Anda di halaman 1dari 35

Accepted Manuscript

Title: Low-temperature carbon monoxide oxidation over

zirconia-supported CuO-CeO2 catalysts: Effect of zirconia
support properties

Authors: Elisa Moretti, Antonia Infantes Molina, Gabriele

Sponchia, Aldo Talon, Romana Frattini, Enrique
Rodriguez-Castellon, Loretta Storaro

PII: S0169-4332(17)30096-X
Reference: APSUSC 34890

To appear in: APSUSC

Received date: 20-10-2016

Revised date: 1-12-2016
Accepted date: 11-1-2017

Please cite this article as: Elisa Moretti, Antonia Infantes Molina, Gabriele
Sponchia, Aldo Talon, Romana Frattini, Enrique Rodriguez-Castellon, Loretta
Storaro, Low-temperature carbon monoxide oxidation over zirconia-supported CuO-
CeO2 catalysts: Effect of zirconia support properties, Applied Surface Science

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Low-temperature carbon monoxide oxidation over zirconia-supported CuO-CeO2 catalysts:
Effect of zirconia support properties

Elisa Morettia*, Antonia Infantes Molinab, Gabriele Sponchiaa, Aldo Talona, Romana Frattinia,
Enrique Rodriguez-Castellonb, Loretta Storaroa

Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, INSTM

Venice Research Unit, Via Torino 155/B, 30172 Mestre Venezia, Italy.
Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias,

Universidad de Málaga, Campus de Teatinos, 29071 Málaga - Spain

Corresponding author:; Phone: +39-0412346745.

Graphical abstract

Research highlights

 CuO-CeO2/ZrO2 materials were investigated in the low temperature CO oxidation.

 High surface area ZrO2 synthetized by sol-gel method.
 Low ZrO2 surface area synthetized by fast precipitation.
 Sol-gel samples showed, after impregnation, a severe decrease of surface area.
 CuO-CeO2/ZrO2 with precipitated ZrO2 led to a very active catalyst.

A study was conducted to investigate the effect of the preparation route of ZrO2 in CuO-CeO2 /ZrO2

catalysts for the oxidation of carbon monoxide at low temperature (COX). Four ZrO2 supports were
synthetized via either type sol-gel methodology or precipitation. The final Cu-Ce-Zr oxide catalysts
were prepared by incipient wetness co-impregnation with copper and cerium solutions (with a
loading of 6 wt% of CuO and 20 wt% of CeO2) The catalyst crystalline phases, texture and active

species reducibility were determined by XRD, N2 physisorption at -196°C and H 2-TPR,


respectively; meanwhile the surface composition and copper-cerium electronic states were studied
by XPS. The catalytic activity was evaluated in the oxidation of CO to CO2, in the 40-215°C
temperature range. Catalytic results evidenced that the samples prepared by a sol-gel methodology
showed, after the impregnation, a severe decrease of specific surface area and pore volume
attributable to a wide degree of pore blockage caused by the presence of metal oxide particles and a
collapse of the structure partially burying the active sites. A simple co-impregnation of a zirconia
support, obtained through facile and fast precipitation, provided instead a catalyst with very good
redox properties and high dispersion of the active phases, which completely oxidizes CO in the
range 115-215°C with T50 of 65 °C. This higher observed activity was ascribed to the formation of a

larger fraction of highly dispersed and easily reducible Cu species and ceria nanocrystallites, mainly
present as Ce(IV), with an average size of 5 nm.
KEYWORDS: Zirconia; copper-ceria; carbon monoxide; CO oxidation; COX.

1. Introduction

The oxidation of carbon monoxide is of paramount interest for its strong environmental impact. The
total oxidation of CO to CO2 (COX) is traditionally carried out on supported noble metals such as
Pt, Pd and Rh that are known to have a high activity for abatement of CO in exhaust emissions [1-3].
Nevertheless, the high cost and low availability of noble metals have required the development of
new and cost-effective catalysts. In the last years an increasing interest in copper-based catalysts
has raised for the peculiar activity, abundance, low toxicity and low cost of this coinage metal.
Copper oxide and supported copper oxides [3, 4] are known to be highly active for CO oxidation.
Most of the studies on copper-based systems have been carried out on supported copper oxides such
as CuO/CeO2 [5-8], CuO/ZrO2 [9], CuO/Al 2 O3 [10] and CuO-Fe2O3 [11]. The use of ceria

guarantees a high availability of surface oxygen and high surface reducibility [12].
In recent years, the interest in this reaction has risen by the need to remove carbon monoxide from
the feed stream of fuel cells and numerous studies have been done on the selective oxidation of CO
in the presence of high amounts of H 2 (CO-PROX reaction) by copper-based catalysts [13-23].

Many investigations have been also carried out on CuO-CeO2-ZrO2 systems as CO oxidation
catalysts, both in the absence and in the presence of hydrogen [16-22]. The performance of these
three-component catalysts has been found strongly dependent on the Cu/Ce/Zr oxides molar ratio
and the synthetic methodology, therefore many different methods have been proposed for the
preparation of Cu-Ce-Zr systems, such as forced co-hydrolysis [24], co-precipitation [25], sol–gel
[26], thermal decomposition [27], freeze-drying method [28].
Based on these results, the CuO/CeO2 /ZrO2 system, containing a low amount of CuO, as an active

component and ceria as a reversible oxygen source on zirconia as a support was recently proposed
as one of the most promising catalyst for the CO-PROX reaction [29]. The use of a support like
ZrO 2 decreases costs of the CuO-CeO2 system and can contribute to stabilize the supported active

components. Aguila et al. [18] studied the effect of different supports on the activity of the CuO-
CeO2 system for CO oxidation in the absence of H2. Oxides as alumina, silica and zirconia were

used as the supports and the results suggested that use of the latter could be an interesting
alternative to be compared with Al2O3 and SiO2 ones.
The physico-chemical properties of zirconia, including crystal structure, specific surface area, pore
size distribution and acid-base characteristics, can be tailored according to the preparation method

and thermal treatments [30-32]. It is known that ZrO2 exhibits three different polymorphs,
monoclinic (m-ZrO2), tetragonal (t-ZrO2) and cubic (c-ZrO2), and low temperatures stabilize t-ZrO2
and c-ZrO2 forms.
The interaction between the different zirconia crystal phases and cerium and copper oxide species
can modify the shape and size of active sites, resulting in systems that exhibit different redox
properties. Particular attention has been given to m-ZrO2, to low temperature stabilized t-ZrO2 form,
and to a mixture of monoclinic and tetragonal phases. Although the effect of the monoclinic or
tetragonal phase on the catalytic performance of zirconia-based catalysts has been found for a
number of reactions [32-35], to the best of our knowledge the influence of crystal structures on the
complete oxidation of CO to CO2 has not been investigated. On these bases, four different zirconia
supports were synthesized either by sol-gel type or precipitation method, obtaining pure or mixed
monoclinic and tetragonal phases and different textural properties.
It is well known that the redox properties of copper oxide species for CO oxidation promotion
depend strongly on their dispersion degree, as well as on the ceria-copper molar ratio in the catalyst
surface and the related degree of interaction between these two oxides. It has also been proved that
the CO conversion increases with the increase in Cu content, until the loading is kept below the
maximum dispersion capacity, while it drops off dramatically with a further amount of copper [13,
14, 18, 21, 22, 36-39]. Therefore, according to previous findings on the reducibility of copper-ceria
catalysts, in this study CeO2 and CuO loadings were kept constant, varying only the phases of
zirconia support, in order to investigate the effect of the preparation route of ZrO2 and the possible
influence of its crystal structure on the CuO-CeO2 /ZrO2 systems.

The final Cu-Ce-Zr oxide catalysts were prepared by the method of incipient wetness impregnation
with copper(II) and cerium(III) nitrates, to obtain a nominal loading of 6 wt% of CuO and 20 wt%
of CeO2, followed by calcination. Their activity was evaluated in the total oxidation of CO to CO2 R

in the range 40-215°C and correlations between catalytic activity and physico-chemical properties
of the materials were made by means of several techniques.

2. Experimental

2.1 Materials
Zirconium propoxide (Zr(OPr) 4 , Aldrich 70 wt% in propanol), aqueous ammonia (NH 3 (aq), Fluka

28 wt%), ethanol (EtOH, Aldrich 99.8%), toluene (Aldrich, 99%) cetyltrimethylammonium

bromide (CTAB, Aldrich 98%), hydrochloric acid (HCl, Fluka 37 wt%) cerium(III) nitrate
hexahydrate (Ce(NO 3 ) 3 ·6H 2 O, Aldrich 99.99%), copper(II) nitrate trihydrate (Cu(NO 3 ) 2 ·3H 2 O,

Aldrich 99.9%), magnesium(II) nitrate hexahydrate (Mg(NO 3 ) 2 ·6H 2 O, Fluka 99%). Reagents were

all used as received.

