C1 chemistry synthesis using yttrium-stabilized catalyst: a review

Shortened title: C1 chemistry using YSZ catalyst: a review

Antonius Indarto

Plasma-Catalyst Chemical Process, Korea Institute of Science and Technology,

PO BOX 131, Cheongryang, Seoul, South Korea
Phone: 010-2296-3748; email: indarto_antonius@yahoo.com
Abstract—It is known that direct methane conversions are still suffering from low yields
and selectivities of products which make unprofitable way to produce products, for
example: methanol, dimetil-ether (DME), etc. However, many experts and researchers are
still trying to find the best method to activate methane and convert it efficiently, for
example by finding the best catalyst to reduce the high barrier energy of the reactions and
conduct selective catalyst-surface reactions.
The application of yttria-stablized zirconia (YSZ) and its combination with other metals for
catalyst purposes are increasing. The existence of interesting sites which act as oxygen
storage can be the main reason for it. Moreover, formation of intermediate species on the
surface of YSZ also gives a significant contribution to increase the production of some
specific products. Understanding of the phenomena inside could be a necessary task to be
known. In this paper, the use of YSZ for oxidative methane conversion reactions was
discussed and reviewed.
1. Introduction

Much work was reported in the past decade on catalytically oxidative coupling of methane
(OCM), a promising process for direct conversion of natural gas into C2 (C2H4 and C2H6)
[1-4], synthesis gas [Zhu, 2004], methanol products.

Among many types of OCM, CH4 combined with CO2 reforming

However, due to deep oxidation reactions in the gas phase as well as on the catalyst surface,
the C2 yield of OCM achieved so far on any catalysts operated in conventional packed-bed
reactor is less than 25% when C2 selectivity is higher than 50%, far below the requirement
for making OCM economically attractive (>30-40%) [4].

2. Oxygen-storage catalyst

Previously, the research was focused on how to activate CH 4 and/or CO2 on the surface of
the catalyst. As the result was not applicable in the economic point of view, it forces the
researchers to find the new ideas to boost the amounts of the products. Recently, many
catalyst studies have increasingly focused on oxygen-ion oxides [16-23]. In partial
oxidation reactions in which oxygen plays as the key role, the existence of space lattice
storage to control the oxygen surface on the catalyst surface is necessary. From this point of
view, the oxygen-ion conduction oxide will be taking a part on the catalytic reaction due to
the oxygen storage/transport of the support [16,19] or to the generation of active centers at
the interface between metal and support [21,78-80]. In general, it is known that defects of
the surface of material surface, e.i. catalyst of metal oxides, can act as oxygen vacancies
site which is important in the surface chemistry [11].
Lattice oxygen ions are often involved in reactions over oxide catalysts. Most of the partial
oxidation reactions proceed via a Mars–van Krevelen mechanism, in which lattice oxygen
ions are incorporated into the products [24]. The cycle for catalytic partial oxidation is
closed via replenishment of the extracted lattice oxygen ions through the dissociative
adsorption of molecular oxygen at the surface [25].
Previous studies indicated that using such materials (a) as supports could significantly
enhance the catalytic activity of 2nd metal addition, e.g. Pt [16], Rh [19] and CuO [20,22]
for CO oxidation and NO reduction, or (b) as catalysts might enhance the selectivity of
specific products, e.g. CO hydrogenation [17,18], and/or reactant conversion rate, e.g.
decomposition of formic acid [23]. Although the detailed mechanisms are still confusing in
some parts, sometimes unclear and ambiguous, and rather controversial, these
improvements in catalytic activity have been attributed to the effects of oxygen ionic
transport [16,19,20,22], interfacial metal-support interaction [16,20,22] or surface oxygen
vacancies of these oxygen-ion conducting oxides [17,18,22,23].
Among all transition metal group compounds, yttrium (oxide) and zirconium (oxide) with
its mixing combinations have attracted many researchers interest. It suggests that either Y3+
or Zr4+ must act as a trapping center for oxygen vacancies in YSZ at low temperatures. An
extended X-ray absorption fine structure (EXAFS) study indicates that an oxygen vacancy
is sited adjacent to Zr4+ [7]. However, the molecular dynamics analysis shows that oxygen
vacancies are trapped at the second-neighbor positions to Y3+ [8]. Some knowledge about
the trapping center would be obtained if Y3+ or Zr4+ ions were partially replaced by other
trivalent or tetravalent ionic species, because such replacements would change the bonding
nature between the trapping center and an oxygen vacancy.

