ELSEVIER

Application
catalysis
today
Catalysis Today 20 ( 1994) 199-2 18
of Zr02 as a catalyst and a catalyst
support
Tsutomu Yamaguchi*
Department of Chemrstry, Faculty of Scrence. Ho!&ardo L~mretxty. Sapporo 060, J apan
Abstract
Examples of the application of ZrO, for catalysts and catalyst supports are reviewed.
The specificity of the structure and the surface properties including the behavior of surface
OH groups are introduced. The catalytic properties of dispersed and promoted ZrO, are
presented. The novel application to the photocatalytic total decomposition of water is also
presented.
1. Introduction
Zirconium dioxide is an oxide with a high melting point (about 27OOC), a
low thermal conductivity, and a high resistance for corrosion which has been used
for refractories, pigments, piezoelectric devices, ceramic condensers, and oxygen
sensors. The development of a partially stabilized zirconia with high mechanical
strength and high tenacity has opened up a new application field of zirconia in
line ceramics.
Attempts have been made to use zirconium dioxide as a catalyst for various
reactions both in the form of a single oxide and combined oxides, and important
and interesting results have been reported (see ref. [ 1 ] and the other chapters in
this issue). Applications as catalyst supports are promising since zirconia has a
high thermal stability and both acid and base properties. Although TiOz, which
is a second generation as a catalyst support after SiO, and A1203, is reducible
under the reduced pressure or the reducing atmosphere, zirconia is stable under
those conditions and even under the photo irradiation.
*Correspondmg author. Present address: Department of Applied Chemistry, Faculty of Engineering,
Ehime University, Matsuyama 790, Japan.
0920-586 l/94/$07.00 0 1994 Elsevler Science B.V. All rights reserved
SSDI 0920-586 1(94)00025-W
200 T Yamaguchl / Catai.vso Today 20 (1994) 199-218
2. Preparation of zirconium compounds
Zirconium compounds are prepared from natural ores, Zircon (ZrSiO,) or
Baddeleyite, by an alkali fusion method, a plasma fusion method, or a carbon
reduction method. For instance the process of the industrial preparation of zir-
conium dioxide by the alkali fusion method is as follows.
1. Fusion of zircon and sodium hydroxide or sodium carbonate; formation of
NazZrSi05
ZrSiO, + 2NaOH (or Na, CO3 ) -Na, ZrSiO, + H2 0 (or CO, )
2. Washing of Na,ZrSi05 and reaction with mineral acid
NazZrSiO, + 4HCl-ZrOClz + 2NaCl+ SiO, + 2H? 0
3. Neutralization of Zr salt with alkali
ZrOCl, + 2NH4 OH- ZrO (OH ) 2 + 2NH4 Cl
4. Calcination
ZrO(OH),-ZrO,
Natural ores usually contain 1 to 3% of Hf. Because of the similarities of the
physical and chemical properties of Zr and Hf, the complete separation is diffi-
cult. Thus Hf contained in ores is always found in the final Zr products. The main
impurities which may be contained in Zr compounds are Si, Na, and Cl. Other
impurities may be Al, Fe, Ti, and S. Since the existence of even a small amount
of such impurities may strongly modify surface properties, careful examination
of the purity levels should be made when necessary.
Contamination of inorganic impurities may be avoided by using zirconium al-
koxide as a starting material to prepare the hydroxide or hydrated zirconia, how-
ever, an appreciable amount of hydrocarbons can be found in the hydroxide, so
attention should be paid to the calcination process.
Partially stabilized zirconia containing Ca or Y is manufactured by:
1. A wet method which consists of coprecipitation of the solutions of a mixture
of zirconium salt and yttrium (or calcium) salt.
2. A thermal method which consists of the calcination of a mixture of ZrO, and
Y203 (or CaO).
3. An electric fusion of ores with Y203 (or CaO).
3. Structure and surface properties
3.1. Structure
Basically three crystalline modifications of zirconium dioxide are known; the
monoclinic which is stable up to 12OOC, the tetragonal which is stable up to
19OOC, and the cubic which is stable above 1900C. In addition, above three
T Yamaguchr / Catalysrs Today 20 (1994) 199-218 201
modifications, a metastable tetragonal form is known and is stable up to 650C.
