Development of New Cu0–ZnII/Al2O3 Catalyst Supported on Copper Metallic Foam for the Production of Hydrogen by Methanol Steam Reforming

Copper metallic foam with thermal conductive properties, manufactured by S.C.P.S., has been investigated as a support for catalysts to improve thermal exchange inside the reactor for the endothermic steam reforming of methanol. Thus, we have developed a procedure for the in situ preparation of a Cu⁰–Zn^II/Al₂O₃ catalyst onto the copper metallic foam. The foam-based Cu⁰–Zn^II/Al₂O₃ catalyst shows an activity three times as high as commercial catalysts for a conversion of 74% of methanol into hydrogen.     

Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina

Methanol steam reforming was studied over several catalysts made by deposition of copper and zinc precursors onto nanoparticle alumina. The results were compared to those of a commercially available copper, zinc oxide and alumina catalyst. Temperature programmed reduction, BET surface area measurements, and N₂O decomposition were used to characterize the catalyst surfaces. XRD was used to study the bulk structure of the catalysts, and XPS was used to determine the chemical states of the surface species. The nanoparticle-supported catalysts achieved similar conversions as the commercial reference catalyst but at slightly higher temperatures. However, the nanoparticle-supported catalysts also exhibited a significantly lower CO selectivity at a given temperature and space time than the reference catalyst. Furthermore, the turnover frequencies of the nanoparticle-supported catalysts were higher than that of the commercial catalyst, which means that the activity of the surface copper is higher. It was determined that high alumina concentrations ultimately decrease catalytic activity as well as promote undesirable CH₂O formation. The lower catalytic activity may be due to strong Cu-Al₂O₃ interactions, which result in Cu species which are not easily reduced. Furthermore, the acidity of the alumina support appears to promote CH₂O formation, which at low Cu concentrations is not reformed to CO₂ and H₂. The CO levels present in this study are above what can be explained by the reverse water-gas-shift (WGS) reaction. While coking is not a significant deactivation pathway, migration of ZnO to the surface of the catalyst (or of Cu to the bulk of the catalyst) does explain the permanent loss of catalytic activity. Cu₂O is present on the spent nanoparticle catalysts and it is likely that the Cu⁺/Cu⁰ ratio is of importance both for the catalytic activity and the CO selectivity.     

Characterization and oxidation states of Cu and Pd in Pd–CuO/ZnO/ZrO2 catalysts for hydrogen production by methanol partial oxidation

Copper and zinc oxide based catalysts prepared by coprecipitation were promoted with palladium and ZrO₂, and their activity and selectivity for methanol oxidative reforming was measured and characterized by N₂O decomposition, X-ray absorption spectroscopy, BET, X-ray photoelectron spectroscopy, X-ray diffraction, and temperature programmed reduction. Addition of ZrO₂ increased copper dispersion and surface area, with little effect on activity, while palladium promotion significantly enhanced activity with little change of the catalytic structure. A catalyst promoted with both ZrO₂ and palladium yielded hydrogen below 150 °C. EXAFS results under reaction conditions showed that the oxidation state of copper was influenced by palladium in the catalyst bulk. A palladium promoted catalyst contained 90% Cu⁰, while the copper in an unpromoted catalyst was 100% Cu¹⁺ at the same temperature. Palladium preferentially forms an unstable alloy with copper instead of zinc during reduction, which persists during reaction regardless of copper oxidation state. A 100-h time on stream activity measurement showed growth in copper crystallites and change in copper oxidation state resulting in decreasing activity and selectivity. A kinetic model of the reaction pathway showed that palladium and ZrO₂ promoters lower the activation energy of methanol combustion and steam reforming reactions.     