2.2 Synthesis of zirconia by type sol-gel synthesis

The synthesis was adapted from the procedure to prepare mesoporous silica nanoparticles (MSNs)
[40]. Shelter measures were taken to avoid uncontrolled hydrolysis of zirconium alkoxides and the
surface area loss. Nitrogen atmosphere affords the removal of the moisture from the reaction
environment and the ice bath during the dropping step was used to slow down the kinetic of
hydrolysis. No complexing agents of the organic precursor are involved during the reaction. In a
typical synthesis, deionized water (37 mL, 2.04 mol), EtOH (4.56 mL, 99.8 mmol) and CTAB
powder (1.45 g, 3.98 mmol) were mixed together and stirred at room temperature (RT) in a round-
bottom flask until the complete dissolution of CTAB. Toluene (1.7 mL) was used as a swelling
agent and added with a CTAB:toluene = 1:4 molar ratio to the solution containing the surfactant.
Later, ammonia solution (0.32 mL, 4.6 mmol) was added to the mixture under continuous stirring.
Dropping funnel was put on the round-bottom flask, all placed inside an ice bath and a nitrogen
atmosphere was generated inside the reactor. The funnel was filled with Zr(OPr) 4 (7.27 mL, 16.2

mmol) which was added dropwise very slowly. Then the temperature was increased to 60 °C with
an oil bath and the reaction was continued for 2 h. The suspension was cooled to RT and the solid
product was recovered and repeatedly washed (initially with deionized water and finally with
EtOH) with four cycles of centrifugation (30 min at 9 krpm). In order to remove the organic
template the method performed by Che et al. [41] was adopted. Thus, magnesium nitrate was milled
with the zirconia powder with a weight ratio 1:1. After one hour step at 140 °C, the powder was
calcined at 500 °C for 6 hours. After that, the magnesium oxide formed inside the zirconia network
was removed with an etching process with HCl 10% for 3 days. The powder was recollected by
centrifugation and the pH was neutralized with five water-washing cycles, then it was dried at
90 °C and calcined for 3 h at 500 °C. The sample was identified as Zr500-a.
The sample Zr500-b was obtained in the absence of toluene as swelling agent. All the synthetic
process remained the same of Zr500-a.

2.3 Synthesis of zirconia by precipitation

An ethanol solution of ZrOCl 2 (0.2 M) was treated with an aqueous solution of NH 3 in a 30%

molar excess. The white precipitate was stirred for 2 hours, centrifuged and washed first with a
diluted NH 3 solution, and then with deionized water until no Cl- was detected (AgNO 3 test). The

obtained precipitate was dried at 90 °C and then calcined for 3 h at two different temperatures, 500
and 700 °C. The samples were named Zr500-c and Zr700-c, respectively.

2.4 Catalysts preparation

The fresh prepared zirconia samples, referred as Zr500-a, Zr500-b, Zr500-c and Zr700-c, were co-
impregnated with cerium and copper nitrates in ethanolic solution in order to load 20 wt% and 6
wt% of the respective oxide. Calcination was performed at 500 °C for 5 hours. The final catalysts
were referred to as CuCexx, where xx stands for the support utilized (e.g. CuCeZr500-a is the
catalyst derived from Zr500-a support). Fresh and used were referred to the catalysts before and
after one cycle of COX reaction test, respectively.
The actual copper and cerium content (nominal 4.8 wt% and 16.3 wt% respectively) determined by
ICP-OES elemental analysis, resulted as 4.7 wt% of Cu for all the samples; 16.2 wt% of Ce for the
samples CuCe Zr500-a, CuCe Zr500-c and CuCe Zr700-c and 16.3 wt.% of Ce for the sample CuCe

2.5 Characterization techniques

Inductively coupled plasma/optical emission spectrometry (ICP-OES) analyses were performed
with a Perkin-Elmer Optima 3100 XL spectrometer.
X-ray Powder Diffraction (XRPD) patterns were obtained using a Philips X'Pert system with a Cu
Kα radiation (λ=0.154056 nm). The average dimension of the crystallites was determined by the
Warren-Averbach’s equation (the estimated errors were 10% ca).
Nitrogen adsorption-desorption measurements were performed at liquid nitrogen temperature (-
196 °C) by a Micromeritics ASAP 2010 apparatus. Before each measurement, the samples (0.1 g)
27T 27T

were outgassed first at 130 °C for 12 h at 0.67 Pa and then at room temperature for 2 h at 1·10-4 Pa. P P

The N 2 isotherms were used to determine the specific surface areas through the BET equation

(S.A. BET ), and the specific pore volume (Vs) calculated at P/P 0 =0.98.

Hydrogen Temperature-Programmed Reduction (H 2 -TPR) experiments were carried out using an


AUTOCHEM 2910 instrument from Micromeritics. Approximately 0.1 g of freshly calcined sample
were placed on top of some wool glass in a quartz reactor. In order to remove contaminants, the
powder was pre-treated in helium (20 cm3 min-1) to 350 °C for 1 h. After cooling to room

temperature, the TPR experiments were carried out in 10 vol.% H 2 /Ar (30 cm3 min-1) increasing the

temperature from 40 to 800 °C (10 °C min-1). A Dewar flask containing a liquid nitrogen/ethanol

slurry was used as cryogenic trap to prevent water to contact the detector.

Raman spectra with the excitation laser at 532 nm were collected by using the 1 × 1 camera of a
Bruker Senterra Raman microscope by averaging spectra during 60-90 min with a resolution of 3–5
cm−1. A CCD camera operating at −50  ºC was used for the Raman detection.

X-Ray Photoelectron Spectrometry (XPS) was performed using a Physical Electronics PHI 5700
spectrometer with non monochromatic Mg Kα radiation (300 W, 15 kV, 1253.6 eV) for the analysis
of the core level signals of C 1s, O 1s, Zr 3d, Ce 3d and Cu 2p and with a multi-channel detector.
Spectra of powdered samples were recorded with the constant pass energy values at 29.35 eV, using
a 720 μm diameter analysis area. During data processing of the XPS spectra, binding energy values
were referenced to the C 1s peak (284.8 eV) from the adventitious contamination layer. The PHI
ACCESS ESCA-V6.0 F software package was used for acquisition and data analysis. A Shirley-
type background was subtracted from the signals. Recorded spectra were always fitted using Gauss-
Lorentz curves, in order to determine the binding energy of the different element core levels more
accurately. The error in BE was estimated to be ca. 0.1 eV. A short acquisition time of 10 min was
used to examine C 1s, Cu 2p and Cu LMM XPS regions in order to avoid, as much as possible,
photoreduction of Cu2+ species. Nevertheless, a Cu2+ reduction in high vacuum during the analysis

cannot be excluded [42].

2.6 Catalytic activity tests

Catalytic activity tests were carried out in a laboratory flow apparatus with a fixed bed reactor
operating at atmospheric pressure. The catalyst, with a defined particle size (0.050-0.110 mm), was
introduced into a tubular Pyrex glass reactor (5 mm i.d.), placed in an aluminum heating block.
Before the catalytic experiments, the sample was heated in situ at 350 °C under flowing filtered
atmospheric air for 30 min. The gas hourly space velocity, GHSV, was 22000 h-1. The feed P P

consisted of 1.25% CO and 1.25% O 2 (% vol.) balanced with He. Calibration of the GC was done

with a gas mixture containing 1% CO, 1% CO 2 , 1% O 2 in He.


