Nano-gold supported on Fe2O3: A highly active catalyst for low temperature oxidative destruction of methane green house gas from exhaust/waste gases

A number of nano-gold catalysts were prepared by depositing gold on different metal oxides (viz. Fe₂O₃, Al₂O₃, Co₃O₄, MnO₂, CeO₂, MgO, Ga₂O₃ and TiO₂), using the homogeneous deposition precipitation (HDP) technique. The catalysts were evaluated for their performance in the combustion of methane (1 mol% in air) at different temperatures (300–600 °C) for a GHSV of 51,000 h⁻¹. The supported nano-gold catalysts have been characterized for their gold loading (by ICP) and gold particle size (by TEM/HRTEM or XRD peak broadening). Among these nano-gold catalysts, the Au/Fe₂O₃ (Au loading = 6.1% and Au particle size = 8.5 nm) showed excellent performance. For this catalyst, temperature required for half the methane combustion was 387 °C, which is lower than that required for Pd(1%)/Al₂O₃ (400 °C) and Pt(1%)/Al₂O₃ (500 °C) under identical conditions. A detailed investigation on the influence of space velocity (GHSV = 10,000–100,000 cm³ g⁻¹ h⁻¹) at different temperatures (200–600 °C) on the oxidative destruction of methane over the Au/Fe₂O₃ catalyst has also been carried out. The Au/Fe₂O₃ catalyst prepared by the HDP method showed much higher methane combustion activity than that prepared by the conventional deposition precipitation (DP) method. The XPS analysis showed the presence of Au in the different oxidation states (Au⁰, Au¹⁺ and Au³⁺) in the catalyst.     

Conversion of biomass to fuel: Transesterification of vegetable oil to biodiesel using KF loaded nano-γ-Al2O3 as catalyst

KF-impregnated nanoparticles of γ-Al₂O₃ were calcinated and used as heterogeneous catalysts for the transesterification of vegetable oil with methanol for the synthesis of biodiesel (fatty acid methyl esters, FAME). The ratio of KF to nano-γ-Al₂O₃, calcination temperature, molar ratio of methanol/oil, transesterification reaction temperature and time, and the concentration of the catalyst were used as the parameters of the study. A methyl ester yield of 97.7 ± 2.14% was obtained under the catalyst preparation and transesterification conditions of KF loading of 15 wt%, calcination temperature of 773 K, 8 h of reaction time at 338 K, and using 3 wt% catalysts and molar ratio of methanol/oil of 15:1. This relatively high conversion of vegetable oil to biodiesel is considered to be associated with the achieved relatively high basicity of the catalyst surface (1.68 mmol/g) and the high surface to volume ratio of the nanoparticles of γ-Al₂O₃.     

Improvement of thermal stability of NO oxidation Pt/Al2O3 catalyst by addition of Pd

The present work has been undertaken to tailor Pt/Al₂O₃ catalysts active for NO oxidation even after severe heat treatments in air. For this purpose, the addition of Pd has been attempted, which is less active for this reaction but can effectively suppress thermal sintering of the active metal Pt. Various Pd-modified Pt/Al₂O₃ catalysts were prepared, subjected to heat treatments in air at 800 and 830 °C, and then applied for NO oxidation at 300 °C. The total NO oxidation activity was shown to be significantly enhanced by the addition of Pd, depending on the amount of Pd added. The Pd-modified catalysts are active even after the severe heat treatment at 830 °C for a long time of 60 h. The optimized Pd-modified Pt/Al₂O₃ catalyst can show a maximum activity limited by chemical equilibrium under the conditions used. The bulk structures of supported noble metal particles were examined by XRD and their surface properties by CO chemisorption and EDX-TEM. From these characterization results as well as the reaction ones, the size of individual metal particles, the chemical composition of their surfaces, and the overall TOF value were determined for discussing possible reasons for the improvement of the thermal stability and the enhanced catalytic activity of Pt/Al₂O₃ catalysts by the Pd addition. The Pd-modified Pt/Al₂O₃ catalysts should be a promising one for NO oxidation of practical interest.     