Steam reforming of methanol using Cu-ZnO catalysts supported on nanoparticle alumina

Methanol steam reforming was studied over several catalysts made by deposition of copper and zinc precursors onto nanoparticle alumina. The results were compared to those of a commercially available copper, zinc oxide and alumina catalyst. Temperature programmed reduction, BET surface area measurements, and N₂O decomposition were used to characterize the catalyst surfaces. XRD was used to study the bulk structure of the catalysts, and XPS was used to determine the chemical states of the surface species. The nanoparticle-supported catalysts achieved similar conversions as the commercial reference catalyst but at slightly higher temperatures. However, the nanoparticle-supported catalysts also exhibited a significantly lower CO selectivity at a given temperature and space time than the reference catalyst. Furthermore, the turnover frequencies of the nanoparticle-supported catalysts were higher than that of the commercial catalyst, which means that the activity of the surface copper is higher. It was determined that high alumina concentrations ultimately decrease catalytic activity as well as promote undesirable CH₂O formation. The lower catalytic activity may be due to strong Cu-Al₂O₃ interactions, which result in Cu species which are not easily reduced. Furthermore, the acidity of the alumina support appears to promote CH₂O formation, which at low Cu concentrations is not reformed to CO₂ and H₂. The CO levels present in this study are above what can be explained by the reverse water-gas-shift (WGS) reaction. While coking is not a significant deactivation pathway, migration of ZnO to the surface of the catalyst (or of Cu to the bulk of the catalyst) does explain the permanent loss of catalytic activity. Cu₂O is present on the spent nanoparticle catalysts and it is likely that the Cu⁺/Cu⁰ ratio is of importance both for the catalytic activity and the CO selectivity.     

Effect of preparation method on structure and catalytic activity of Cr-promoted Cu catalyst in glycerol hydrogenolysis

Relationships between surface structure and catalytic properties were investigated for a series of copper chromium catalysts. The catalysts were prepared using methods involving impregnation and precipitation, and their catalytic activities were evaluated for the hydrogenolysis of glycerol. Catalyst (10I and 50I) prepared by the impregnation method contained a mixed phase of both individual copper and chromium oxide structures, while the catalyst (50P) prepared by precipitation showed a single phase, with a copper chromite spinel structure (CuCr₂O₄). XPS data indicated that, after the reduction step, the copper species in the impregnated catalyst was reduced to Cu⁰, but the catalyst prepared by the precipitation method retained a spinel structure evidenced by the large amount of Cu²⁺ species. In hydrogenolysis reactions, the precipitated catalyst showed a higher catalytic activity than the impregnated catalyst. Thus, the reduced copper chromite spinel structure, which constitutes a single phase, appears to be responsible for the high catalytic activity in the hydrogenolysis of glycerol to propylene glycol.     

Mechanistic Aspects of Hydrogen Production by Partial Oxidation of Methanol Over Cu/ZnO Catalysts

In this work, mechanistic aspects of the partial oxidation of methanol (POM) to hydrogen and carbon dioxide over Cu/ZnO catalysts have been investigated. The data obtained with different catalyst compositions and different Cu^o metal surface areas showed that the reaction depends on the presence of both the phases ZnO and Cu^o. On the other hand, for catalysts with Cu concentrations in the range 40-60 wt%, the copper metal surface area seems to be the main factor determining the reaction rate. Kinetic isotope effects using CH₃OH and CH₃OD showed that both C–H and O–H bonds are at least partially involved in the rate-limiting step. TPD experiments with pure Cu^o, pure ZnO and the catalyst Cu/ZnO showed that methanol can be activated by both ZnO and copper. On the ZnO surface methanol can form intermediates which in the presence of copper might react and desorb more easily probably via a reverse spillover process. The isotopic product distribution of H₂, HD, D₂, H₂O, HDO and D₂O in the temperature-programmed reaction of CH₃OD revealed a slight enrichment of the products with H, suggesting that during methanol activation on the ZnO some of the D atoms might be retained by the support. The effect of oxygen partial pressure suggests that oxygen atoms on the copper surface strongly promote methanol activation and H₂ and CO₂ formation. It is proposed that oxygen atoms participate in methanol activation by the abstraction of the hydroxyl H atom to form methoxide and OH_surf. This OH_surf species rapidly loses H to the surface regenerating the O_surf.     