3. Property YSZ catalyst

Figure 1

The oxides of zirconium form three different phases, monoclinic, tetragonal and cubic [8-
10]. The monoclinic phase is stable below 1200 oC. The tetragonal phase is normally stable
above 1200 °C, but can he obtained in a metastable condition at much lower temperatures
and is the crystal structure of zirconia particles under 300 angstrom in diameter [11]. The
stable cubic phase is only formed at temperatures >2280 oC, but at room temperature it can
be by the addition of other oxides such as Y2O3 and CaO. Moreover, it has a very low
thermal conductivity which allow us to operate at higher temperatures and preventing the
deactivation of possible 2nd doping metal on it surface, e.g. due to agglomeration.
Yttria doping of ZrO2 was used to generate a single phase (cubic) and to introduce known
concent cations of anion vacancies. The stabilization of the cubic structure is accomplished
by direct substitution of trivalent yttria cations to the host lattice Zr4+ cation. Since the
dopant cation is of lower valence than the host cation, oxygen vacancies are created to
preserve lattice neutrality. Spectroscopic studies have shown that the trivalent Y and
tetravalent Zr cations are statistically distributed [12] and that the Zr cations are nearest
neighbors to the anion vacancies [13]. These vacancies increase the electrical conductivity,
with diffusing oxygen ions being the primary charge carrier [14-16]. This diffusion of
oxygen ions has been associated with lattice vacancy migration [14,15].
The number of oxygen vacancies in ZrO2 can be increased significantly by doping with
lower valence metal ions, such as Y3+ and Ca2+. Compared with single ZrO2, the improved
catalytic performance of YSZ in oxidation catalysis has been attributed to a high
concentration of oxygen vacancies [3,12].

4. YSZ as a catalyst and its mechanism

Although YSZs has received extensive attention with respect to oxygen sensors and fuel
cells [8], the role of catalysis on the chemical synthesis reaction has seldom been addressed.

4.1. Oxidative methane conversion to synthesis gas

The use of YSZ for the oxidative methane conversion to synthesis gas was investigated first
by Steghuis (1998) and Stobber (1999). They used some oxide catalysts, such as ZrO2,
Y2O3, La2O3/ZrO2, yttrium-stabilized zirconia (YSZ), and TiO2 for the comparison work.
Among these irreducible oxides, YSZ was the most active catalyst for synthesis gas
production. All these catalysts show lower activity and selectivity compared to metal
catalysts but very superior in term of stability. The conversion of methane was <5% below
800oC [Zhu, 20042]. Introduction of second metal-based reforming catalyst was proposed in
order to increase the activity and selectivity. The second metal-based reforming catalyst,
doped on the YSZ, will be stable as contact reaction with oxygen at high temperatures is
avoided [Zhu, 20041].
Stobbe [21] concluded, based on the relation between methane conversion and selectivities
over ZrO2, that CO and H2 are primary products of oxidative methane conversion over
ZrO2, whereas CO2 is formed by water-gas shift and oxidation of CO. Steghuis [20]
proposed a reaction mechanism of CPOM over YSZ, including homolitic dissociation of
methane over oxygen vacant sites followed by conversion to CO, H2, and H2O via the
formation and decomposition of formaldehyde (CH2O) as a single intermediate species.
CO2 is produced by further oxidation of the reaction intermediate. Instead of only
formaldehyde, the existence of formate (CHOO-) species on the surface of catalyst should
be counted also as the H2/CO ratio in the product mixture significantly larger than one was
observed, implying that formaldehyde cannot be the only source of CO and H2 [Zhu,
20042].

O 2 CO 2 + H 2O
C H 2O

CO 2 + O 2 H 2O + C H 2O CO + H 2
O O C H 2O O CO + 0 .5 H 2O
2
0 .5 H 2O + C H O O
CO 2 + 0 .5 H 2

C O + 0 .5 H 2 O + 0 .5 O

O
Note: means absorbed oxygen on the surface of the catalyst (YSZ). The above
mechanism has been investigated further by controlling the input of water to the system
[Zhu, 20063]. Higher concentration of water will decrease the rate formation of formate
means that the selectivity of CO and H2 will increase.