Two interpretations why this tetragonal form can exist even at low temperature
have been proposed; an impurity effect [ 2-5 ] and a crystallite size effect [ 6-8 1.
Temperature ranges where the above-mentioned crystal forms are stabilized
are varied upon the presence of impurities or additives. Transformation of the
metastable tetragonal form to the monoclinic form is sensitive to the existence of
impurities or additives and they usually stabilize the metastable tetragonal form
to higher temperatures.
Transformation of the metastable form of pure ZrO, is complete at around
650-700C. Phase transformation between the monoclinic and the tetragonal
takes place above 1000C and since this transformation is accompanied with a
volume change, mechanical and thermal stability is not satisfactory for the use of
ceramics. The addition of yttria or calcia stabilizes the cubic form and the tetra-
gonal form (partially stabilized zirconia; PSZ).
Zirconium dioxides used as catalysts are the metastable tetragonal, the mono-
clinic, and the tetragonal. Recently, the use of hydrated zirconium dioxide (zir-
conium hydroxide ) for organic syntheses has been reported [ 91.
The surface area is not large compared with SiO, or A1203 which have fre-
quently been used as catalyst supports. A typical change in the surface area caused
by a change in the calcination temperatures is shown in Fig. 1 as well as a change
in the crystal form.
The surface area depends on the calcination temperature, as typically shown in
Fig. 1, and starting hydroxides, and is in the range of 40- 100 m/g when calcined
at 600C. A higher surface area may be obtained by adding a second component
or by dispersing it on the high surface area supports. However, these method may
modify the surface properties of resultant ZrO? itself.
DTA-TG analysis shows a sharp, exothermic peak at around 420C without
weight change. This has been attributed to the phase change from the amorphous
200 300 600 800 lOi0
Calcination Temp. I C
Fig. 1. Changes in the surface area and crystal form of Zr02 by calcination temperature.
202 T. Yamaguchr / Catalysu Today 20 (1994) 199-218
0 0.5 I 1.5 2 2.5 3 3.5
G)nc. of 112SOj I mol I- *
-iOO
r:
0 0.s 1.0 I.5 2.0
Cr content I mm01 g l
Fig. 2. Effect of additives on the temperature of the exothermic peak m DTA. (a) SO:-. (b) Cr Ion.
()\ /()
Z /()
T /()
ttti/~rot~
i
,Zr
%r
\
HO
to, //Ott HO,\ ,()I
/ \
,()/ \ 0 ll(/j.j(),
Zr,
(y&It (\//o
I\ / (\ /OH
HO y/;; \OH
1
\
\ /
tto~~y/r 0
0
Zr/
OH
tttf OH
otr HO
/ OH HO
a -type p -type
Fig. 3. Model structures of zirconium polycation.
y -type
phase to the crystallized phase, though an apparent crystallographic change could
not be observed by the XRD analysis. The peak position shifts usually to higher
temperatures due to the presence of contaminants or additives regardless of an-
ions or cations. Examples are shown in Fig. 2 where SO,- ions and Cr ions were
added to the hydroxide.
Zirconium dioxide can be obtained by the calcination of its hydroxide which
is prepared by hydrolysis of zirconium salts. The crystal forms of ZrO, depend
on how the hydroxide is prepared and treated. Aging for a long period (e.g. 100 C,
120 h) results in a preferred formation of the monoclinic form after calcination
while the tetragonal is dominant when aging is omitted [ lo]. Steaming of the
hydroxide results in the formation of the monoclinic form, while a vacuum treat-
ment results in the tetragonal form [ 111. The influence of the precipitation con-
ditions and the heating program of the hydroxide on the final crystal form of
ZrO, is interpreted in terms of the change of the unit structure of the hydroxide,
T. Yamaguchi / Catalym Today 20 (1994) 199-218
203
which was proposed by Murase et al. by taking the original model of Zaitsev [ 12 ]
into consideration, and a proposed model is shown in Fig. 3. An a-type of the
hydroxide is the major product just after the precipitate is formed by the hydrol-
ysis. However, the aging brings about a modification of the structure from an a-
type hydroxide to a P-type, and finally a y-type by the loss of OH groups. The CY-
type hydroxide is the precursor of the tetragonal ZrOz and the y-type is the
monoclinic.