The gas lines were heated at 120 °C, to avoid water condensation before the reactor inlet. An ice-
cooled water condenser was used to trap the excess of water downstream of the reactor. A HP6890
GC gas chromatograph equipped with a thermal conductivity detector was used to analyze the
outlet composition. A CP Carboplot P7 column was used, with helium as carrier. The detection
limit for CO was 10 ppm. The temperature was varied in the 40-215 °C range, and measurements
were carried out till a steady state was achieved. The carbon monoxide and oxygen fractional
conversions were calculated based on the CO (Eq.1) and O 2 (Eq.2) consumption, respectively:

n𝑖𝑛 𝑜𝑢𝑡
CO Conversion (%) = ∙ 100 (1)

n𝑖𝑛 𝑜𝑢𝑡
𝑂2 −n𝑂2
O2 Conversion (%) = ∙ 100 (2)
𝑂 2

The tests were conducted for two cycles to evaluate the stability of the catalysts (used samples were
heated again in situ at 350°C under flowing filtered atmospheric air for 30 min and tested using the
same operating conditions).
To determine the apparent activation energy, Ea, experiments in differential conditions were
performed in the temperature range 50-90 °C, to obtain CO conversion values below 25%. The total
feed flow rate and the mass of the catalyst were varied in order to assure differential conditions in
the reactor. The reaction rate was calculated as follows:
𝑚𝑜𝑙𝐶𝑂 𝐹𝐶𝑂,0 ∙𝑋𝐶𝑂
−𝑟𝐶𝑂 ( )= (3)
𝑔𝑐𝑎𝑡 ∙𝑚𝑖𝑛 𝑊

where (-r CO ) is the reaction rate of CO oxidation, W the catalyst weight (in g), X CO the carbon

monoxide fractional conversion obtained from equation (1), and F CO,0 is the molar flow of CO at

3. Results and Discussion

3.1. Catalytic activity in CO total oxidation at low temperature

The catalytic activity of the samples was evaluated in the COX reaction and the conversion profiles
as a function of the reaction temperature are presented in Fig. 1. All samples were tested twice. The
second catalytic cycle was carried out using the same conditions used in the first one and the
reaction profile resulted superimposable to the first one in all cases.
As shown in Figure 1, samples with the same amount of copper (4.7 wt%) and cerium (about 16.2
wt%), kept constant in order to investigate the possible influence of zirconia crystal structure on the
systems, but using ZrO 2 supports prepared by different synthesis approaches, exhibit a quite

different catalytic behavior, indicating the important role of the support in this reaction. All samples
showed a good catalytic performance, reaching conversions near 100% at 140 °C. Sample
CeCuZr500-c shows the highest catalytic performance in the 40-215 °C temperature range, proving
to be able to oxidize completely CO to CO 2 in the temperature range 115-215 °C, with a T 50

(temperature at which conversion is 50%) of 65 °C. CeCuZr500-a and CeCuZr500-b show a similar
CO oxidation efficiency being the CeCuZr500-b catalyst slightly more active in the 40-115 °C
range, with a T 50 =78 °C, few degrees lower than CeCuZr500-a (T 50 =83 °C). CeCuZr700-c catalyst

shows a poor catalytic performance, with a T 50 rather high (T 50 =102 °C).


As stated in the introduction section, no work was found about the role of zirconia support in the
activity of Cu-Ce based catalysts in COX reaction. However, in order to highlight the interesting
results of the prepared catalysts, a comparison of the reaction rates and the CO conversion (%)
values measured in the present work and those from literature for Cu-Ce catalysts is shown in Table
1. Although the reaction conditions are often slightly different, the studied catalyst activities are
comparable to the literature systems here reported. This is an important observation because it
underlines that a simple co-impregnation of a zirconia support, prepared through precipitation and
calcination, can lead to the realization of a catalyst with very good redox properties and high
dispersion of the active phases (see below), and with appreciable activity comparable or even higher
than that obtained by catalysts obtained by more complex synthetic methodologies.

On the other hand, the apparent activation energies (Ea) for the reaction of total CO oxidation were
obtained by Arrhenius plot and reported in Tab. 1. These values are in good agreement with those
reported in literature for the CO oxidation process over CuO/CeO 2 and CuO/CeO 2 /ZrO 2 catalysts. R R R R R R

In this sense, Jia et al. [45] reported for CuO/Ce 1−x Cu x O 2 and Ce 1−x Cu x O 2 catalysts, apparent

activation energy values of 42±2 kJ mol−1 and 95±5 kJ mol−1, respectively. Some authors, studying

the oxidation of CO at low temperature over CuO/CeO 2 catalysts by TPD and IR spectroscopic data

[46], found that CO forms on CuO clusters, at low temperature, bridging and mono/bidentate
carbonate complexes that decompose, with an Ea of 64 kJ/mol, with the release of CO 2 . It is worth R R

noting here that the catalyst CuCeZr500-c shows a quite low apparent activation energy,
comparable with that of CuO/CeO 2 catalysts prepared through more complex synthethic stategies.

Finally, a durability test was performed at 90 °C on the sample with the highest catalytic
performance, CuCeZr500-c. The reaction was monitored for 80 h maintaining the temperature
constant (using GHSV = 22,000 h−1; 1.25% CO, 1.25% O 2 , He balance (vol.%)). The catalyst

showed a diminution of CO conversion from 93% to 91% within the first 8 h, remaining stable for
the further operation time.

3.2 Characterization results

In order to better understand the catalytic behavior of the studied catalysts, they were characterized
by several experimental techniques.
The textural properties of the zirconia supports and those of the corresponding CuO-CeO 2 loaded R R

samples were calculated from their corresponding N 2 adsorption-desorption isotherms at -196°C


(Fig. 2). The obtained values, in terms of BET specific surface area and cumulative pore volume,
are included in Table 1.

N 2 physisorption analyses of the bare zirconia prepared by different methodologies are reported in

Figure 2. As shown, the isotherm of the Zr500-a sample is an intermediate between type I and IV
isotherm, characteristic of a material with an important contribution of microporous, as seen from
the sharp increase of the pore volume at low p/p 0 . The Zr500-b zirconia support exhibits reversible

type IV isotherm, according to the IUPAC classification. It presents an inflection at p/p 0 =0.35-0.40,

characteristic of capillary condensation within uniform mesopores. This uniformity is also shown
by the narrow pore size distribution calculated by the BJH method on the adsorption branch of the
isotherm. The very narrow hysteresis loop can be ascribed to a similar mechanism for the
adsorption-desorption processes, which reflects the absence of adsorbate pore blocking in sample
Zr500-b. Zr500-c support shows a type IV isotherm of a mesoporous material with a broad pore
size distribution, while the corresponding sample treated at higher temperature, Zr700-c, exhibits an
isotherm typical of a low surface area material with a very broad pore size distribution. The BET
specific surface area of the zirconia supports, showed in Table 2, ranges between 375 m2g-1, in theP P P P

case of the Zr500-a sample, and 21 m2g-1 in the case of the zirconia obtained by precipitation and

calcined at 700 °C, Zr700-c sample.

A decrease of specific surface area and pore volume (Table 2) was observed after the impregnation
of the support with cerium and copper nitrates and subsequent calcination, most probably
attributable to a certain degree of pore blockage caused by the presence of metal oxide particles.
The decrease in the textural properties is much more significant in the case of samples prepared by
a sol-gel methodology (CuCeZr500-a and CuCeZr500-b), pointing to a possible partial collapse of
the structure after metal incorporation. Instead, the structure of catalysts prepared by precipitation is
more stable, with surface area values similar to that of the bare support.

After one cycle of activity, not evident changes were found in specific surface area, pore volume,
and pore size distribution, which remained almost unchanged, within the experimental error.
The X-ray diffraction profiles of the Cu-Ce-Zr oxide catalysts were analysed in order to evaluate
the crystalline phases formed. The single phases were resolved by following a careful Rietveld
study of the diffraction patterns (Fig. 3) to obtain quantitative information on the composition and
the distribution of the different phases. The Rietveld’s method was used for the diffraction peak
decomposition and the content evaluation of detected zirconia phases. Only tetragonal zirconia

phase (100 wt% of t-ZrO 2 ) was detected when a type sol-gel synthesis was used to prepare the

supports Zr500-a and Zr500-b, as assumed by developing this peculiar synthetic methodology. On
the contrary, a high percentage of monoclinic phase was detected when ZrO 2 was prepared by

precipitation and thermally treated at 500 °C or 700 °C (Fig. 3). In detail, 80 wt% of m-ZrO 2 and 20

wt% of t-ZrO 2 phases were calculated for the sample CuCeZr500-c and 91 wt% of m-ZrO 2 and 9

wt% of t-ZrO 2 phases for the catalyst CuCeZr700-c.


Moreover, the characteristic reflections of cerianite, CeO2, clearly appear and match well with the

peaks of the cubic fluorite crystal structure in JCPDS database (No. 43-1002).
The mean size of cubic cerium oxide crystallites (Table 3) obtained for CuCeZr500-a and
CuCeZr500-b catalysts was 7.9 nm and 6.6 nm, respectively, and it was found very small, 5.2 nm,
for the sample CuCeZr500-c. The catalyst CuCeZr700-c exhibited a ceria crystallite size of 14.0 nm,
as expected larger than that observed for sample CuCeZr500-c, and very similar to that found in the
literature for a Cu–Ce-Zr mixed oxide system with a very low specific surface area [47].

