Direct production of hydrogen peroxide from CO, O2, and H 2O over a novel alumina-supported Cu catalyst

Article abstract of DOI:10.1039/b410559a

The direct production of hydrogen peroxide from CO, O₂, and H₂O over a novel catalyst system based on highly dispersed Cu supported on alumina has been demonstrated. Under optimized conditions, a high H₂O₂ formation rate of ca. 0.326 mmol (g cat.) ^-1 h^-1 could be achieved.

Full text of DOI:10.1039/b410559a

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L E T T E R
Direct production of hydrogen peroxide from CO, O2, and H2O
over a novel alumina-supported Cu catalyst
Wei-Liang Feng, Yong Cao,* Nan Yi, Wei-Lin Dai and Kang-Nian Fan*
Department of Chemistry & Shanghai Key Laboratory of Molecular Catalysis and Innovative
Materials, Fudan University, Shanghai, 200433 P. R. China. E-mail: yongcao@fudan.edu.cn;
Fax: +86-21 65642978; Tel: +86-21 65643792-5
Received (in Toulouse, France) 10th July 2004, Accepted 31st August 2004
First published as an Advance Article on the web 17th November 2004
The direct production of hydrogen peroxide from CO, O2, and
H2O over a novel catalyst system based on highly dispersed Cu
supported on alumina has been demonstrated. Under optimized
conditions, a high H2O2 formation rate of ca. 0.326 mmol
(g cat.)ꢀ1 hꢀ1 could be achieved.
Table 1 shows the catalytic results for H2O2 production from
CO/O2/H2O over several types of metal nanoparticles dis-
persed on alumina prepared by the wet reduction (WR)
method, which has recently been shown to be an effective
method for the preparation of various amorphous alloy cata-
lysts for versatile hydrogenation applications.11,12 All the
results presented in Table 1 were obtained using an autoclave
with aqueous 0.01 M sulfuric acid as the reaction medium. It is
remarkable that a much higher H2O2 formation rate could be
achieved over the 1st row transition metal catalyst systems.
Among these, the Cu/Al2O3 catalyst was the most active,
giving a formation rate of ca. 0.236 mmol (g cat.)ꢀ1 hꢀ1 for
the H2O2 production at 273 K. Note that this result is
drastically improved with respect to the patent value of
0.1 mmol (g cat.)ꢀ1 hꢀ1 achieved over the Pd/CaCO3 catalyst
reported by Brill.9 As also shown in Table 1, the less active
samples of alumina-supported Fe and Co particles present a
much lower rate of H2O2 production. It should be noted that
the present sample of Ni/Al2O3 shows a moderate activity of
0.075 mmol (g cat.)ꢀ1 hꢀ1 for H2O2 formation at room
temperature, which is comparable to that obtained over the
amorphous alloy catalysts Ni–La–B/Al2O3.10 It is also clear
from Table 1 that the rates of H2O2 formation over the
alumina-supported noble metal catalysts (Au/Al2O3, Ru/
Al2O3 and Pd/Al2O3) are extremely low. Although noble
metals such as Pd and Au were reported to be superior
candidates for the direct synthesis of H2O2 from H2/O2,13 the
results listed in Table 1 suggest that neither Pd nor Au appears
to be suitable material for direct H2O2 production from the
CO/O2/H2O system. While further work is needed to fully
understand why the performance of copper appears to be so
much better than that of other metals, we suggest that the
superior performance of the copper catalyst system is asso-
ciated with a two-step reaction mechanism involving the
initial step of the water gas shift (WGS) reaction (CO +
H2O = CO2 + H2) and subsequent reaction between the
produced H2 and O2. In this respect, it is reasonable that the
copper catalyst exhibits superior performance with respect to
other metals for H2O2 synthesis, as it is known to be one of the
most efficient systems for the WGS reaction.14
Hydrogen peroxide is a clean oxidizing agent that is useful
for highly selectively converting organic compounds into va-
lue-added products, as well as for industrial or municipal
wastewater treatment and water disinfection.1 Currently, the
commercial production of H2O2 is mainly based on a multi-
step process involving cyclic hydrogenation and oxidation of
an alkyl anthraquinone in a complex working solution.2 This
high-energy consuming process often has disadvantages, such
as the cost of the quinone solvent system and the elaborate
treatments required to remove degradation products due to
non-selective hydrogenation. Hence, it is highly attractive to
develop more economical and ‘‘green’’ processes that can allow
the direct synthesis of H2O2 from H2 and O2 or from CO, O2
and H2O. Although notable recent progress in this area is the
use of noble metal based catalysts to achieve efficient produc-
tion of H2O2 from mixtures of H2/O2,3–5 the latter process
(Scheme 1) in particular has attracted recent interest due to its
high safety.