Zirconium hydroxide (or hydrated zirconia) adsorbs both cations and anions
in an aqueous solution. In an acidic solution, it adsorbs anions such as SO:-
ions, while in a basic solution, cations are preferentially absorbed.
3.2. Surface properties
The surface of the metal oxides exhibit acidic, basic, oxidizing, and/or reduc-
ing properties. Most metal oxides show one of the properties stronger than the
others at the surface. A characteristic property of ZrO, is that both acidic and
basic properties are found on the surface though their strength is rather weak;
oxidizing and reducing properties are also found. In solutions, acid and base are
neutralized immediately, however, they may exist independently at the surface.
Thus acidic and basic sites on the surface of oxides work both independently and
cooperatively. In this sense, ZrO, is an acid-base bifunctional oxide. One exam-
ple indicating the existence of both properties is evidenced by the adsorption of
CO, and NH3 (Fig. 4) [ 13 1. SiO?-AllO adsorbs ammonia, which is a basic mol-
ecule, but not COz, which is an acidic one. Thus Si02-A&O3 is a typical solid
acid. MgO adsorbs CO2 but not ammonia. Thus MgO behaves as a typical solid
base. On the other hand, ZrO, adsorbs both CO* and ammonia and thus pos-
sesses both acidic and basic properties. ZrO, is an typical acid-base bifunctional
100
10
)r
SA
4
M60
. co2
b)
.
l *
.
.
.
Temperature I C
Fig. 4. TPD profiles of NH3 and CO2 on Si02-A1203, MgO and Zr02.
204 T. Yamaguchl / Catalps Today 20 (1994) 199-218
oxide. Part of the ammonia and the CO2 interact with each other via through-
bond interaction [ 13 1.
The numbers of acid sites and basic sites have been measured as the amount of
irreversibly adsorbed ammonia and COz, respectively. ZrO? calcined at 600C
exhibits 0.6 pmol/m of acidic sites and 4 pmol/m of basic sites. Infrared spec-
troscopic studies of adsorbed pyridine revealed the presence of Lewis type acid
sites, but not protonic (Bronsted acid) sites [ 141.
3.3. Surface OH groups
SOOC-evacuated ZrO, exhibits two types of OH groups. They appear at 3780
and 3680 cm- [ 15-l 71. The latter appears after the low temperature evacuation
and the former is observed by increasing the evacuation temperature. 3780 and
3680 cm- bands have been assigned to the terminal and bridged OH groups,
respectively [ 171.
A detailed IR study on the adsorption of H2 on ZrO, is investigated by Domen
et al. [ 18-201. They found four types of adsorbed species:
1. Molecularly adsorbed hydrogen appeared at 4029 cm- which is observed be-
low 173 K and disappears during the evacuation.
2. Zr < E species ( 1540 cm- ) produced by homolytic dissociative adsorption
which is observed below 373 K and is stable below 178 K.
3. ZrH ( 1560 cm- ) and ZrOH (3668 cm- ) which are produced by heterolytic
dissociative adsorption and are observed at 223-373 K.
4. Two OH groups (3772 and 3668 cm-) which are stable above room
temperature.
ZrOz catalyzes the CO hydrogenation [ 2 l-27 ] and the hydrogenation of ok-
fins [ 28,291 and dienes [ 30-33 1. He and Eckerdt investigated IR spectroscopi-
cally the adsorptions and the interactions of OH groups with CO, CO,, H7.
HCOOH and CH30H [ 221 and found the formation of carbonate, bicarbonate.
formate, and methoxide species. They pointed out that surface OH groups were
involved in the formation of formate and methoxide species. The carbonates or
the bicarbonate species were formed by the interaction of CO- with terminal OH
groups and the formate was produced with bridged OH groups. The details of the
mechanism of the hydrogenation of ethylene is also discussed by Domen et al.
~291.