4.2. Methanol from synthesis gas

Methanol can be produced from synthesis gas in a catalytic reaction over ZrO2 at

1
J. Zhu, M.S.M. Mujeebur Rahuman, J.G. van Ommen, L. Lefferts, Appl. Catal. A 259 (2004) 95.
2
Jianjun Zhu, Jan G. van Ommen, and Leon Lefferts, Reaction scheme of partial oxidation of methane
to synthesis gas over yttrium-stabilized zirconia, Journal of Catalysis 225 (2004) 388–397.
3
Jianjun Zhu, Jan G. van Ommen, Leon Lefferts, Effect of surface OH groups on catalytic performance
of yittrium-stabilized ZrO2 in partial oxidation of CH4 to syngas, Catalysis Today 117 (2006) 163–167
atmospheric pressure [52,58] and over both ZrO2 and YSZ at 35 atm [54]. CO and CO/H2
interaction with YSZ could be the key point of the reaction. On the surface of the YSZ, the
absorbed CO will be transformed into intermediate formate species at an earlier stage
[Ekerdt, 54b]. It was supported by FTIR analysis which shows the existence assigned
formate bands [57]. Then, the reduction of formate to methoxide will be occurred on the
surface oxygen anion vacancy [Jackson and Ekerdt, 1986; Ekerdt, 54b] and finalized by
reaction between absorbed H2O and metoxide to form methanol. The schematic paths are
illustrated as follows:
H H H CH
H 2
H 2
H 2
3 HO H O H
CO C. C + C H 3O H
O O O O O

In the high temperature process, the methanol still could be formed [He, et al., 19854].
However, the mechanisms could be different as the existence of H2O is not sufficient. He et
al. and co-coworkers proposed that this methanol derives from a surface methyl formate-
like intermediate. This intermediate was postulated to form by nucleophilic attack of CH3O-
[8,46] on formyl [465] or formate [86]. The simplified mechanisms could follow:

O CH 3 O CH 3
H H H 2
C O C O C H 3O H
... (1)

H CH 3 H CH 3
C. O C O H 2
O O O O
C H 3O H
… (2)
Real quantitative experiments of methane synthesis using YSZ was done by Indarto et al. It
showed that the methanol produced by addition of YSZ was significantly higher that other

4
M.Y. He, J. M. White, and J. G. Ekerdt, CO and CO2 hydrogenation over metal oxides: a comparison
of ZnO, TiO2 and ZrO2, J. Molecular Catalysis, 30 (1985) 415-430.
5
E. L. Muetterties and J. Stein, J. Chem. Rev., 79 (1979) 479.
6
M.-Y. He and J. G. Ekerdt, J. Catal. 90 (1984) 17.
metal oxide catalyst, such as Al2O3 and TiO2. Moreover, the addition of 2nd metal to the
catalyst was able to improve the selectivity of methanol up to c.a. 20%. Unfortunately, no
investigation on the reactions mechanism was done.

4.3. Hydrocarbons from synthesis gas and methane conversion

Ekerdt and co-workers found that certain hydrocarbons can be synthesized over ZrO 2 and
YSZs from CO/H2 [44-46] and methane oxidation [Lapena-Ray and Middleton7]. During
the past year the research involved yttria-stabilized zirconia (CZA) in the chemical
synthesis process have focused on two issues: confirmation that anion vacancies are the
active slues for CO activation and hydrogenation, and the influence of additives on the
reactions that occur during isosynthesis.
In the case of CO hydrogenation reaction, oxygen vacancies of the oxides are the active
sites which formaldehyde and formate were both shown to be reaction intermediates proved
by FTIR analysis. The hydrocarbons formation from syngas is initiated by reaction between
CO (or CO2) with absorbed OH or H. It means that it requires having OH or H attached on
the surface of the catalyst to formate. Based on the results of in situ FTIR and both steady-
state and transient experiments, a reaction scheme was proposed.