Au/Ce1−xZrxO2 as effective catalysts for low-temperature CO oxidation

The physico-chemical properties and activity of Ce-Zr mixed oxides, CeO₂ and ZrO₂ in CO oxidation have been studied considering both their usefulness as supports for Au nanoparticles and their contribution to the reaction. A series of Ce_1−xZr_xO₂ (x = 0, 0.25, 0.5, 0.75, 1) oxides has been prepared by sol–gel like method and tested in CO oxidation. Highly uniform, nanosized, Ce-Zr solid solutions were obtained. The activity of mixed oxides in CO oxidation was found to be dependent on Ce/Zr molar ratio and related to their reducibility and/or oxygen mobility. CeO₂ and Ce_0.75Zr_0.25O₂, characterized by the cubic crystalline phase show the highest activity in CO oxidation. It suggests that the presence of a cubic crystalline phase in Ce-Zr solid solution improves its catalytic activity in CO oxidation. The relation between the physico-chemical properties of the supports and the catalytic performance of Au/Ce_1−xZr_xO₂ catalysts in CO oxidation reaction has been investigated. Gold was deposited by the direct anionic exchange (DAE) method. The role of the support in the creation of catalytic performance of supported Au nanoparticles in CO oxidation was significant. A direct correlation between activity and catalysts reducibility was observed. Ceria, which is susceptible to the reduction at the lowest temperature, in the presence of highly dispersed Au nanoparticles, appears to be responsible for the activity of the studied catalysts. CeO₂-ZrO₂ mixed oxides are promising supports for Au nanoparticles in CO oxidation whose activity is found to be dependent on Ce/Zr molar ratio.     

Nanodispersed Au/Al2O3 catalysts for low-temperature CO oxidation: Results of research activity at the Boreskov Institute of Catalysis

This paper presents some important results of the studies on preparation and catalytic properties of nanodispersed Au/Al₂O₃ catalysts for low-temperature CO oxidation, which are carried out at the Boreskov Institute of Catalysis (BIC) starting from 2001. The catalysts with a gold loading of 1–2 wt.% were prepared via deposition of Au complexes onto different aluminas by means of various techniques (“deposition-precipitation” (DP), incipient wetness, “chemical liquid-phase grafting” (CLPG), chemical vapor deposition (CVD)). These catalysts have been characterized comparatively by a number of physical methods (XRD, TEM, diffuse reflectance UV/vis and XPS) and catalytically tested for combustion of CO impurity (1%) in wet air stream at near-ambient temperature. Using the hydroxide or chloride gold complexes capable of chemical interaction with the surface groups of alumina as the catalyst precursors (DP and incipient wetness techniques, respectively) produces the catalysts that contain metallic Au particles mainly of 2–4 nm in diameter, uniformly distributed between the external and internal surfaces of the support granules together with the surface “ionic” Au oxide species. Application of organogold precursors gives the supported Au catalysts of egg shell type which are either close by mean Au particle size to what we obtain by DP and incipient wetness techniques (CVD of (CH₃)₂Au(acac) vapor on highly dehydrated Al₂O₃ in a rotating reactor under static conditions) or contain Au crystallites of no less than 7 nm in size (CLPG method). Regardless of deposition technique, only the Cl-free Au/Al₂O₃ catalysts containing the small Au particles (d_i ≤ 5 nm) reveal the high catalytic activity toward CO oxidation under near-ambient conditions, the catalyst stability being provided by adding the water vapor into the reaction feed. The results of testing of the nanodispersed Au/Al₂O₃ catalysts under conditions which simulate in part removal of CO from ambient air or diesel exhaust are discussed in comparison with the data obtained for the commercial Pd and Pt catalysts under the same conditions.     