4. Application to catalyst and catalyst support
4.1. Single oxide
Table 1 summarizes examples of ZrO, being used as catalysts as a single com-
ponent. Typical reactions such as the synthesis of cu-olefins from alcohols, for-
mation of 1 -butene from 2-butanamine, acetonitrile from triethylamine, allyl-al-
cohol from epoxide, ketone synthesis, reductions of aldehydes, carboxylic acids,
Table 1
T Yarnaguchr / Catal.vsls Today 20 (1994) 199-218 205
Application of ZrOz for catalytic reactions as a single component
Reaction Reactant Ref. No.
Orrglnal paper
Alkylation
Amination
Ammoxidation
Cracking
Cyclization
Deamination
Dehydration
Dehydrogenation
HC synthesis
Hydrocrackmg
hydrogenation
Hydrolysis
Isomerizatron
Oxidation
Polymerization
Patent
Alkylation
.Amination
Ammoxidation
Condensation
Cracking
Cyclization
Deacetylation
Dehydration
Dehydrogenation
Esterification
Etherilication
Hydration
Hydrogenation
Isomerization
Oxidation
o-Cresol
Phenol
Methylamsole
Ethylbenzene
Hydrazones
Butanamine
Alcohols
Alcohols
co
Coal
CO, benzene, butadiene
Et, Me acetate
Alkene. epoxy
CO, NH,
Lactams
Aromatic compounds
[491
Aliph. aldehydes
[501
Alkenes
1511
Aldehydes, carboxyhc acids
1521
Gas 011
[531
Ethanol amme
[541
Acetylcaprolactum
[551
Hydroxy(methyl)propanamide
[561
Ale.. alk., ethylbenzene
1571
Dibasic acids
[581
Phenol derivatives
1591
Alkenes
1601
Caprolactum. adiponitrile
Lb11
Alkenes
[621
Alkane. alkene
1631
341
351
361
371
381
391
401
411
421
431
[441
1451
1461
1471
(481
and esters with alcohols, esteritication and ester exchange, amination and acetal-
ization, hydrogenation of olefins and dienes by HI! and cyclohexadiene, hydro-
genation of carbon dioxide, and hydrogenation of aromatic carboxylic acids to
the corresponding aldehydes have been introduced [ 11.
Only one example is presented here. One characteristic catalytic property of
ZrOz is selective dehydration. This properties is successfully applied to the selec-
tive dehydration of I-amino-2-propanol to form allylamine by Koei Chemicals
[ 641.
Hz N-CH2 -CH2-CH3 -+ H2 N-CH? -CH=CH? + H7 0
OH
206 T. Yatnaguchr / Catalws Today 20 (1994) 199-215
Table 2
Reaction of 1-ammo-2-propanol over various catalystsa
Catalyst Reaction condltlon Conv. (%) Select. (% )
Reactlon
temp. (C)
Space
velocity hk
ZrOz 400 2000 98 64
Y*O, 430 1900 67 52
La203 400 1800 80 54
CeO, 400 3200 21 59
TiOz 400 600 48 15
41203 410 1800 58 12
ZrOz+LizO 400 2000 91 75
ZrOz + NazO 400 1800 92 74
ZrOz + KS0 400 1800 98 82
ZrOz + RbzO 400 1800 95 79
ZrOz+ MgO 400 1800 94 79
ZrOz+CaO 400 1800 99 74
ZrOz+TI,O 400 1800 95 72
Allylamine can be synthesized from allylchloride, acrylonitrile, or allylalcohol,
but the above process is more attractive. The result is shown in Table 2.
4.2. Dispersed and promoted oxide and support
Table 3 also summarizes the use of ZrOz as mixed oxides including promoted
ZrOz, and as a support for various reactions.
4.2. I. Dispersed ZrOz
Since the surface area of ZrO, is not large, attempts have been carried out to
obtain large surface area ZrO, by utilizing various preparation methods or by
adding second components.
Attempts were also performed by dispersing the oxide to large surface area sup-
ports as in the case of dispersing metals. The dispersion of metal oxides may have
two objectives. One is to obtain a large exposed surface area of active components
and the other is to control the orientation of exposed surfaces such as ( 1 1 1 ),
(110) andsoon.