Comparative Study of the Physico-Chemical Properties of Nanocrystalline CuO–ZnO–Al2O3 Prepared from Different Precursors: Hydrogen Production by Vaporeforming of Bioethanol

The physico-chemical and catalytic properties of CuO–ZnO–Al₂O₃, synthesised by sol–gel process (SG), impregnation method (IMP) and a combination of both preparative procedures (ISG), were comparatively studied. Samples were characterised with thermogravimetric-differential thermal analysis (TG–DTA), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) techniques and oxygen chemisorption. XPS study was not consistent with the bulk findings and revealed the presence of Cu²⁺, Cu⁺ and/or Cu⁰ species at the catalysts surface. Surface analysis revealed also that copper enrichment occurred mainly at the surface of SG and IMP solids. The reducibility of the mixed oxides catalysts was always modified with respect to that of pure copper oxides phases and the reduction of CuO was markedly affected by the presence of ZnO–Al₂O₃. Temperature programmed reduction (H₂-TPR) analysis showed that the temperature corresponding to maximum reduction rate of copper oxide was ca. 256 °C for IMP sample and ca. 296 °C for both SG and ISG solids. These latter showing a high resistance to reduction suggest a strong interaction of copper species with ZnO–Al₂O₃, limiting thus copper particles sintering. CuO particle size was found to be ca. 20 nm for both SG and ISG solids and ca. 40 nm for IMP catalysts. Besides, at 300 °C SG and ISG samples showed superior amount of reversible O₂ uptake with respect to IMP solids. Catalytic activity of CuO–ZnO–Al₂O₃ was measured with bio-ethanol steam reforming reaction. SG catalysts exhibited both high selectivity to hydrogen and high stability with time on stream than IMP and ISG catalysts. This was attributed both to the particles size of copper species, their amount on the catalytic surface and to their strong interaction with ZnO–Al₂O₃.     

Selective production of methanol from syngas over LaTi1−xCuxO3 mixed oxides

Carbon monoxide hydrogenation was studied over partially substituted copper-containing LaTi_1–xCu_xO₃ oxides and on copper supported on La₂O₃. The unsubstituted (x = 0) oxide was weakly active for CO hydrogenation, whereas all the other oxides were more active and exhibited high selectivity to methanol. Particularly, for substitutions x = 0.5–0.6, where the perovskite structure was observed, CO conversions close to 22% and selectivity close to 80% were found. Cu/La₂O₃ was, however, less active and yielded CO₂ and hydrocarbons as the major products. Using X-ray photoelectron spectroscopy it was determined that under reaction conditions copper exists as reduced species. The L₃VV X-ray induced Auger transition at 1849.2 eV observed for a representative LaMn_0.5Cu_0.5O₃ catalyst prereduced and used in CO hydrogenation at 573 K, suggests that Cu⁺ species dominates in spent catalyst. These Cu⁺ species are believed to be stable under reaction conditions in the perovskite structure, only a slight Cu enrichment occurs on the topmost layer of catalysts.     

Hydrogen production by steam reforming of methanol over Cu–CeZrYOx-based catalysts

Active and selective Cu_x(CeZrY)_1−xO_y catalysts (pure and with addition of Al₂O₃ and Cr) for the steam reforming of methanol were synthesized via the urea–nitrate combustion method. Structural, surface and redox characteristics of these catalysts were investigated by XRD, BET, IR spectroscopy, differential dissolution (DD), H₂-TPR and XPS methods. It was shown that addition of alumina and Cr leads to the steep increase in H₂ production due to appearance of highly dispersed copper species and stabilizes their activity. The parallel change of SRM rate constants and maximal rates of reduction with hydrogen characterizing mobility of lattice oxygen at variation of the catalyst composition was revealed that shows the importance of lattice oxygen mobility for steam reforming of methanol.     