CO
OH

CO H H H CH
H H 2 H 2
3 H 2
C. C CH
O 4
O O O O
CO 2
O H

O H H
CO 2
C.
O O

For the second case of higher hydrocarbon (ethane and ethylene) synthesis from methane
oxidation, the ratio of methane to oxygen could be an important point. Lapena-Ray and
7
N. Lapeña-Rey, P.H. Middleton, The selective oxidation of methane to ethane and ethylene in a sol-
id oxide electrolyte reactor, Applied Catalysis A: General 240 (2003) 207–222.
Middleton mentioned that at high oxygen flows, mean low methane to oxygen ratios, the
catalyst was not useful as the gaseous phase reaction is more dominant and reaction goes to
methane oxidation reaction or methane combustion. By measuring the polarization of
oxygen evolution or reduction, it was postulated that oxygen transfers are most likely
involved in catalytic partial oxidation of methane. The C2 selectivity among the products
was claimed very high (~86%) at 4% of C2 yield. However, the mechanistic details,
particularly the role of oxygen vacancies and that of lattice oxygen ions in the partial
oxidation of methane, are still not clear. Moreover, the nature of the oxygen species, such as
surface lattice oxygen ions or adsorbed oxygen, in the activation of methane is still a matter
of controversy [49,50].

4.4. Methane oxidation using CO2

Currently the reaction of methane oxidation using CO2 is becoming hot topic and attracted
interest of many people for environmental and industrial reasons. Both CO2 and CH4 are
considered as harmful greenhouse gases [18–21] and this reaction provides a means of
disposing of or recycling these gases. CH4/CO2 reforming also provides an important route
to produce CO-rich synthesis gas or extremely pure CO for the synthesis of chemicals such
as acetic acid, dimethyl ether and alcohols [22]. Numerous authors have investigated
various metals, such as: Ni, Ru, Rh, Pt, Ir and Pd [21,23-27] for CH4/CO2 reforming. Most
authors preferred Rh catalysts, owing to their good activity and stability. Meanwhile, Ni
catalysts are commercially more interesting than noble metals but suffer the disadvantage
of a high rate of coke formation [19,21,28]. From the perspective of relative price and good
availability, Pt is a reasonable compromise.
Several works [64,65,66] have confirmed that ZrO2 is a very effective support for the Pt
catalysts; such combinations not only are more active but also more stable than Pt
supported on other materials [64]. Bitter et al. (1996, [64]) showed that only 5% of catalyst
deactivation was occurred after 50 hours of the operation. It was hypothesized that the
oxygen vacancies could be used to activate CO2 for CO2 reforming of CH4 at higher
temperature (>600oC). Some other dopant metals were also tried on the YSZ to enhance the
better performance of the original one but some were suffer from the deactivation, such as
carbon deposition on Ni catalyst. The last case was also faced when YSZ and Ni used as the
electrode for the electrochemical process. In this case, more complex catalyst system to
avoid this problem has been proposed for example by addition of Cerium. The investigation
of nickel catalyst on ceria has been done and appears to be appropriate to develop a catalyst
that is resistant to carbon deposition and that exhibits stable operation for extended periods
of time.