Niemantsverdriet and co-workers [ 891 prepared SiO?-supported ZrO? by the
reaction of zirconium ethoxide with a SiOz surface using CH,OOH/EtOH as a
solvent, followed by calcination. The good dispersion of thus obtained ZrO, was
confirmed by SIMS, IR, TPO, and XPS. When a traditional impregnation method
was applied by using zirconyl nitrate as a starting material, poorly dispersed ZrO,
was obtained.
Dispersed ZrO, on SiO? was also prepared by using zirconyl nitrate or zirco-
nium isopropoxide as a starting material where water, methanol, or toluene was
used as a solvent and the acid and base properties of the resultant Zr0,/Si02
were evaluated by temperature-programmed desorption (TPD) of CO, and NH3
Table 3
T Yamaguchr / Catalysis Today 20 (I 994) 199-218 201
Application of ZrO, for catalytic reactions as mixed oxide and support
Reaction Reactant Ref. No.
As axed oxide
Acylation
Alkylation
Ammation
Ammoxidation
Cracking
Dehydration
FT synthesis
HC conversion
qy synthesis
Hydropolymerization
Isomerization
MeOH synthesis
Oxtdation
Reforming
As support
Dehydrogenation
Homologation
Hydrocracking
Hydrogenation
Metathesis
Methanation
Oxidation
Polymerization
Reduction
Reformmg (steam)
( Friedel-Crafts )
Benzene with propene
Pyridine
Toluene
Gas oils
Alcohols
CO, syn gas
Alkene
Alkane, alkene, xylenes
Isobutyric acid
Alkene
Diphenylmethane
CO, COz, alkene
Alkene
co
Alcohol, alkene, toluene
Ethylene
NO, with Hz, NH3
Lb51
1661
Lb71
1681
[ 691
1701
[ 711
1721
[ 731
[ 741
[ 751
1761
[ 771
[ 781
[ 791
[ gOI
[ 811
[ =I
[ 831
[ 841
[ 851
[ 861
1871
[ 881
[ 901. ZrO? possesses both acidic and basic properties. However, when this was
dispersed on SiOz, the basic properties were selectively lost though the acidic
properties were conserved.
The surface electronic structure of ZrOJSiOz was studied by means of XPS
and the decrete variational (DV) X, cluster model calculation [ 9 11. The results
showed that when ZrO, was dispersed on the SiOz surface, the Si-0 bond of Si04,
neighboring ZrO,, became stronger and that the Bronsted acid site H which was
located on the SiOj unit exhibited stronger acidity.
Below 10 wt.-% loading, the structure of dispersed ZrO, was found to be amor-
phous. However, the tetragonal form of ZrO? was developed by the increase in
ZrO, loaded [ 92 1. This means that the transformation of the metastable tetra-
gonal form to the monoclinic form was retarded by the dispersion. Although a
strong anisotropic crystal growth was found when a thin film of ZrOz was pre-
pared by the CVD method from Zr (acac) on the surfaces of Si and a glass plate
[ 93 1, no such anisotropy was observed in ZrO,/SiOz [ 921. XAFS analysis re-
vealed the existence of a precursor of tetragonal form, with an imperfect struc-
208 T. Yamaguchl / Catalws Today 20 (I 994) 199-218
ture, at low loading, growing to a perfect tetragonal structure when the amount of
loading was increased [ 92 1.
Zr02 was deposited on an oxidized surface of Si ( 100) from Zr ethoxide [ 941.
Since a charge-up phenomena can be avoided in these type of samples, an excel-
lent, well-resolved XPS spectrum was obtained.
4.2.2. Promotes ZrUz
Acid and base properties of ZrC& can be modified by the addition of cationic
or anionic substances. Acidic properties may be suppressed by the addition of
alkali cations whereas they may be promoted by the addition of anions such as
halogen ions. The suppression of acidic properties improves the selectivity in the
dehydration of alcohols and propanolamine.