The XRD profiles of the catalysts do not present any change after one cycle of COX test reaction in
the 40-215 °C range (Fig. 4). It is worth noting that neither tenorite, CuO, nor other copper-based
phases were detected both in the fresh and used catalysts, suggesting that copper is present in a
highly dispersed form or amorphous structure. Anyway, due to the complex X-ray profile of the
supports, the presence of copper oxide cannot be discarded in samples CuCeZr500-c and

3.4. Raman spectroscopy

Figure 5 shows the Raman profile of Zr500-c and Zr700-c supports as well as their respective
CuCeZr catalysts. The materials prepared from a sol-gel process showed very low intense Raman
lines probably ascribed to their much lower crystallinity, as observed from XRD. In line with this,
the spectrum corresponding to Zr700-c sample is more intense than that of Zr500-c one, in
agreement with the higher degree of crystallinity of the former.

Considering the Raman spectra of the supports prepared from the precipitation method, similar
bands are observed. From XRD results, both samples present tetragonal and monoclinic ZrO 2 . The R R

most important differences between the monoclinic and tetragonal phase in Raman spectroscopy are
that bands located at ca. 149, 269 and 312 cm-1 are exclusively assigned to the t-ZrO 2 ; meanwhile

bands at 178, 191 and 337 cm-1 are assigned to the monoclinic phase. Moreover, the bands at 470

and 635 cm-1 are common for both phases but their relative intensity is different. Thus, for the

tetragonal phase, the intensities of the bands at 470 and 635 cm-1 are about the same or slightly

stronger for the band at 635 cm-1; but the intensity of the band at 470 cm-1 is much stronger for the

monoclinic phase. Besides, there are some small bands in between 470 and 635 cm-1 for the P P

monoclinic phase, but these weak bands are absent for the tetragonal phase [48].
In these spectra, the bands at 176, 188, 221, 332, 335, 380, 502, 536, 558, 583 and 610 cm-1 can be P P

ascribed to the Vibration of Zr-O monoclinic zirconia [48, 49] and those at 142 and 305 cm-1 to the P P

tetragonal phase. In both cases the intensity of the band at 470 cm-1 is higher than that at 635 cm-1,

indicating that the monoclinic phase is that predominant in good agreement with the results from X-
ray diffraction.
The spectra of the catalysts present similar features but with much lower intensity and the peaks not
well resolved.
The CuO–CeO 2 /ZrO2 catalysts were characterized by H2-temperature programmed reduction (H 2 -

TPR) to evaluate the reduction behavior of the catalysts. The profiles of all the materials are
displayed in Fig. 6 and the corresponding experimental H 2 consumption are listed in Table 2.

Cu–Ce-Zr mixed oxides, with different copper loadings and different CeO 2 /ZrO 2 ratios, have been R R R R

deeply investigated [16, 17, 50-52]. It has been generally reported a lowering of the reduction
temperature of supported CuO, with respect to pure CuO, that usually reduces above 250 °C,
attributed to a strong interaction between highly dispersed copper oxide species and ceria, and a
partial reduction of ceria at relatively low temperatures [53]. As known, pure zirconia cannot be
reduced in hydrogen flow below 930 °C, while ceria gave a very broad peak starting at 650 °C, and
centered at about 750 °C (not shown), related to a limited surface reduction of cerium atoms from
+4 to +3 oxidation state, while the reduction of CeO 2 to Ce 2 O 3 usually occurs at higher

temperatures [54].
In all the prepared Cu-Ce-Zr samples, the presence of some partially overlapped reduction peaks
was observed in the range 100-165 °C, indicating the presence of at least two types of copper
Ratnasamy et al. [15], studying the reducibility of supported copper species on different supports,
evidenced that Cu2+ species reducibility increases in the order CuO-ZrO 2 < CuO-CeO 2 < CuO-

CeO 2 -ZrO 2 that was assigned to the different dispersion of the surface copper species. Manzoli et al.

[16] found, by H 2 -TPR measurements, a clear correlation between the Ce x Zr 1-x O 2 support

composition and the reduction temperature of copper oxide species. They reported a moderate shift
of the reduction temperatures of CuO towards higher values with increasing the ZrO 2 content of the R R

support up to Ce 0.5 Zr 0.5 O 2 , while the reduction temperature was found to decrease at higher ZrO 2

Literature data for CuO-CeO 2 -ZrO 2 mixed oxides, when CeO 2 is the most abundant component,

report overlapped TPR profiles composed by up to four peaks. This quite complex behavior has
been attributed to the reduction of finely dispersed copper oxide species highly associated with
ceria; to small two- and three-dimensional clusters of CuO that weakly interact with ceria; to the
presence, in the ceria lattice, of copper oxide both in solid solution and interstitial or substitutional
defects; and, eventually, to the reduction of Cu2+ ions of the bulk-type particles in CuO crystalline

phase usually observed in XRD patterns [52, 54, 55].

In this specific case, where zirconia is the support and ceria is present in amount of 20 wt%, the H 2 - R R

TPR profiles seem to be composed by two or three overlapped peaks.

The CuCeZr500-a catalyst exhibits a H 2 -TPR profile composed by two large peaks, the first one at

106 °C and the second one at 163 °C. CuCeZr500-b appears slightly different, showing the first
peak at the same position, 106 ºC, and the second one at lower temperature, 134 °C. This different
behavior could be attributed to the presence of micropores in the former material. In this sense, after
active phase deposition and thermal treatment at 500 °C, it is observed a sharp decrease in the
surface area and in the total pore volume of this catalyst. These data and TPR results point to the
blockage of the micro- and mesoporous structure and the formation of CuO larger particles, in the
explaining the reduction peak at higher temperature that is absent in other samples.
The profile of CuCeZr500-c, more similar to that of CuCeZr500-b, shows a reduction peak at
101 °C followed by a second peak at 125 °C with a shoulder at 136 °C. The component attributed to
the bulk-type CuO particles in crystalline phase cannot be observed, as also confirmed by XRD
The profile of CuCeZr700-c sample shows the almost total absence of the lowest temperature
reduction peak.
In this class of catalysts, with the same chemical composition, the reducibility of copper species in
H 2 flow seems to depend both on their dispersion on the support, their size and their interaction

with ceria [10]. By comparing the TPR profiles, they seem to be quite sensitive on the conditions of
catalyst preparation. Moreover, it is seen that CeCuZr500c, supported on precipitated ZrO 2 , shows R R

to contain the more easily reducible Cu species, as indicated by the peak at low temperature.
Quantitative analysis of H 2 consumed for the reduction of the copper species in the CuO-CeO 2 -

ZrO 2 systems is shown in Table 2 1. The theoretical H 2 consumption required for the complete

reduction of all the copper species of the catalysts from Cu2+ to Cu0 in comparison with the P P P P

experimental H 2 uptake (H 2 /Cu molar ratio) is also reported. As shown in Table 2 1, there is a large

discrepancy between theoretical and experimental values. In fact, except in the case of CuCeZr700-
c sample, total H 2 consumption is always higher than the stoichiometric one. The experimental

H 2 /Cu ratio indicates that the H 2 consumption for CeCuZr500-a CeCuZr500-b and CeCuZr500-c

catalysts is higher than the theoretical amount necessary for the complete reduction of copper oxide
present in the samples, suggesting that some CeO 2 reduction must occur at low temperatures [56].

On the other hand, the presence of hydrogen spillover on the support in a wide temperature range
cannot be discarded [57-59]. Sample CeCuZr500-c is that presenting the highest amount of uptake
hydrogen that suggests the support is reduced easily than in the other cases.
Zhao et al. [60], studying the effect of zirconia phase on the reduction behavior of highly dispersed
zirconia-supported copper oxide, reported that exists some differences between the reduction
behavior of CuO supported either on tetragonal or monoclinic zirconia. They surprisingly found, in
the H2-TPR profile, only a reduction peak at low temperature for t-ZrO2 and two reduction peaks in
the CuO supported on m-ZrO 2 . However, in our case, this behavior is not clearly observed since

ceria is also present into the catalyst formulation. In this sense, no relationship with the presence of
monoclinic or tetragonal phase can be clearly evidenced. The different copper reducibility can be
related, as found by many authors, to the different crystal size of ceria nanoparticles calculated by
X-ray diffraction measurements.