During the past decade, a complex homogeneous palladium-
ligand catalytic system that requires extra separation
steps or acid additives has been extensively studied for the
synthesis of H2O2 from CO, O2 and water.6–8 Nevertheless,
comparatively little attention has been paid to the develop-
ment of new heterogeneous catalytic systems that can allow
easy removal of the catalysts from reaction mixtures and
recycling/reuse of catalysts.9,10 Catalyst systems based on
supported noble metals, such as Pd/CaCO3 or Ru/graphite,
have recently been proposed for H2O2 synthesis from CO/O2/
H2O,9 but the catalytic results in terms of H2O2 formation
rate are far from satisfactory. More recently, Ma and co-
workers reported a much cheaper catalyst system consisting
of a rare earth modified alumina-supported amorphous
alloy catalyst, Ni–La–B/Al2O3, for the catalytic production
of H2O2 from CO/O2/H2O;10 moreover, it exhibited an activity
only slightly inferior to that of the noble metal catalysts
mentioned above.9 Here, for the first time, we report an
alternative new heterogeneous catalyst system based on highly
dispersed copper supported on alumina, which exhibits super-
ior performance for the catalytic synthesis of H2O2 from
CO, O2 and water.
On the other hand, it was found that the catalytic activity of
Cu/Al2O3 is greatly dependent on a number of important
factors such as the reaction temperature, relative pressure of
carbon monoxide with respect to O2 and the choice of solvent
as the reaction medium. Fig. 1 compares the formation rate of
H2O2 over the present Cu/Al2O3 catalyst in a reaction medium
consisting of 10 ml of 0.01 M H2SO4 and 40 ml of organic
solvent or water at 273 K. Under the same reaction condi-
tions, the organic solvents acetone, methanol, ethanol and iso-
propanol were examined, along with pure water as a reference.
Obviously, all organic solvents gave a much higher rate of
Scheme 1
T h i s j o u r n a l i s & T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
N e w J . C h e m . , 2 0 0 4 , 2 8 , 1 4 3 1 – 1 4 3 3
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Table 1 Formation of H2O2 from the reaction of CO/O2/H2O over
various alumina-supported catalystsa
analysis of the two samples reveals that this is probably due to
the low dispersion of the Cu particles deposited on alumina
when prepared by the GA method. As shown in Fig. 2, Cu
nanoparticles (the darker spots as verified by EDX) with an
average diameter of ca. 12 nm were highly dispersed on the
surface of alumina by the wet reduction method, in contrast to
a much larger particle size of 20 nm (not shown) for Cu
nanoparticles deposited on alumina prepared by the GR
method. Therefore, it appears that the size of the Cu
particles deposited is also an important factor to achieve a
high rate of H2O2 formation from CO/O2/H2O over the Cu/
Al2O3 catalyst.
In summary, we have successfully demonstrated that the
direct production of hydrogen peroxide from CO, O2, and
water can be effectively achieved over a novel alumina-sup-
ported Cu catalyst prepared by a chemical reduction method.
Although the mechanism of the superior performance of the
Cu/Al2O3 catalyst system needs further clarification, this work
presents a highly efficient approach for improving the direct
synthesis of H2O2 from the CO/O2/H2O system under hetero-
geneous conditions.
R[H2O2]b/mmol
Catalyst
Prep. method
T/K
PCO : PO
(g cat.)ꢀ1 hꢀ1
2
Cu/Al2O3
WR
WR
WR
WR
GRc
WR
WR
WR
WR
WR
WR
WR
WR
WR
273
273
273
293
273
273
293
273
293
273
293
273
273
273
1 : 1
3 : 1
1 : 3
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
0.236
0.178
0.202
0.177
0.150
0.095
0.075
0.055
0.045
0.023
0.016
0.005
0.002
0.002
Ni/Al2O3
Co/Al2O3
Fe/Al2O3
Ru/Al2O3
Au/Al2O3
Pd/Al2O3
a
Reaction conditions: total pressure ¼ 4 MPa, reaction medium ¼
b
water, 0.01 M of sulfuric acid, reaction time ¼ 3 h. Average rate of
c
H2O2 formation over 3 h experimental time. The reduction of the
copper catalyst by gas phase reduction in H2/Ar at 250 1C for 3 h.