A typical and drastic improvement of acidic properties [ 951 can be seen by the
addition of sulfate ions to produce the solid superacid. This type of solid super-
acid was employed to catalyze the skeletal isomerization of alkanes, the Friedel-
Crafts acylation and alkylation, and many other reactions. One disadvantage of
the catalyst is its relatively quick deactivation which is typically seen in the skel-
etal isomerization. The deactivation may originate from the removal of sulfur,
reduction of sulfur and the formation of carbonaceous polymers. This may be
overcome by the addition of platinum and by using hydrogen as an atmosphere
[ 96,971. More investigations are necessary to improve catalytic stabilities.
Details on the use of sulfated ZrO, as a superacid may be found in the literature
[98-1001.
4.2.3. sup,nort
Although the surface area of ZrO, is not large, it is stable under oxidizing and
reducing atmospheres and possesses both acid and base properties. Thus the use
of ZrO, as a support may be promising. An addition of a second component brings
about the formation of new compounds or solid solutions as in the case of Al,03.
However, ZrOz does not form such compounds, as is typically seen in CrO,fZrO?
and Cr203-Zr02 which has been pointed by Wu et al. [ 1011. The reaction of
alkoxysilane with the surface of TiOz resulted in the formation of a surface sub-
layer of mixed oxide, whereas a Si02 thin film about 1 nm thick forms on ZrO?
without the formation of a mixed oxide [ 102 1.
Hence unique catalytic activities and/or selectivities can be obtained by using
proper combination of metals or metal oxides with Zr02. One example is the
supported perovskite (La-Sr-Co-O ) catalyst for the propane oxidation [ 103 1.
AllO and SiOz, both of which are known as high surface area supports, were not
effective, while the dispersion of perovskite on ZrO, was found to be quite effec-
tive, catalytic activity being enhanced 10 times higher than that of the original
perovskite. ZrOz was also found to be an superior support for Re and Rh in the
hydrogenation of CO? [ 104- 106 1.
As can be seen in a following example, ZrO, can be used as the additive for
supported metal catalysts. When ZrO, was dispersed on a SiO? support and the
T Yamaguchl / Catalym Today 20 (1994) 199-218 209
Table 4
CO/H2 and C02/HZ reaction over ZrO,-supported catalysts
Component Reactant Reaction Ref. No.
CU
Cu (ammine complex)
CU
Rh
Rh
Rh (Rh4(C0),20rRhCl,)
Rh
Rh (Rh cluster)
Re
Nl
Ni
NI. Co-N1
Cu/La2Zr,0,
Cu,Zr,
Cu-Zr alloy
4uz5Zr7, alloy
Rhzs-, Pdz5-,
Ok-, Ir,,-,
Ptz5-ZrTS
Ni6,ZrX3 alloy
Pdj5Zr,, alloy
CO/Hz, CWHz
MeOH +H20
COJH2
CO/Hz. COz/Hz
CO/Hz. CO/HI
CO/H?
CO/H2
CO/Hz
COJHZ
CO/Hz
CO/H,
CO/H2
COJHZ
COJHz
CO/H2
CO/HZ
CO/HZ
CO/H2
MeOH synthesis
Steam reforming
MeOH synthesis
Hydrocarbon
Hydrocarbon
MeOH synthesis
Methanatton
Methanation
MeOH synthesis
Methanation
Methanatton
Methanation
Methanation
[ 108,109]
[1101
[1111
[112]
11131
11141
[1151
11161
11171
[1181
[I191
[ 1201
11211
[ 122.1231
11241
11251
[I261
~1271
resultant combined support was used to anchor a Rh carbonyl cluster, selectivity
for the formation of alcohol in the CO/H, reaction was markedly enhanced [ 107 1.
ZrO,-supported metals and/or metal catalysts with better dispersion can be
obtained by the oxidative decomposition of amorphous alloys such as Cu,Zr,.
Examples of ZrO?-supported catalysts for CO/H2 and COJH2 reactions are
summarized in Table 4.