3.5 X-ray Photoelectron Spectroscopy

Redox properties of the catalysts, both fresh and used, were investigated by X-ray photoelectron
spectroscopy. C 1s, O 2p, Cu 2p, Ce 3d and Zr 3d core level spectra were recorded and analyzed to
determine the species present on the sample surface.
The O 1s core excitation envelope (not shown) displays in all cases two contributions assigned to
oxygen in the metal oxide lattice (close to 529-530 eV) and surface oxygen (O-, OH-, CO32-, -CO22-)
(531-532 eV) [61] The first species, at BE of approximately of 529.3 eV, was found as the
predominant contribution. If all the spectra are compared, CuCeZr500-c sample is that presenting
the larger proportion of surface oxygen that is reported to be involved in total oxidation reactions,
with beneficial spillover phenomena on the surface, controlling the formation and regeneration of
the active centers [49]. The Zr 3d5/2 core excitations only showed the presence of one component
centered at 181.8 eV, close to the values reported for Zr4+ in the zirconia lattice 182-182.5 eV [62].

The chemical state of copper ions was evaluated from Cu 2p and CuLMM Auger signals. The Cu
2p core level spectra of sample CeCuZr500-c, before and after COX reaction, are presented in Fig.
7a as an example. The main Cu 2p 3/2 peak is centered in all cases between 932.8-933.5 eV, close to

the values observed in previous works, where Cu1+, Cu2+ and Cu0 species coexist [47, 59]. The

presence of the clear defined shake up satellite suggests the presence of Cu2+. No major changes in
the spectra are observed before and after the catalytic tests.

Copper also showed the well-known CuLMM Auger signal in the kinetic energy range 916-918 eV.
The modified Auger parameter (’) was calculated from photoelectron and Auger signal as follows:
where E B is the binding energy of the Cu 2p core level and E K is the kinetic energy of the CuLMM

Auger electron [61, 63]. The obtained values, as well as the Cu 2p 3/2 main peak binding energy

values, are included in Table 4. Combining the kinetic energy of the X-ray induced Auger lines and
the binding energy of the photoelectron lines of copper in a two-dimensional plot, the Wagner
chemical state plot was obtained for copper species of the investigated catalysts (Fig. 8). This
diagram gives an idea about the chemical state of copper: metallic and oxidized Cu(I) and Cu(II).

All the samples showed the presence of copper ions with a valence between +2 and +1.
Nevertheless, the three samples supported on zirconia calcined at 500 °C exhibit a larger amount of
Cu species with an intermediate state between +2 and +1; while the sample calcined at 700 ºC is
that presenting values closer to CuO species. In fact, if the ratio of shake up satellites to respective
main photoelectron peak is calculated (Table 4), CuCeZr700-c sample exhibits a significant
contribution of Cu2+ ions in the surface composition, with a value close to that reported for CuO

(0.55). Instead, the samples thermally treated at lower temperature show much lower values, in
accordance to the data obtained from the Wagner plot. Moreover, this ratio decreases after catalytic
testing, suggesting that copper ions are slightly reduced during the reaction.

With regard to Ce 3d core level spectra (Fig. 8), in all cases five spin-orbit doublets denoted as v(n)
and u(n) can be observed. Three doublets are ascribed to the presence of Ce4+: v (~882.8 eV) and u

(~ 901.3 eV); v’’ (~888.9 eV) and u’’ (~ 907.6 eV); v’’’ (~898.5 eV), u’’’ (~917.1 eV)-. Meanwhile
two doublets: v 0 (~881.2 eV) and u 0 (~900 eV); v’(~885.3) and u’ (~ 903.7 eV)- are assigned to

Ce3+ [56, 58].


From Fig. 7b 6b it is seen that cerium species are mainly present in Ce4+ oxidation state. However,

Ce3+ species also seem to be present but in much lesser proportion. Although component v 0 is not

noticeable, v’-u’ doublet is distinguishable. The component v’ as a shoulder between v-v’’ is more
pronounced for CeCeZr500-c sample, therefore indicating that on this material there is a larger
proportion of reduced Ce ions.

With regard to the surface atomic concentration, it can be seen that samples prepared from
precipitated zirconia, Zr500-c, show a much higher surface enrichment of Cu and Ce with respect to
the other samples, most probably due to the preferential location of Cu and Ce species on the
external surface of the support. Instead it is observed how samples CuCeZr500-a and CuCeZr500-b
suffer a sharp decrease in the porosity after Cu and Ce incorporation: micro and mesopores are
blocked by the active phase and the formation of larger particles occur as seen from XRD and also
evidenced from H2-TPR measurements.

As outlined in the Introduction section, an important feature of catalysts supported on ZrO 2 is the

possible activity dependence on its polymorphic structure.

If the catalytic results are considered, some differences among the samples containing pure or
mixed t-ZrO 2 and m-ZrO 2 phases were found. The sample CuCeZr500-c, that presents both

tetragonal and monoclinic crystalline zirconia polymorphs (support constituted by 20 wt% t-ZrO 2 R R

and 80 wt% of m-ZrO 2 ) exhibits the highest activity in concomitance with the lowest value of

activation energy. On the other hand, in the case of CuCeZr700-c sample, where both tetragonal
and monoclinic crystalline structures (9 wt% t-ZrO 2 and 91 wt% of m-ZrO 2 ) are present too, the

assistance of both the phases was offset by a very low surface area and by the presence of copper
ions less easily reducible, as shown by H 2 -TPR measurements (Fig. 2). The very low surface area

and the different redox behavior of CuCeZr700-c sample can be ascribed to the high calcination
temperature of the support (700 °C), chosen to obtain a larger fraction of monoclinic phase (91
wt%), and to the presence of larger ceria crystallite size, as shown by XRD measurements. Samples
only containing tetragonal phase, CuCeZr500-a and CuCeZr500-b, present an intermediate catalytic
behavior between CuCeZr500-c and CuCeZr700-c. Therefore no linear relationship with the
presence of the different zirconia phases can be observed. This suggests that the zirconia
polymorphs are not a key factor in the complete oxidation of carbon monoxide to carbon dioxide at
low temperature.
If the preparation method is deeper analyzed, it plays an important role not only in the zirconia
phase formation. It is observed in fact that the sol-gel type methodology, that gives rise to ZrO2
mainly composed of tetragonal phase, has the advantage of providing very high specific surface
area and pore volume materials. Nevertheless, after active phase deposition a severe decrease of
specific surface area and pore volume (Table 2), attributable to a wide degree of pore blockage
caused by the presence of metal oxide particles and a collapse of the structure partially burying the
active sites, is observed.

Instead, the precipitation route that produces both tetragonal and monoclinic phases, the latter
always more important, and the amount of each one dependent on the calcination temperature, gives
rise to zirconia supports with relatively low surface area and thermally more stable, with the
advantage of being hardly affected by active phase deposition.
As reported in literature, the CO oxidation over copper oxide catalysts obeys a Mars-van Krevelen
redox mechanism [4] and the reaction rate is enhanced when more surface lattice oxygen is
withdrawn from the metal oxide; copper valence can change during CO oxidation from Cu(II) to
Cu(I), which is considered more active than Cu(II) because it can seize or release surface lattice
oxygen more readily than CuO or Cu [64]. Moreover in systems copper-ceria, it is described that
the high dispersion and facile reducibility of CuO on CeO2 and CeO2–ZrO2 supports are responsible
for their superior activity/selectivity over CuO–ZrO2 catalysts. The high activity of the surface
copper species induced by the interaction with CeO2 was attributed to the promotion of the
concerted redox capability of surface copper clusters and cerium species. The interaction CuO-
CeO2 causes the reduction of the support and of the small CuO clusters to occur at low temperature
[18]. In this way, adsorption of CO produces an easy reduction of the catalyst’s surface with the
generation of CO2 at low temperature. Therefore, the CO oxidation activity is linked to the presence
of active copper sites in close interaction with the ceria.
In conclusion, in our case the very good performance in total CO oxidation shown by the sample
CuCeZr500-c, obtained by a precipitation-impregnation process, can be ascribed to the presence of
both a larger fraction of highly dispersed and easily reducible Cu species and nanocrystallites of
ceria, present both as Ce4+, in the largest fraction, and Ce3+ species, in much lesser proportion. In

addition, the higher stability and the easier accessibility of the reactants to the active sites play a
significant role in the catalytic behaviour of the CuO-CeO2-ZrO2 system.

