. Catal. A Gen. 162, 121–131.
(doi:10.1016/[Link].2005.05.014) 1023/B:JMSC.0000039229.35551.9e) (doi:10.1016/S0926-860X(97)00089-6)
32. Zhou F, Zhao XM, Xu H, Yuan CG. 2007 CeO2 47. Deshpande S, Patil S, Kuchibhatla SV, Seal S. 61. Xiaoyuan J, Guanglie L, Renxian Z, Jianxin M, Yu
spherical crystallites: synthesis, formation 2005 Size dependency variation in lattice C, Xiaoming Z. 2001 Studies of pore structure,
mechanism, size control, and electrochemical parameter and valency states in nanocrystalline temperature-programmed reduction
property study. J. Phys. Chem. C 111, cerium oxide. Appl. Phys. Lett. 87, 133113. performance, and micro-structure of CuO/CeO2
1651 –1657. (doi:10.1021/jp0660435) (doi:10.1063/1.2061873) catalysts. Appl. Surf. Sci. 173, 208. (10.1016/
33. Schaffer GB, McCormick PG. 1992On the kinetics 48. Zhang F, Chan S-W, Spanier JE, Apak E, Jin Q. S0169-4332(00)00897-7)
of mechanical alloying. Metall. Trans. A 23, 2002 Cerium oxide nanoparticles: size-selective 62. Bera P, Priolkar KR, Sarode PR, Hegde MS,
1285 –1290. (doi:10.1007/BF02665060) formation and structure analysis. Appl. Phys. Emura S, Kumashiro R, Lalla NP. 2002 Structural
34. Zazhigalov VA, Haber J, Stoch J, Bogutskaya LV, Lett. 80, 127. (doi:10.1063/1.1430502) investigation of combustion synthesized Cu/CeO2
Bacherikova IV. 1996 Mechanochemistry as 49. Luo M-F, Ma J-M, Lu J-Q, Song Y-P, Wang Y-J. catalysts by EXAFS and other physical
activation method of the V-P-O catalysts for n- 2007 High-surface area CuO –CeO2 catalysts techniques: formation of a Ce12xCuxO22d solid
butane partial oxidation. Appl. Catal. A: Gen. 96, prepared by a surfactant-templated method for solution. Chem. Mater. 14, 3591. (doi:10.1021/
135–155. (doi:10.1016/0926-860X(95)00223-5) low-temperature CO oxidation. J. Catal. 246, cm0201706)
35. Mori S, Xu WC, Ishidzuki T, Ogasawara N, Imai J, 52– 59. (doi:10.1016/[Link].2006.11.021) 63. Wang J, Tsai D, Huang T. 2002 Synergistic
Kobayashi K. 1996 Mechanochemical activation 50. Wang X, Rodriguez JA, Hanson JC, Gamarra D, catalysis of carbon monoxide oxidation over
of catalysts for CO2 methanation. Appl. Catal. A: Martı́nez-Arias A, Fernández-Garcı́a M. 2005 copper oxide supported on samaria-doped ceria.
Gen 137, 255– 268. (doi:10.1016/0926- Unusual physical and chemical properties of Cu J. Catal. 208, 370. ([Link]/10.1006/jcat.2002.
860X(95)00319-3) in Ce12xCuxO2 oxides. J. Phys. Chem. B 109, 19 3580)
36. Trovarelli A, Matteazzi P, Dolcetti G, Lutman A, 595–19 603. (doi:10.1021/jp051970h) 64. Wrobel G, Lamonier C, Bennani A, D’Huysser A,
Miani F. 1993 Nanophase iron carbides as 51. Pintar A, Batista J, Hocevar S. 2005 TPR, TPO, Aboukais A. 1996 Effect of incorporation of
catalysts for carbon dioxide hydrogenation. Appl. and TPD examinations of Cu0.15Ce0.85O22ymixed copper or nickel on hydrogen storage in ceria.
Catal. A: Gen. 95, L9 –L13. (doi:10.1016/0926- oxides prepared by co-precipitation, by the Mechanism of reduction. J. Chem. Soc. Faraday
860X(93)85070-6) sol –gel peroxide route, and by citric acid- Trans. 92, 2001. (10.1039/FT9969202001)
37. Trovarelli A, Zamar F, Llorca J, de Leitenburg C, assisted synthesis. J. Colloid Interface Sci. 285, 65. Zhang S, Huang W, Qiu X, Li B, Zheng X, Wu S.
Dolcetti G, Kiss JT. 1997 Nanophase fluorite- 218–231. (doi:10.1016/[Link].2004.11.049) 2002 Comparative study on catalytic properties
structured CeO2 –ZrO2 catalysts prepared by 52. Shyu JZ, Weber WH, Gandhi HS. 1988 Surface for low-temperature CO oxidation of Cu/CeO2
high-energy mechanical milling. J. Catal. 169, characterization of alumina-supported ceria. and CuO/CeO2 prepared via solvated metal atom
490–502. (doi:10.1006/jcat.1997.1705) J. Phys. Chem. 92, 17. (doi:10.1021/ impregnation and conventional impregnation.
38. Enzo S, Delogu F. 2000 Structural j100328a029) Catal. Lett. 80, 41. (doi:1011-372X/02/0500-
characterization of ceria– zirconia powder 53. Fierro G, Lo Jacono M, Inversi M, Porta P, 0041/0)
catalysts prepared by high-energy mechanical Lavecchia R, Cioci F. 1994 A study of anomalous 66. Tang X, Zhang B, Li Y, Xu Y, Xin Q, Shen W.
milling: a neutron diffraction study. J. Mater. temperature-programmed reduction profiles of 2005 CuO/CeO2 catalysts: redox features and
Res. 15, 1538 –1545. (doi:10.1557/JMR.2000. Cu2O, CuO, and CuO-ZnO catalysts. J. Catal. 148, catalytic behaviors. Appl. Catal. A Gen. 288,
0220) 709–721. (doi:10.1006/jcat.1994.1257) 116–125. (doi:10.1016/[Link].2005.04.024)