Two examples are shown below:
4.2.3.1. Supported chromium oxide. Tan-no and co-workers have investigated
[ 128,129 ] the structure and morphology of supported chromium oxide by using
XRD and EPR and concluded that a two dimensional octahedral or square py-
ramidal chromium oxide species was developed over ZrOz and this grew to
-Cr203 by increasing the amount of chromium oxide loaded, while a three di-
mensional tetrahedral species was obtained as crystallites even at low loading on
SiO,. Surface properties of CrO,/SiO1, CrO,/ZrOz, and CrO,/Al,O~ were ex-
amined by IR and TPD of adsorbed NO, CO, NzO, and 02, and by catalytic
reactions of CO-O?, CO-NO, and CO-N,0 [ 130 1. The catalytic activity of CrO,/
ZrO, (0.5 mmol Cr/g ZrO,) was the highest of the three catalysts for all the
reactions as shown in Fig. 5.
Extensive work on supported chromium oxide have also been reported by Cim-
ino et al. [ 13 1 1, Indovina et al. [ 132 1, and Ghiotti et al. [ 133 1.
210 T. Yamaguchl / Catalps Today 20 (I 994) 199-218
Fig. 5. Catalytic activities of chromium oxide supported on !30z, ZrOz, and A1203 for CO oxldatlon.
Since ZrO, is transparent to an IR beam down to 800 cm-l, the structure and
the reactivity of oxo-species can be examined. Cr=O species which show absorp-
tions around 1000 cm- can be removed by 200C reduction and are recovered
by contact with 02, NO, and NzO below 200C [ 1341.
4.2.3.2. Supported copper oxide. The methanol synthesis from CO2 and H, was
examined under 50 atm using binary or ternary copper catalysts and the highest
yield was obtained over a Cu/ZrOl catalyst [ 135 1.
Methanol synthesis from CO, or CO with H2 was investigated under I, 10, and
26 atm by using supported copper catalysts [ 136,137]. A high methanol yield
from CO/H, was obtained over MgO-, La203-, and Sm,O,-supported catalysts,
though the C02/H2 reaction did not take place over these catalysts. The reactiv-
ity of the two reactions was reversed over A1103- and ZnO-supported catalysts.
Cu/ZrO* catalyzed both reactions and gave a high methanol yield.
Takezawa et al. have reported that Cu/ZrO, which was prepared from a copper
ammine complex exhibited a high activity and selectivity for the steam reforming
of methanol [ 138 1. Highly dispersed precursor species of copper compounds are
readily reduced on ZrO, to form Cu crystallite. On a ZrO, support calcined at
700 C, bulky CuO was obtained above 3OOC, whereas on ZrOz calcined at 300 o C
it was obtained above 700 C [ 139 1.
4.2.4. Photocatalytic decomposition of water
Photocatalytic decomposition of water consists for the most part in photosyn-
thesis and the artificial reconstruction of the photosynthesis is being explored in
both fundamental and applied research. The production of hydrogen from water
may become very important in the near future when considering the expected
shortage of petroleum which is now an important source of hydrogen. The pho-
tocatalytic total decomposition of water ( 2H,0+2H2+02) should be a quite
interesting target.
The photocatalytic total decomposition of Hz0 was discovered by Sato and
White using Pt/TiO? in a liquid phase [ 1401 and by Kawai and Sakata using
T Yamagucht /Catalysts Today 20 (1994) 199-1718 211
RuOJTiOz in a gas phase [ 14 11, both in 1980. Since then numerous attempts
have been made. Recently, high activities of a series of A4Nb6017 (A=K, Rb)
compounds and a layered perovskite family doped with Pt or Ni [ 142-1441 as
well as Wadsley-Anderson type and pentagonal prism type metal oxides with a
tunnel structure combined with RuO, have been reported [ 145 147 1. Very re-
cently, Sayama et al. found a pronounced activity of ZrOz for the photocatalytic
total decomposition of water under UV irradiation [ 148- 150 1. This is an inter-
esting finding, since a combination with metals is necessary to improve the pho-
tocatalytic activity of metal oxide semiconductors to constitute photochemical
diodes. However, in the case of ZrO, the assistance of such metals is not neces-
sary to promote the reaction. The addition of metals tends to retard the reaction.
Thus a novel type of reaction mechanism may be operating on ZrOz and this will
encourage us to develop a new type of photocatalyst.
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