Different ZrO 2 supports were synthesized by either type sol-gel methodology or precipitation to

investigate the effect of the preparation route of ZrO2 in CuO-CeO 2 /ZrO 2 catalysts for the oxidation

of carbon monoxide at low temperature (COX). Calcination of these materials produced pure or
mixed tetragonal (t-) and monoclinic (m-) phases. In this study CeO2 and CuO loadings were kept
constant, varying only the phases of zirconia support, in order to investigate the possible influence
of zirconia crystal structure on the systems. The supports were then impregnated with cerium and
copper nitrates, followed by calcination, to obtain a loading of 20 wt% of CeO2 and 6 wt% of CuO.

The studied catalysts exhibited a good catalytic behavior in the total conversion of CO to CO 2 , R R

reaching conversion values near 100% at 140 °C.

Samples prepared by a sol-gel methodology showed a severe decrease of specific surface area and
pore volume after the impregnation of the support most probably attributable to a certain degree of
pore blockage caused by the presence of metal oxide particles. The decrease in the porosity points
out also a partial collapse of the structure after metal incorporation. The catalysts prepared from
precipitation are instead more thermally stable, with surface area values similar to that of the bare
Although the effect of the monoclinic or tetragonal phases on the catalytic performance of zirconia-
based catalysts has been found in the literature for a number of reactions, a relationship cannot
clearly be observed since ceria is also present into the catalysts formulation. A clear correlation
among the reducibility and crystallite size of copper and ceria species and activity in the CO
oxidation was instead found. The sample CuCeZr500-c exhibited the highest activity proving to be
able to oxidize completely CO in the range 115-215°C, with T 50 of 65 °C, showing that a simple

co-impregnation of a zirconia support, obtained through facile and fast precipitation, can provide a
catalyst with very good redox properties and high dispersion of the active phases, and with
appreciable activity comparable or ever higher than that obtained by catalysts prepared by more
complex synthetic methodologies.

The authors acknowledge Mrs. Martina Marchiori for nitrogen physisorption analyses and the
Ministerio de Economía y Competitividad, Project CTQ2015-68951-C3-3-R and FEDER funds.
A.I.M. thanks the Ministry of Economy and Competitiveness (Spain) for a Ramón y Cajal contract

[1] I. Heo, D.Y. Yoon, B.K. Cho, I.-S. Nam, J.W. Choung, S. Yoo, Activity and thermal stability of Rh-
based catalytic system for an advanced modern TWC, Applied Catalysis B: Environmental, 121-122 (2012)
[2] J. Kašpar, P. Fornasiero, N. Hickey, Automotive catalytic converters: current status and some
perspectives, Catalysis Today, 77 (2003) 419-449.
[3] X. Liu, P. Ning, L. Xu, Q. Liu, Z. Song, Q. Zhang, Low-temperature catalytic oxidation of CO over
highly active mesoporous Pd/CeO2–ZrO2–Al2O3catalyst, RSC Adv., 6 (2016) 41181-41188.
[4] T.-J. Huang, D.-H. Tsai, CO Oxidation Behavior of Copper and Copper Oxides, Catalysis Letters, 87
(2003) 173-178.

[5] B. Skårman, T. Nakayama, D. Grandjean, R.E. Benfield, E. Olsson, K. Niihara, L.R. Wallenberg,
Morphology and Structure of CuOx/CeO2Nanocomposite Catalysts Produced by Inert Gas
Condensation: An HREM, EFTEM, XPS, and High-Energy Diffraction Study, Chemistry of Materials, 14
(2002) 3686-3699.
[6] D. Gamarra, C. Belver, M. Fernandez-Garcia, A. Martinez-Arias, Selective CO oxidation in excess H2
over copper-ceria catalysts: identification of active entities/species, Journal of the American Chemical
Society, 129 (2007) 12064-12065.
[7] G. Avgouropoulos, T. Ioannides, Selective CO oxidation over CuO-CeO2 catalysts prepared via the
urea–nitrate combustion method, Applied Catalysis A: General, 244 (2003) 155-167.
[8] C. Deng, Q. Huang, X. Zhu, Q. Hu, W. Su, J. Qian, L. Dong, B. Li, M. Fan, C. Liang, The influence of
Mn-doped CeO2 on the activity of CuO/CeO2 in CO oxidation and NO+CO model reaction, Applied
Surface Science, 389 (2016) 1033-1049.
[9] L. Kundakovic, M. Flytzani-Stephanopoulos, Reduction characteristics of copper oxide in cerium and
zirconium oxide systems, Applied Catalysis A: General, 171 (1998) 13-29.
[10] X.-y. Jiang, R.-x. Zhou, P. Pan, B. Zhu, X.-x. Yuan, X.-m. Zheng, Effect of the addition of La2O3 on
TPR and TPD of CuOγ-Al2O3 catalysts, Applied Catalysis A: General, 150 (1997) 131-141.
[11] A.E.-A.A. Said, M.M.M. Abd El-Wahab, M.N. Goda, Synthesis and characterization of pure and (Ce,
Zr, Ag) doped mesoporous CuO-Fe2O3 as highly efficient and stable nanocatalysts for CO oxidation at low
temperature, Applied Surface Science, 390 (2016) 649-665.
[12] A. Trovarelli, P. Fornasiero, Catalysis by Cerya and Related Materials, in, Imperila College Press,
London, 2013, pp. 565-621.
[13] E. Moretti, L. Storaro, A. Talon, M. Lenarda, One-pot mesoporous Al–Ce–Cu oxide systems as
catalysts for the preferential carbon monoxide oxidation (CO-PROX), Catalysis Communications, 10 (2009)
[14] E. Moretti, L. Storaro, A. Talon, R. Moreno-Tost, E. Rodríguez-Castellón, A. Jiménez-López, M.
Lenarda, CO Preferential Oxidation Activity of CuO/CeO2 Supported on Zirconium Doped Mesoporous
MSU Type Silica, Catalysis Letters, 129 (2009) 323-330.
[15] P. Ratnasamy, D. Srinivas, C.V.V. Satyanarayana, P. Manikandan, R.S. Senthil Kumaran, M. Sachin,
V.N. Shetti, Influence of the support on the preferential oxidation of CO in hydrogen-rich steam reformates
over the CuO–CeO2–ZrO2 system, Journal of Catalysis, 221 (2004) 455-465.
[16] M. Manzoli, R.D. Monte, F. Boccuzzi, S. Coluccia, J. Kašpar, CO oxidation over CuOx-CeO2-ZrO2
catalysts: Transient behaviour and role of copper clusters in contact with ceria, Applied Catalysis B:
Environmental, 61 (2005) 192-205.
[17] X. Dong, H. Zou, W. Lin, Effect of preparation conditions of CuO–CeO2–ZrO2 catalyst on CO removal
from hydrogen-rich gas, International Journal of Hydrogen Energy, 31 (2006) 2337-2344.
[18] G. Águila, F. Gracia, P. Araya, CuO and CeO2 catalysts supported on Al2O3, ZrO2, and SiO2 in the
oxidation of CO at low temperature, Applied Catalysis A: General, 343 (2008) 16-24.
[19] J. Astudillo, G. Águila, F. Díaz, S. Guerrero, P. Araya, Study of CuO–CeO2 catalysts supported on
SiO2 on the low-temperature oxidation of CO, Applied Catalysis A: General, 381 (2010) 169-176.
[20] V.P. Pakharukova, E.M. Moroz, V.V. Kriventsov, D.A. Zyuzin, G.R. Kosmambetova, P.E. Strizhak,
Copper–cerium oxide catalysts supported on monoclinic zirconia: Structural features and catalytic behavior
in preferential oxidation of carbon monoxide in hydrogen excess, Applied Catalysis A: General, 365 (2009)
[21] J. Zhu, L. Zhang, Y. Deng, B. Liu, L. Dong, F. Gao, K. Sun, L. Dong, Y. Chen, Influence of preparation
method on the catalytic activities of CuO/Ce0.67Zr0.33O2 catalysts in CO+O2 reaction, Applied Catalysis
B: Environmental, 96 (2010) 449-457.