Experimental
H2O2 production than the aqueous reaction medium. Acetone
appears to be the best organic media by affording a remarkably
The alumina-supported copper catalyst was prepared by an
impregnation-wet reduction method previously established by
our group.11,12 Alumina (40–60 mesh, from Shanghai Super
Chemical Material Co., Ltd, 203 m2 gꢀ1) was first impregnated
in a 0.1 M CuCl2 aqueous solution overnight. Then the
excessive solution was removed. After being calcined at 383 K
for 12 h, this was followed by reduction with a 2 M KBH4
aqueous solution containing 0.2 M NaOH [n(BH4ꢀ) : n(Cu2+) =
3]. After reduction, the catalysts were thoroughly washed by
oxygen-free distilled water and absolute ethanol successively.
The as-prepared catalyst is denoted as Cu/Al2O3, where the
loading of Cu is 5 wt %. For comparison purposes, the
catalysts loaded with other types of metal ions (i.e., Ni, Co,
Fe, Ru, Au and Pd) were prepared by following the same
procedure.
high H2O2 production rate of ca. 0.326 mmol (g cat.)ꢀ1 hꢀ1
,
although the use of acetone as a solvent may result in addi-
tional safety concerns due to the possible formation of explo-
sive organic peroxides in the reaction system. It was recently
shown that the catalytic activity of a palladium catalyst system
for direct H2O2 synthesis from a H2/O2 mixture is greatly
dependent on the reaction medium,5 where the rate of produc-
tion of H2O2 from H2 and O2 has been suggested to be strongly
influenced by the mass transfer rate of the gas into the liquid
reaction medium. Thus, the dramatic increase in reaction
efficiency upon the proper choice of organic solvent in the
present case also confirms the presence of mass transfer
limitations in the H2O2 synthesis from the CO/O2/H2O
mixture.15,16
Catalytic activity measurements were carried out using a
150 ml stainless steel autoclave fitted with a Teflon liner. The
reaction conditions were: 1.0 g of catalyst, 50 ml of distilled
water containing H2SO4 (the concentration of the acid is ca.
0.01 M), CO and O2 total pressure of 4 MPa, reaction
temperature of 273 K or 293 K and a stirring rate of 1000
rpm. After the reaction was allowed to proceed for 3 h, the
aqueous samples taken out were analyzed by colorimetry after
complexation with a TiOSO4/H2SO4 reagent.17
From these experiments, it was found that the choice of
solvent was the most important factor to achieve a high rate of
H2O2 formation from CO, O2, and water over the Cu/Al2O3
catalyst, which is a consequence of enhanced solubility of the
CO and O2 reactant gases in the reaction media.5 Under
optimized conditions, CO/O2/H2O could be transformed effi-
ciently into H2O2, with the highest rate attained being 0.326
mmol (g cat.)ꢀ1 hꢀ1 for H2O2 formation. This result is much
superior to that for noble metal catalysts reported in the
literature,9 showing attractive potential for practical applica-
tions. On the other hand, it should be noted that the Cu/Al2O3
prepared by gas phase reduction (GR) is less active for H2O2
production than the wet reduced sample (see Table 1). TEM
Fig. 1 Comparison of different reaction media used with 0.01 M
sulfuric acid (Vsolvent : VH O = 3) , PCO = 2 MPa, PO = 2 MPa,
reaction temperature 273 K, reaction time 3 h.
Fig. 2 TEM image of as-prepared Cu/Al2O3 catalyst obtained by the
chemical reduction method.
2
2
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6
D. Bianchi, R. Bortolo and R. D’ Aloisio, J. Mol. Catal. A., 1999,
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Acknowledgements
Financial support by the National Nature Science Foundation
of China (Grant No. 20203003), the National Major Basic
Research Program of China (Grant No. 2003CB615807), and
the Committee of Shanghai Science and Technology (Grant
No. 02QA14006) is kindly acknowledged.
7
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11 B. Liu, M. H. Qiao, J. Q. Wang and K. N. Fan, Chem. Commun.,
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