Conclusions
References
[1] J.S. Lee and S.T. Oyama, Catal. Rev. Sci. Eng., Oxidative Coupling of Methane to
Higher Hydrocarbons, 30 (1988) 249.
[2] G.J. Hutchings, M.S. Scurrell and J.R. Woodhouse, Chem. Soc. Rev., Oxidative
Coupling of Methane Using Oxide Catalysts, 18 (1989) 251.
[3] Y. Amenomiya, V.I. Birss, M. Goledzinowski, J. Galuszka and A.R. Sanger, Catal.
Rev. Sci. Eng., Conversion of Methane by Oxidative Coupling, 32 (1990) 163.
[4] J.M. Fox, Catal. Rev. Sci. Eng., The Different Catalytic Routes for Methane
Valorization:. An Assessment of. Processes for Liquid Fuels, 35 (1993) 169.
[5] A.T. Ashcroft, A.K. Cheetham, M. Green, P.D.F. Vernon, Nature, Partial oxidation
of methane to synthesis gas using carbon dioxide, 352 (1991) 225.
[6] J.T. Richardson, S.A. Paripatyadar, Appl. Catal. Carbon dioxide reforming of
methane with supported rhodium, 61 (1990) 293.
[7] J.H. Edwards, A.M. Maitra, Fuel Proc. Tech., The chemistry of methane reforming
with carbon dioxide and its current and potential applications, 42 (1995) 269.
[8] J.R. Rostrup-Nielsen, J.H. Bakhansen, J. Catal. CO2-Reforming of Methane over
Transition Metals, 144 (1993) 38.
[9] G. Kurz, S. Teuner, Erdol. Kohle, Calcor Process for CO Production, 43 (1990)
171.
[10] S. Wang, G.Q. Lu, Appl. Catal. A Reforming of methane with carbon dioxide over
Ni/Al2O3 catalysts: Effect of nickel precursor, 169 (1998) 271.
[11] A. Erdohelyi, J. Cserenyi, E. Papp, F. Solymosi, J. Catal. Activation of CH 4 and Its
Reaction with CO2 over Supported Rh Catalysts, 141 (1993) 287.
[12] Z.L. Zhang, V.A. Tsipouriari, A.M. Efstathiou, X.E. Verykios, J. Catal., Reforming
of Methane with Carbon Dioxide to Synthesis Gas over Supported Rhodium Catalysts: I.
Effects of Support and Metal Crystallite Size on Reaction Activity and Deactivation
Characteristics,158 (1996) 51.
[13] J.H. Bitter, W. Hally, K. Seshan, J.G. van Ommen, J.A. Lercher, Catal. Today The
role of the oxidic support on the deactivation of Pt catalysts during the CO2 reforming of
methane, 29 (1996) 349.
[14] A. Erdohelyi, J. Cserenyi, E. Papp, F. Solymosi, Appl. Catal. A: Gen., Catalytic
reaction of methane with carbon dioxide over supported palladium, 108 (1994) 205.
[15] D. Oin, J. Lapszewicz, Catal. Today, Study of mixed steam and CO2 reforming of
CH4 to syngas on MgO-supported metals, 21 (1994) 551.
[16] I.S. Metcalfe and S. Sundaresan, Oxygen transfer between metals and oxygen-ion
conduction supports, AIChE J., 34(2) (1988) 195.
[17] R.G. Silver, C.J. Hou and J.G. Ekerdt, J. Catal., The role of lattice anion vacancies
in the activation of CO and as the catalytic site for methanol synthesis over zirconium
dioxide and yttria-doped zirconium dioxide, 118 (1989) 400.
[18] N.B. Jackson and J.G. Ekerdt, J. Catal., The surface characteristics required for
isosynthesis over zirconium dioxide and modified zirconium dioxide, 126 (1990) 31.
[19] B.K. Cho, J. Catal., Chemical modification of catalyst support for enhancement of
transient catalytic activity: nitric oxide reduction by carbon monoxide over rhodium, 131
(1991) 74.
[20] W.-P. Dow and T.-J. Huang, J. Catal., Effects of Oxygen Vacancy of Yttria-
Stabilized Zirconia Support on Carbon Monoxide Oxidation over Copper Catalyst, 147
(1994) 322.
[21] W.-P. Dow, Y.-P. Wang and T.-J. Huang, J. Catal., Yttria-Stabilized Zirconia
Supported Copper Oxide Catalyst: I. Effect of Oxygen Vacancy of Support on Copper
Oxide Reduction, 160 (1996) 155.
[22] W.-P. Dow and T.-J. Huang, J. Catal., Yttria-Stabilized Zirconia Supported Copper
Oxide Catalyst: II. Effect of Oxygen Vacancy of Support on Catalytic Activity for CO