[22] Á. Reyes-Carmona, A. Arango-Díaz, E. Moretti, A. Talon, L. Storaro, M. Lenarda, A. Jiménez-López,
E. Rodríguez-Castellón, CuO/CeO2 supported on Zr doped SBA-15 as catalysts for preferential CO
oxidation (CO-PROX), Journal of Power Sources, 196 (2011) 4382-4387.
[23] P.S. Barbato, S. Colussi, A. Di Benedetto, G. Landi, L. Lisi, J. Llorca, A. Trovarelli, CO preferential
oxidation under H2-rich streams on copper oxide supported on Fe promoted CeO2, Applied Catalysis A:
General, 506 (2015) 268-277.
[24] M. Hirano, T. Miwa, M. Inagaki, Low-Temperature Direct Synthesis of Nanoparticles of Fluorite-Type
Ceria–Zirconia Solid Solutions by “Forced Cohydrolysis” at 100°C, Journal of Solid State Chemistry, 158
(2001) 112-117.
[25] A.S. Deshpande, N. Pinna, P. Beato, M. Antonietti, M. Niederberger, Synthesis and Characterization of
Stable and Crystalline Ce1-xZrxO2Nanoparticle Sols, Chemistry of Materials, 16 (2004) 2599-2604.
[26] M. Alifanti, B. Baps, N. Blangenois, J. Naud, P. Grange, B. Delmon, Characterization of
CeO2−ZrO2Mixed Oxides. Comparison of the Citrate and Sol−Gel Preparation Methods, Chemistry of
Materials, 15 (2003) 395-403.
[27] T. Masui, Y. Peng, K.-i. Machida, G.-y. Adachi, Reduction Behavior of CeO2−ZrO2Solid Solution
Prepared from Cerium Zirconyl Oxalate, Chemistry of Materials, 10 (1998) 4005-4009.
[28] A. Arango-Díaz, E. Moretti, A. Talon, L. Storaro, M. Lenarda, P. Núñez, J. Marrero-Jerez, J. Jiménez-
Jiménez, A. Jiménez-López, E. Rodríguez-Castellón, Preferential CO oxidation (CO-PROX) catalyzed by
CuO supported on nanocrystalline CeO2 prepared by a freeze-drying method, Applied Catalysis A: General,
477 (2014) 54-63.
[29] G.R. Kosmambetova, V.I. Gritsenko, P.E. Strizhak, A.M. Korduban, Effect of the nature of the support
for copper-cerium oxide catalysts on selective oxidation of CO in hydrogen-rich mixtures, Theoretical and
Experimental Chemistry, 42 (2006) 133-138.
[30] G.K. Chuah, S. Jaenicke, The preparation of high surface area zirconia — Influence of precipitating
agent and digestion, Applied Catalysis A: General, 163 (1997) 261-273.
[31] K.T. Jung, A.T. Bell, The effects of synthesis and pretreatment conditions on the bulk structure and
surface properties of zirconia, Journal of Molecular Catalysis A: Chemical, 163 (2000) 27-42.
[32] M. Rhodes, A. Bell, The effects of zirconia morphology on methanol synthesis from CO and H2H2 over
Cu/ZrO2Cu/ZrO2 catalystsPart I. Steady-state studies, Journal of Catalysis, 233 (2005) 198-209.
[33] K.T. Jung, A.T. Bell, Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported
Copper, Catalysis Letters, 80 (2002) 63-68.
[34] L.-C. Wang, Q. Liu, M. Chen, Y.-M. Liu, Y. Cao, He, K.-N. Fan, Structural Evolution and Catalytic
Properties of Nanostructured Cu/ZrO2Catalysts Prepared by Oxalate Gel-Coprecipitation Technique, The
Journal of Physical Chemistry C, 111 (2007) 16549-16557.
[35] M.C. Campa, G. Ferraris, D. Gazzoli, I. Pettiti, D. Pietrogiacomi, Rhodium supported on tetragonal or
monoclinic ZrO2 as catalyst for the partial oxidation of methane, Applied Catalysis B: Environmental, 142-
143 (2013) 423-431.
[36] E. Moretti, M. Lenarda, L. Storaro, A. Talon, R. Frattini, S. Polizzi, E. Rodríguez-Castellón, A.
Jiménez-López, Catalytic purification of hydrogen streams by PROX on Cu supported on an organized
mesoporous ceria-modified alumina, Applied Catalysis B: Environmental, 72 (2007) 149-156.
[37] J.L. Ayastuy, A. Gurbani, M.P. González-Marcos, M.A. Gutiérrez-Ortiz, Effect of copper loading on
copper-ceria catalysts performance in CO selective oxidation for fuel cell applications, International Journal
of Hydrogen Energy, 35 (2010) 1232-1244.
[38] E. Moretti, M. Lenarda, P. Riello, L. Storaro, A. Talon, R. Frattini, A. Reyes-Carmona, A. Jiménez-
López, E. Rodríguez-Castellón, Influence of synthesis parameters on the performance of CeO2–CuO and
CeO2–ZrO2–CuO systems in the catalytic oxidation of CO in excess of hydrogen, Applied Catalysis B:
Environmental, 129 (2013) 556-565.

[39] J.A. Cecilia, A. Arango-Díaz, F. Franco, J. Jiménez-Jiménez, L. Storaro, E. Moretti, E. Rodríguez-
Castellón, CuO-CeO2 supported on montmorillonite-derived porous clay heterostructures (PCH) for
preferential CO oxidation in H2-rich stream, Catalysis Today, 253 (2015) 126-136.
[40] G. Sponchia, R. Marin, I. Freris, M. Marchiori, E. Moretti, L. Storaro, P. Canton, A. Lausi, A. Benedetti,
P. Riello, Mesoporous silica nanoparticles with tunable pore size for tailored gold nanoparticles, Journal of
Nanoparticle Research, 16 (2014).
[41] H. Che, S. Han, W. Hou, A. Liu, S. Wang, Y. Sun, X. Cui, Mesoporous nanocrystalline zirconium
oxide: novel preparation and photoluminescence property, Journal of Porous Materials, 18 (2010) 57-67.
[42] S. Poulston, P.M. Parlett, P. Stone, M. Bowker, Surface Oxidation and Reduction of CuO and Cu2O
Studied Using XPS and XAES, Surface and Interface Analysis, 24 (1996) 811-820.
[43] A. Martı́nez-Arias, M. Fernández-Garcı́a, O. Gálvez, J.M. Coronado, J.A. Anderson, J.C. Conesa, J.
Soria, G. Munuera, Comparative Study on Redox Properties and Catalytic Behavior for CO Oxidation of
CuO/CeO2 and CuO/ZrCeO4 Catalysts, Journal of Catalysis, 195 (2000) 207-216.
[44] G. Avgouropoulos, T. Ioannides, H.K. Matralis, J. Batista, S. Hocevar, CuO–CeO2 mixed oxide
catalysts for the selective oxidation of carbon monoxide in excess hydrogen, Catalysis Letters, 73 (2001) 33-
[45] A.-P. Jia, G.-S. Hu, L. Meng, Y.-L. Xie, J.-Q. Lu, M.-F. Luo, CO oxidation over CuO/Ce1−xCuxO2−δ
and Ce1−xCuxO2−δ catalysts: Synergetic effects and kinetic study, Journal of Catalysis, 289 (2012) 199-209.
[46] A.N. Il’ichev, V.A. Matyshak, V.N. Korchak, Oxidation of co with catalyst oxygen and with oxygen
from the gas phase over CuO/CeO2 according to TPD and IR spectroscopic data, Kinetics and Catalysis, 56
(2015) 115-124.
[47] E. Moretti, L. Storaro, A. Talon, P. Riello, A. Infantes-Molina, E. Rodríguez-Castellón, 3-D flower like
Ce–Zr–Cu mixed oxide systems in the CO preferential oxidation (CO-PROX): Effect of catalyst composition,
Applied Catalysis B: Environmental, 168-169 (2015) 385-395.
[48] C. Li, M. Li, UV Raman spectroscopic study on the phase transformation of ZrO2, Y2O3-ZrO2 and
SO42?/ZrO2, Journal of Raman Spectroscopy, 33 (2002) 301-308.
[49] M. Li, Z. Feng, G. Xiong, P. Ying, Q. Xin, C. Li, Phase Transformation in the Surface Region of
Zirconia Detected by UV Raman Spectroscopy, The Journal of Physical Chemistry B, 105 (2001) 8107-8111.
[50] L. Li, Y. Zhan, Q. Zheng, Y. Zheng, X. Lin, D. Li, J. Zhu, Water–Gas Shift Reaction Over Aluminum
Promoted Cu/CeO2 Nanocatalysts Characterized by XRD, BET, TPR and Cyclic Voltammetry (CV),
Catalysis Letters, 118 (2007) 91-97.
[51] A. Arango-Díaz, J.A. Cecilia, E. Moretti, A. Talon, P. Núñez, J. Marrero-Jerez, J. Jiménez-Jiménez, A.
Jiménez-López, E. Rodríguez-Castellón, Comparative study of CuO supported on CeO2, Ce0.8Zr0.2O2
and Ce0.8Al0.2O2 based catalysts in the CO-PROX reaction, International Journal of Hydrogen Energy, 39
(2014) 4102-4108.
[52] A. Pintar, J. Batista, S. Hocevar, TPR, TPO, and TPD examinations of Cu0.15Ce0.85O(2-y) mixed
oxides prepared by co-precipitation, by the sol-gel peroxide route, and by citric acid-assisted synthesis,
Journal of colloid and interface science, 285 (2005) 218-231.
[53] L. Kundakovic, M. Flytzani-Stephanopoulos, Cu- and Ag-Modified Cerium Oxide Catalysts for
Methane Oxidation, Journal of Catalysis, 179 (1998) 203-221.
[54] A. Piras, S. Colussi, A. Trovarelli, V. Sergo, J. Llorca, R. Psaro, L. Sordelli, Structural and
morphological investigation of ceria-promoted Al(2)O(3) under severe reducing/oxidizing conditions, The
journal of physical chemistry. B, 109 (2005) 11110-11118.
[55] T. Caputo, L. Lisi, R. Pirone, G. Russo, On the role of redox properties of CuO/CeO2 catalysts in the
preferential oxidation of CO in H2-rich gases, Applied Catalysis A: General, 348 (2008) 42-53.
[56] F. Mariño, C. Descorme, D. Duprez, Supported base metal catalysts for the preferential oxidation of
carbon monoxide in the presence of excess hydrogen (PROX), Applied Catalysis B: Environmental, 58
(2005) 175-183.