Influence of preparation method on performance of Cu(Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol

The selective production of hydrogen via steam reforming of methanol (SRM) was performed using prepared catalysts at atmospheric pressure over a temperature range 200–260^∘C. Reverse water gas shift reaction and methanol decomposition reactions also take place simultaneously with the steam reforming reaction producing carbon monoxide which is highly poisonous to the platinum anode of PEM fuel cell, therefore the detailed study of effect of catalyst preparation method and of different promoters on SRM has been carried out for the minimization of carbon monoxide formation and maximization of hydrogen production. Wet impregnation and co-precipitation methods have been comparatively examined for the preparation of precursors to Cu(Zn)(Al₂O₃) and Cu(Zn)(Zr)(Al₂O₃). The catalyst preparation method affected the methanol conversion, hydrogen yield and carbon monoxide formation significantly. Incorporation of zirconia in Cu(Zn)(Al₂O₃) catalyst enhanced the catalytic activity, hydrogen selectivity and also lower the CO formation. Catalyst Cu(Zn)(Zr)(Al₂O₃) with composition Cu/Zn/Zr/Al:12/4/4/80 prepared by co-precipitation method was the most active catalyst giving methanol conversion up to 97% and CO concentration up to 400 ppm. Catalysts were characterized by atomic absorption spectroscopy (AAS), Brunauer-Emett-Teller (BET) surface area, pore volume, pore size and X-ray powder diffraction (XRPD). The XRPD patterns revealed that the addition of zirconia improves the dispersion of copper which resulted in the better catalytic performance of Cu(Zn)(Zr)(Al₂O₃). The time-on-stream (TOS) catalysts stability test was also conducted for which the Cu(Zn)(Zr)(Al₂O₃) catalyst gave the consistent performance for a long time compared to other catalysts.     

Influence of preparation method on performance of Cu(Zn)(Zr)-alumina catalysts for the hydrogen production via steam reforming of methanol

The selective production of hydrogen via steam reforming of methanol (SRM) was performed using prepared catalysts at atmospheric pressure over a temperature range 200–260^°C. Reverse water gas shift reaction and methanol decomposition reactions also take place simultaneously with the steam reforming reaction producing carbon monoxide which is highly poisonous to the platinum anode of PEM fuel cell, therefore the detailed study of effect of catalyst preparation method and of different promoters on SRM has been carried out for the minimization of carbon monoxide formation and maximization of hydrogen production. Wet impregnation and co-precipitation methods have been comparatively examined for the preparation of precursors to Cu(Zn)(Al₂O₃) and Cu(Zn)(Zr)(Al₂O₃). The catalyst preparation method affected the methanol conversion, hydrogen yield and carbon monoxide formation significantly. Incorporation of zirconia in Cu(Zn)(Al₂O₃) catalyst enhanced the catalytic activity, hydrogen selectivity and also lower the CO formation. Catalyst Cu(Zn)(Zr)(Al₂O₃) with composition Cu/Zn/Zr/Al:12/4/4/80 prepared by co-precipitation method was the most active catalyst giving methanol conversion up to 97% and CO concentration up to 400 ppm. Catalysts were characterized by atomic absorption spectroscopy (AAS), Brunauer-Emett-Teller (BET) surface area, pore volume, pore size and X-ray powder diffraction (XRPD). The XRPD patterns revealed that the addition of zirconia improves the dispersion of copper which resulted in the better catalytic performance of Cu(Zn)(Zr)(Al₂O₃). The time-on-stream (TOS) catalysts stability test was also conducted for which the Cu(Zn)(Zr)(Al₂O₃) catalyst gave the consistent performance for a long time compared to other catalysts.     

Bimetallic Pd–Cu/ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pd–Cu/ZrO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for methanol synthesis

Monometallic copper and bimetallic palladium-copper catalysts supported on ZnO–Al₂O₃ and ZrO₂–Al₂O₃ were prepared by conventional impregnation method and tested in methanol synthesis reaction under elevated pressure (3.5 MPa) in gradientless reactor at 220°C. The physicochemical properties of prepared catalytic systems were studied using BET, X-ray, TPR-H₂, TPD-NH₃ techniques. The promotion effect of palladium on catalytic activity and selectivity of copper supported catalyst in methanol synthesis reaction was proven. The highest activity of this system is explained by the Pd–Cu alloy formation.     

CuO and CuO-ZnO catalysts supported on CeO2 and CeO2-LaO3 for low temperature water-gas shift reaction

This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO₂ and CeO₂-La₂O₃ oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts' activities were tested in the forward WGSR, and the CuO/CeO₂ catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO₂ catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu⁰ and Cu¹⁺ species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst.     