Oxidation, 160 (1996) 171.
[23] P.A. Dilara and J.M. Vohs, J. Phys. Chem., TPD and HREELS investigation of the
reaction of formic acid on zirconium dioxide(100), 97 (1993) 12919.
[23b] M.A. Barteau, J. Vac. Sci. Technol. A, Site requirements ofreactions on oxide
surfaces, 11 (1993) 2162.
[24] Z.X. Liu, Q.X. Bao, N.J. Wu, J. Catal., Mechanism for promoting the evolution of
lattice oxygen by the interaction between V2O5 and TiO2, 113 (1988) 45.
[25] A. Belansky, J. Haber, Marcel Dekker, New York, 1996.
[25b] E.C. Subbarao, H.S. Maiti, Solid State Ionics, Solid electrolytes with oxygen ion
conduction, 11 (1984) 317.
[26] Iguchi E, Nakamaura S, Munakata F, Kurumada M, Fujie Y. J Appl Phys, Ionic
conduction due to oxygen diffusion in La0.8Sr0.2GaO3–δ electrolyte, 2003, 93:3662.
[27] Iguchi E, Mochizuki S. J Appl Phys, Electric conduction and dielectric relaxation
processes in solid oxide fuel cell electrolyte La0.5Sr0.5Ga0.6Ti0.4O3–δ, 2004;96:3889.
[28] Huang K, Feng M, Goodenough JB. J Am Ceram Soc, Synthesis and electrical
properties of dense Ce0.9Gd0.1O1.95 ceramics, 1998;81:357.
[28] Kurumada M, Hara H, Munakata F, Iguchi E. Solid State Ionics Electric
conductions in La0.9Sr0.1GaO3−δ and La0.9Sr0.1Ga0.9Mg0.1O3−δ, 2005;176:245.
[30] Catlow CRA, Chadwick AV, Greaves GV, Moroney LM. J Am Ceram Soc, EXAFS
Study of Yttria-Stabilized Zirconia, 1986;69:272.
[31] Yamamura Y, Kawasaki S, Sakai H. Solid State Ionics, Molecular dynamics
analysis of ionic conduction mechanism in yttria-stabilized zirconia, 1999;126:181.
[32] McCullough, J. D., and Trueblood, K. N., Acta Cryst, 12, 507 (1959).
[33] Evans, P. A., Stevens, E., and Binner, J. G. P., Trans, J, Brit. Ceram. Soc. 83, 39
(1984).
[34] Scott, H. G., J, Mater, Sol, 10, 1527 (1975).
[35] Garvie, R.C., J, Phys, Chem, The Occurrence of Metastable Tetragonal Zirconia as
a Crystallite Size Effect, 69, 1238 (1965).
[36] Dexpert-Ghys, J., Faucher, M., and Caro, P., J. Solid State Chem, 84, 179 (1984).
[37] Catlow, G. R. A., Chadwick, A. V., Greaves, G. N., and Moroney, L. M., J, Amer.
Ceram. Soc. 69, 272 (1986).
[38] Etsell, T. H., and Flengas, S. N., Chem Rev., The electrical properties of solid oxide
electrolytes, 70, 339 (1970).
[39] Beyne, L., in "Mass Transport in Oxides", National Bureau of Standards Special
Publication 296, 149 (1968).
[40] Kingerly, W. D., Pappis, J., Dory, M. E., and Hill, D. C., J. Amer. Ceram. Soc. 42,
393 (1959).
[41] J. Zhu, J.G. van Ommen, A. Knoester, L. Lefferts, J. Catal., Effect of surface
composition of yttrium-stabilized zirconia on partial oxidation of methane to synthesis gas,
230 (2005) 291.
[42] M. Labaki, S. Siffert, J.F. Lamonier, E.A. Zhilinskaya, A. Aboukais, Appl. Catal. B,
Total oxidation of propene and toluene in the presence of zirconia doped by copper and
yttrium: Role of anionic vacancies, 43 (2003) 261.
[43] Luo J, Hairetdinov, Almond DP, Stevens R. Solid State Ionics, The characteristic
frequencies for ionic conduction in 12 mol.% Y2O3 doped ZrO2, 1999;122:205.
[44] M.Y. He, J.G. Ekerdt, J. Catal. Temperature-programmed studies of the adsorption
of synthesis gas on zirconium dioxide, 87 (1984) 238.
[45] N.B. Jackson, J.G. Ekerdt, J. Catal. The surface characteristics required for
isosynthesis over zirconium dioxide and modified zirconium dioxide, 126 (1990) 31.
[46] N.B. Jackson, J.G. Ekerdt, J. Catal. Isotope studies of the effect of acid sites on the
reactions of C3 intermediates during isosynthesis over zirconium dioxide and modified
zirconium dioxide, 126 (1990) 46.
[47] J. Zhu, J.G. van Ommen, L. Lefferts, J. Catal. Reaction scheme of partial oxidation