Morphology effects of Co3O4 on the catalytic activity of Au/Co3O4 catalysts for complete oxidation of trace ethylene

Au/Co₃O₄ catalysts with different morphologies (nanorods, nanopolyhedra and nanocubes) were successfully synthesized and evaluated for ethylene complete oxidation. We found that support morphology has a significant effect on catalytic activity, which is related to the exposed planes of different morphological Co₃O₄. HRTEM revealed the Co₃O₄-nanorods predominantly exposes {110} planes, while the dominant exposed planes of Co₃O₄-nanopolyhedra and -nanocubes are {011} and {001} planes, respectively. Compared with {011} and {001} planes, {110} planes exhibit the maximum amount of oxygen vacancies, which play a major role in ethylene oxidation. Therefore, Au/Co₃O₄-nanorods exhibits extraordinary catalytic activity, yielding 93.7% ethylene conversion at 0 °C.     

Preferential CO oxidation in H2-rich gas mixtures over Au/doped ceria catalysts

Nanosized gold catalysts supported on doped ceria were prepared by deposition–precipitation method. A deep characterization study by HRTEM/EDS, XRD, FT-Raman, TPR and FTIR was undergone in order to investigate the effect of ceria modification by various cations (Sm³⁺, La³⁺ and Zn²⁺) on structural and redox properties of gold catalysts. Doping of ceria affected in different way catalytic activity towards purification of H₂ via preferential CO oxidation. The following activity order was observed: Au/Zn–CeO₂ > Au/Sm–CeO₂ > Au/CeO₂ > Au/La–CeO₂. The differences in CO oxidation rates were ascribed to different concentration of metallic gold particles on the surface of Au catalysts (as confirmed by the intensity of the band at 2103 cm⁻¹ in the FTIR spectra collected during CO–O₂ interaction). Gold catalysts on modified ceria showed improved tolerance towards the presence of CO₂ and H₂O in the PROX feed. The spectroscopic experiments evidence enhanced reactivity when PROX is performed in the presence of H₂O already at 90 K.     

Cu/Al2O3 catalysts for soot oxidation: Copper loading effect

Cu/Al₂O₃ catalysts with metal loading from 0.64 to 8.8 wt.% have been prepared and characterized by different techniques: N₂ adsorption at −196 °C (BET surface area), ICP (Cu loading), XRD, selective copper surface oxidation with N₂O (Cu dispersion), TPR-H₂ (redox properties), and XPS (copper surface species). The catalytic activity for soot oxidation has been tested both in air and NO_x/O₂. The activity in air depends on the amount of easily-reduced Cu(II) species, which are reduced around 275 °C under TPR-H₂ conditions. The amount of the most active Cu(II) species increases with the copper loading from Cu_1% to Cu_5% and remains almost constant for higher copper loading. In the presence of NO_x, the first step of the mechanism is NO oxidation to NO₂, and the catalytic activity for this reaction depends on the copper loading. For catalysts with copper loading between Cu_1% and Cu_5%, the catalytic activity for soot oxidation in the presence of NO_x depends on NO₂ formation. For catalysts with higher copper loading this trend is not followed because of the low reactivity of model soot at the temperature of maximum NO₂ production. Regardless the copper loading, all the catalysts improve the selectivity towards CO₂ formation as soot oxidation product both under air and NO_x/O₂.     

Liquid phase selective hydrogenation of phthalic anhydride to phthalide over titania supported gold catalysts

Au/TiO₂ catalysts with different gold loadings were prepared by deposition–precipitation method and used for the liquid phase hydrogenation of phthalic anhydride. All the studied Au/TiO₂ catalysts exhibited excellent activity with high selectivity (>92%) to phthalide under mild reaction conditions (180 °C and 3.0 MPa H₂). Specially, catalysts with 2–3 wt.% gold loading were highly active and selective for the formation of phthalide. When reused, the catalyst showed a certain deactivation, but still was highly selective to phthalide. The deactivation was attributed to the leaching of gold, collapse of the pore structure and accumulation of organic species on the surface.     