11C-Radiolabeling study of methanol decomposition on chromium modified SBA-15 silica

Chromium modified mesoporous SBA-15 silica was prepared by incipient wetness impregnation of the silica support with toluene solution of chromium acetylacetonate. Powder X-ray diffraction, Nitrogen physisorption, FTIR, UV?CVis and XPS techniques as well as temperature programmed reduction with hydrogen were used for the characterization of the obtained materials. The catalytic behaviour of the samples was tested in methanol decomposition to CO and hydrogen. Novel catalytic radio isotopic based method was applied for the elucidation of the role of different chromium surface species in the catalytic process. This approach is based on the selective coverage of the surface active sites with ¹¹C- and ¹²C-methanol and simultaneous observation of the products of their conversion. It was found that the supported active phase represents a complex mixture of chromium oxide nanoparticles (mainly Cr₂O₃, CrO₃) and anchored to the silica surface mono- and polychromate structures. It was established that these species differ significantly in their catalytic behavior during the methanol decomposition and the reaction mechanism of the formation of different products was discussed.     

Methane Combustion Over Copper Chromites Catalysts Prepared by the Sol–Gel Process

Abstract  

Methane combustion was performed over a series of copper chromites (CuCr₂O₄) catalysts prepared by the sol–gel process (SG). The results were compared with those obtained over commercial CuCr₂O₄. The samples were characterised by elemental analysis, thermal analysis, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The as-synthesised CuCr₂O₄ sample exhibited higher specific surface area (248 m² g⁻¹) with respect to commercial solids (42 m² g⁻¹). The surface properties were established using XPS. Simultaneously, an increase in the atomic Cr⁶⁺/Cr³⁺ ratio (0.56 for SG catalyst vs. 0.39 for commercial sample) and a decreasing surface copper concentration (8.3%, for SG specimen vs. 17.6% for commercial catalyst) are observed. XPS study revealed also that Cu²⁺/(Cu° + Cu⁺) ratio of copper species remained constant (ca. 5) in both catalysts. Structure transformations of CuCr₂O₄ under reduction-reoxidation conditions showed that the reduction of copper and/or chromium cations from the CuCr₂O₄ and from delafossite (CuCrO₂) structure (CuCr₂O₄↔CuCrO₂ + Cu + Cr₂O₃↔Cu + Cr₂O₃) were different. This has lead to a difference in catalytic properties of the catalysts. Catalytic activity of SG catalysts was superior to that of commercial CuCr₂O₄ tested under the same conditions. Complex hysteresis behaviour for CuCr₂O₄ catalysts ramped over a temperature range of 220–850 °C where the stables active phases were obtained only after the first ramp of heating under reactants. No catalysts deactivation was further observed after several cycles of heating and cooling. The stabilisation of catalytic activity was attributed to the formation of mixed crystalline phases containing both copper and chromium species.     

Gas phase hydrogenation of maleic anhydride to γ-butyrolactone by Cu–Zn–Ti catalysts

Cu–Zn–Ti catalysts were prepared by coprecipitation method. The calcined and reduced Cu–Zn–Ti catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and N₂ adsorption. The calcined Cu–Zn–Ti catalysts were composed of CuO, ZnO, and amorphous TiO₂. There were two kinds of CuO species present in the calcined Cu–Zn–Ti catalyst. At a lower copper content, CuO species interacted with ZnO and TiO₂; at a higher copper content, both the surface-anchored and bulk CuO species were present. After reduction, metallic copper (Cu^o) appeared in all Cu–Zn–Ti catalysts. Cu^o produced by reduction of the surface-anchored CuO favored the deep hydrogenation of maleic anhydride. ZnO and TiO₂ had synergistic effect on the catalytic activity of Cu–Zn–Ti catalysts in hydrogenation of maleic anhydride.     