of methane to synthesis gas over yttrium-stabilized zirconia, 225 (2004) 388.
[49] J.H. Lunsford, Stud. Surf. Sci. Catal. 81 (1994) 1.
[50] Z. Zhang, X.E. Verykios, M. Baerns, Catal. Rev.-Sci. Eng. 36 (1994) 507.
[51] He, M-Y., and Ekerdt, J. G., J. Catal. Methanol formation on zirconium dioxide,
90, 17 (1984).
[52] Jackson, N. B., and Ekerdt, J. G., J. Catal. Methanol synthesis mechanism over
zirconium dioxide, 101, (1986) 90.
[53] Yamaguchi, T., Jin, T., and Tanabe, K., J, Phys. Chem, Structure of acid sites on
sulfur-promoted iron oxide, 90, 3148 (1986).
[54] Tseng, S. C., Jackson, N. J.,-and Ekerdt, J. G., J. Catal., Isosynthesis reactions of
CO/H2 over zirconium dioxide, 109, 284 (1988).
[54b] Ekerdt, J. G., Study of synthesis gas conversion over metal oxides, Progress report,
1987-8.
[55] Jin, T., Yamaguchi, T., and Tanabe, K., J, Phys. Chem., Mechanism of acidity
generation on sulfur-promoted metal oxides, 90, 4794 (1986).
[56] Bensitel, M., Saur, O., Lavalley, J-G., and Morrow, B. A., Mater, Chem. Phys. 19,
147 (1988).
[57] He, M-Y, and Ekerdt, J. G., J. Catal. Infrared studies of the adsorption of synthesis
gas on zirconium dioxide, 87, 381 (1984).
[58] Abe, H., Maruya, K-I., Domen, K., and Onlshi, T., Chem. Lett. Chem. Soc. Japan,
1875 (1984).
[59] I.S. Metcalfe, S. Sundaresan, Chem. Eng. Sci. Oxygen storage in automobile
exhaust catalyst, 41 (1986) 1109.
[64] J.H. Bitter, W. Hally, K. Seshan, J.G. van Ommen, J.A. Lercher, Catal. Today The
role of the oxidic support on the deactivation of Pt catalysts during the CO2 reforming of
methane, 29 (1996) 349.
[65] K. Seshan, H.W. ten Barge, W. Hally, A.N.J. van Keulen, J.R.H. Ross, Stud. Surf.
Sci. Catal. 81 (1994) 285.
[66] J.A. Lercher, J.H. Bitter, W. Hally, W. Niessen, K. Seshan, Stud. Surf. Sci. Catal.
101 (1996) 463.
[67] J.W. Hightower, Stud. Surf. Sci. Catal., 1 (1976) 615.
[68] G.I. Straguzzi, H.R. Aduriz and C.E. Gigola, J. Catal., Redispersion of platinum on
alumina support, 66 (1980) 171.
[69] H. Lieske, G. Lietz, H. Spindler and J. Vtilter, J. Catal., Reactions of platinum in
oxygen- and hydrogen-treated Pt/γ-Al2O3 catalysts : I. Temperature-programmed reduction,
adsorption, and redispersion of platinum, 81 (1983) 8.
[70] T.J. Lee and Y.G. Kim, J. Catal., Redispersion of supported platinum catalysts, 90
(1984) 279.
[71] G.C. Bond, R.R. Rajaram and R. Burch, J. Phys. Chem., Hydrogenolysis of
propane, n-butane, and isobutane over variously pretreated ruthenium/titanium dioxide
catalysts, 90 (1986) 4877.
[72] M. Guenin, P.N. da Silva and R. Frety, Appl. Catal., Influence of chlorine towards
metal-support and metal-sulphur support interactions, 27 (1986) 313.
[73] M. Valigi, A. Cimino, D. Gazzoli and G. Minelli, Solid State Ionics. The influence
of additives (Cl-, ReO-4, Ti(IV)) on some properties of ZrO2, 32-33 (1989) 698.
[74] D.W. Goodman and M. Kiskinova, Surf. Sci., Chemisorption and reactivity studies
of H2 and CO on sulfided Ni(100), 105 (1981) L265.
[75] M. Kiskinova and D.W. Goodman, Surf. Sci., Modification of chemisorption
properties by electronegative adatoms: H2 and CO on chlorided, sulfided, and phosphided
Ni(100), 108 (198l) 64.
[78] J.B. Wang, W.H. Shih, T.J. Huang, Appl. Catal. A: Gen., Study of Sm 2O3-doped
CeO2/Al2O3-supported copper catalyst for CO oxidation, 203 (2000) 191.
[79] R.G. Silver, C.J. Hou, J.G. Ekerdt, J. Catal. The role of lattice anion vacancies in
the activation of CO and as the catalytic site for methanol synthesis over zirconium dioxide
and yttria-doped zirconium dioxide, 118 (1989) 400.