[57] P. Bera, K.R. Priolkar, P.R. Sarode, M.S. Hegde, S. Emura, R. Kumashiro, N.P. Lalla, Structural
Investigation of Combustion Synthesized Cu/CeO2Catalysts by EXAFS and Other Physical
Techniques: Formation of a Ce1-xCuxO2-δSolid Solution, Chemistry of Materials, 14 (2002) 3591-3601.
[58] J.M. Gatica, R.T. Baker, P. Fornasiero, S. Bernal, G. Blanco, J. Kašpar, Rhodium Dispersion in a
Rh/Ce0.68Zr0.32O2Catalyst Investigated by HRTEM and H2Chemisorption, The Journal of Physical
Chemistry B, 104 (2000) 4667-4672.
[59] E. Moretti, L. Storaro, A. Talon, M. Lenarda, P. Riello, R. Frattini, M.d.V.M. de Yuso, A. Jiménez-
López, E. Rodríguez-Castellón, F. Ternero, A. Caballero, J.P. Holgado, Effect of thermal treatments on the
catalytic behaviour in the CO preferential oxidation of a CuO–CeO2–ZrO2 catalyst with a flower-like
morphology, Applied Catalysis B: Environmental, 102 (2011) 627-637.
[60] Y. Zhao, K. Tao, W. H.-L., Effect of zirconia phase on the reduction behaviour of highly dispersed
zirconia-supported copper oxide, Catalysis Communications, 5 (2004) 249-252.
[61] M. Piumetti, S. Bensaid, N. Russo, D. Fino, Investigations into nanostructured ceria–zirconia catalysts
for soot combustion, Applied Catalysis B: Environmental, 180 (2016) 271-282.
[62] A. Infantes-Molina, J. Mérida-Robles, P. Maireles-Torres, E. Finocchio, G. Busca, E. Rodríguez-
Castellón, J.L.G. Fierro, A. Jiménez-López, A new low-cost synthetic route to obtain zirconium containing
mesoporous silica, Microporous and Mesoporous Materials, 75 (2004) 23-32.
[63] S. Velu, K. Suzuki, C.S. Gopinath, H. Yoshida, T. Hattori, XPS, XANES and EXAFS investigations of
CuO/ZnO/Al2O3/ZrO2 mixed oxide catalysts, Physical Chemistry Chemical Physics, 4 (2002) 1990-1999.
[64] K. Nagase, Y. Zheng, Y. Kodama, J. Kakuta, Dynamic Study of the Oxidation State of Copper in the
Course of Carbon Monoxide Oxidation over Powdered CuO and Cu2O, Journal of Catalysis, 187 (1999)

Figure 1. CO complete oxidation over the Cu-Ce-Zr oxide systems. Operating conditions: GHSV =
22,000 h−1; feed gas: 1.25% CO, 1.25% O 2 , He balance (vol.%).

Figure 2. Nitrogen physisorption isotherms at -196 ºC of: ▲ Zr500-a;  Zr500-b;  Zr500-c; 
Zr700-c. Filled symbols are referred to the adsorption branch and empty symbols to the desorption

Figure 3. Rietveld analyses of the four fresh calcined CuO-CeO 2 /ZrO 2 catalysts.

Figure 4. X-Ray diffraction patterns of the Cu-Ce-Zr oxide catalysts, before and after one cycle of
COX reaction.

Figure 5. Raman spectra of the samples prepared from the precipitation method.

H2 consumption (a.u.)





50 100 150 200 250 300 350 400

Temperature (°C)

Figure 6. H 2 -TPR profiles of the catalysts.


Figure 7. a) Cu 2p core level spectra of sample CuCeZr500-c before and after one cycle of COX; b)
Ce 3d core level spectra corresponding to fresh CuCeZr oxide samples.

1858 1856 1854 1852

Modified Auger Parameter (')

920 CeCuZr500a 1851
CeCuZr500c 1850
L3M45M45 (eV)

918 1849


916 1847

CuO 1846

914 Cu 1845

937 936 935 934 933 932 931

Binding Energy (eV)

Figure 8. Wagner plot for CuCeZr based catalysts before and after reaction.

Table 1. Comparative CO oxidation activity results over Cu-Ce and Cu-Ce-Zr oxide sytems.
Feed X COR -rCO
W/F composition at Ea R R at 77 °C
Catalyst loading Reference
(g·s·cm-3) 77°C (kJ·mol−1) (µmolCO

(wt%) R

(%) (%) (%) g cat-1s-1)


Cu/CeO2 1 1.8·10-1
P 1 0.5 50 - 1.2 [43]

CuO/CeO2 5.7 3.0·10-2

P 1 0.5 - - 2.3 [44]

CuO/Ce0.15Zr0.85O2 5 3.1·10-3
P 1 1 5.5 - 0.8 [16]

CuCeZr500-a 4.7 1.5·10-2

P 1 1 10 60 3.0 This work

CuCeZr500-b 4.7 1.5·10-2

P 1 1 12 58 3.2 This work

CuCeZr500-c 4.7 1.5·10-2

P 1 1 19 41 5.8 This work

CuCeZr700-c 4.7 1.5·10-2

P 1 1 7 63 0.9 This work

Table 2. Textural parameters and H 2 -TPR data of the bare supports and the final catalysts.

a b c
SBET Vp H 2 uptake H2/Cu

P P (cm3·g-1)
P (mol g-1·10-3)
P (mol mol-1)

Zr500-a 375 0.42 - -

Zr500-b 153 0.22 - -

Zr500-c 81 0.10 - -

Zr700-c 21 0.07 - -

CuCeZr500-a 67 0.15 0.86 1.14

CuCeZr500-b 60 0.12 0.91 1.20

CuCeZr500-c 74 0.06 0.97 1.28

CuCeZr700-c 25 0.04 0.71 0.94

P N 2 isotherms at -196 ºC were used to determine the specific surface areas through the BET equation (S BET )

P Specific pore volume calculated at P/P 0 =0.98

P Nominal amount of CuO =7.54 (mol CuO g cat -1)x 10-4

Table 3. XRD crystallites size for the final fresh catalysts.
a a
ZrO 2 crystal size CeO 2 crystal size

(nm) (nm)

CuCeZr500-a 12.7 t 7.9

CuCeZr500-b 3.7 t 6.6

20.0 t
CuCeZr500-c 5.2
20.8 m
12.4 t
CuCeZr700-c 14.0
34.8 m
Pd = crystallite size calculated by Warren-Averbach’s equation

t = tetragonal phase
m = monoclinic phase

Table 4. Electronic state of copper and surface atomic ratios among Cu, Ce and Zr.
BE Cu 2p 3/2
R ’

Sample I mp /I Sat
R R R Ce/Zr Cu/Zr
(eV) (eV)
Fresh 933.4 1849.5 0.36 0.09 0.19
Used 933.0 1849.5 0.24 0.15 0.17
Fresh 932.9 1849.4 0.29 0.13 0.15
Used 933.0 1849.5 0.25 0.11 0.12
Fresh 933.1 1849.8 0.33 1.06 0.83
Used 933.0 1849.6 0.26 0.97 0.73
Fresh 933.0 1850.8 0.46 1.18 1.16
Used 933.5 1850.9 0.49 1.15 1.08