Catalytic combustion of volatile aromatic compounds over CuO-CeO<Subscript>2</Subscript> catalyst

Ce_1?x Cu _x O₂ oxide solid solution catalysts with different Ce/Cu mole ratios were synthesized by the one-pot complex method. The prepared Ce_1?x Cu _x O₂ catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and H₂ temperature-programmed reduction (H₂-TPR). Their catalytic properties were also investigated by catalytic combustion of phenyl volatile organic compounds (PVOCs: benzene, toluene, xylene, and ethylbenzene) in air. XRD analysis confirmed that the CuO species can fully dissolve into the CeO₂ lattice to form CeCu oxide solid solutions. XPS and H²-TPR results indicated that the prepared Ce_1?x Cu _x O₂ catalysts contain abundant reactive oxygen species and superior reducibility. Furthermore, the physicochemical properties of the prepared Ce_1?x Cu _x O₂ catalysts are affected by the Ce/Cu mole ratio. The CeCu₃ catalyst with Ce/Cu mole ratio of 3.0 contains abundant reactive oxygen species and exhibits superior catalytic combustion activity of PVOCs. Moreover, the ignitability of PVOCs is also affected by the respective physicochemical properties. The catalytic combustion conversions of ethylbenzene, xylene, toluene, and benzene are 99%, 98.9%, 94.3%, and 62.8% at 205, 220, 225, and 225 °C, respectively.     

Cu–Zn–Cr2O3 Catalysts for Dimethyl Ether Synthesis: Structure and Activity Relationship

The CuO dispersed on ZnCr₂O₄ catalysts derived from Cu–Zn–Cr hydrotalcite like layered double hydroxide precursors with varying Zn/Cr ratios have been synthesized, characterized by BET—Surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), electron spin resonance (ESR), N₂O titrations and the activities were evaluated for single step dimethyl ether (STD) synthesis from syngas. It is observed that the copper species were in highly dispersed state over Cu–ZnO–Cr₂O₃ at high Zn/Cr ratios while the copper cluster were present at low Zn/Cr ratios. The ESR analysis revealed signals due to isolated Cu²⁺ at high Zn/Cr ratios and clustered Cu²⁺ at low Zn/Cr ratio in fresh catalysts and only Cr³⁺ species in used catalysts. The TPR results indicated that the reduction peak shifted to high temperatures with an increase in chromium content due to large copper crystallites, which was supported by XRD analysis. The conversion of syngas to DME was well correlated with the copper metal surface areas, indicating that STD synthesis can be controlled by methanol synthesis rate.     

Comparative Study on Catalytic Performances for Low-temperature CO Oxidation of Cu–Ce–O and Cu–Co–Ce–O Catalysts

Two series of Cu–Ce–O and Cu–Co–Ce–O catalysts were prepared by co-precipitation method. The prepared catalysts were characterized by XRD, IR, TPR, XPS, BET and ICP-AES. The catalytic activities of the catalysts for low-temperature CO oxidation were evaluated through a microreactor-GC system. TPR results indicate that the addition of cobalt to the Cu–Ce–O can increase the dispersion of copper oxide, and the interaction between cobalt and copper can enhance the reducibility of each other. XPS analysis show that Ce⁴⁺, Cu²⁺, along with Co₃O₄, are present on the surface of Cu_0.4Co_0.6Ce₄ catalyst. The Co/Cu atomic ratio and the calcination temperature have significant effect on the activities of the catalysts. Compared with Cu₁Ce₄ catalyst, the Cu_0.4Co_0.6Ce₄ catalyst has better activity and thermal stability.     

Effects of catalyst composition on methanol synthesis from CO2/H2

Effects of catalyst composition have been studied for Cu/support and Cu/ZnO/supports in methanol synthesis from CO₂/H₂. A strong effect of support has been observed. Different supports brought about different behavior in temperature-programmed reduction of copper, different copper surface areas, and different catalytic activity and selectivity. It seemed possible to find catalyst supports that might perform better than commercial Cu/ZnO/Al₂O₃ catalysts. A correlation was observed between catalytic activity and the copper surface area which was varied by using different supports. However, the sup]>orts appeared to influence other catalytic properties as well, for example, the surface oxygen coverage.