Styrene epoxidation over gold supported on different transition metal oxides prepared by homogeneous deposition–precipitation

Epoxidation of styrene by anhydrous tert-butyl hydroperoxide over a number of transition metal oxide (viz. TiO₂, Cr₂O₃, MnO₂, Fe₂O₃, Co₃O₄, NiO, CuO, ZnO, Y₂O₃, ZrO₂, La₂O₃ and U₃O₈) supported nano-size gold catalysts, prepared by the homogeneous deposition–precipitation method, has been investigated. The supported gold catalysts (except Au/MnO₂ and Au/U₃O₈) showed good styrene conversion activity and selectivity for styrene oxide in the epoxidation. The Au loading, Au particle size and performance in the epoxidation of the supported gold catalysts are found to be strongly influenced by the transition metal oxide support used in the catalyst. The Au/TiO₂ and Au/CuO are promising catalysts for the selective epoxidation.     

A comparative study of the selective oxidation of NH3 to N2 over gold, silver and copper catalysts and the effect of addition of Li2O and CeOx

This paper describes the selective oxidation of ammonia into nitrogen over copper, silver and gold catalysts between room temperature and 400 °C using different NH₃/O₂ ratios. The effect of addition of CeO_x and Li₂O on the activity and selectivity is also discussed. The results show that copper and silver are very active and selective toward N₂. However the multicomponent catalysts: M/Li₂O/CeO_x/Al₂O₃ (M: Au, Ag, Cu) perform the best. On all three metal containing catalysts the activity and selectivity is influenced by the particle size and the interaction between metal particles and support.     

Activity, Selectivity, and Long-Term Stability of Different Metal Oxide Supported Gold Catalysts for the Preferential CO Oxidation in H2-Rich Gas

A comparative study of the catalytic performance and long-term stability of various metal oxide supported gold catalysts during preferential CO oxidation at 80°C in a H₂-containing atmosphere (PROX) reveals significant support effects. Compared to Au/-Al₂O₃, where the support is believed to behave neutrally in the reaction process, catalysts supported on reducible transition metal oxides, such as Fe₂O₃, CeO₂, or TiO₂, exhibit a CO oxidation activity of up to one magnitude higher at comparable gold particle sizes. The selectivity is also found to strongly depend on the employed metal oxide, amounting, e.g., up to 75% for Au/Co₃O₄ and down to 35% over Au/SnO₂. The deactivation, which is observed for all samples with increasing time on stream, except for Au/-Al₂O₃, is related to the build-up of surface carbonate species. The long-term stability of the investigated catalysts in simulated methanol reformate depends crucially on the ability to form such by-products, with magnesia and Co₃O₄ supported catalysts being most negatively affected. Overall, Au/CeO₂ and, in particular, Au/-Fe₂O₃ represent the best compromise under the applied reaction conditions, especially due to the superior activity and the easily reversible deactivation of the latter catalyst.     

Novel promoting effect of SO2 on the selective catalytic reduction of NOx by ammonia over Co3O4 catalyst

Spinel nano-Co₃O₄ was prepared by solid-state reaction at room temperature and investigated for selective catalytic reduction of NO_x by NH₃ (NH₃-SCR). Although suffering from pore filling and plugging, treatment of this catalyst by SO₂ showed novel promoting effect on NH₃-SCR above 250 °C. Bulk cobalt sulfate was observed over the sulfated Co₃O₄ with XRD, which would be an active component for NH₃-SCR. The sulphated Co₃O₄ catalyst exhibited good resistance to SO₂ (500 ppm, 100 ppm) and 10% H₂O at a space velocity of about 25 000 h⁻¹ at 300 °C, as tested for 12 h.     

Effect of washcoat modification with metal oxides on the activity of a monolithic Pd-based catalyst for methane combustion

The deposition of Ni, Co, Ce or Fe oxides onto the washcoat surface in the 0.5%Pd/Al₂O₃ catalyst enhances conversion of CH₄. Catalytic activity of the Pd-catalysts containing cobalt oxide depends on the incorporated amount of cobalt oxide and the method of incorporation. The highest activities were those of the 0.5%Pd/0.3%Co/Al₂O₃ and 1%Pd/0.3%Co/Al₂O₃ catalysts (cobalt oxide deposited onto the surface of Al₂O₃) and the 0.5%Pd/5%Co₃O₄–Al₂O₃ catalyst (mixed washcoat). Total SSA, Pd dispersion and Pd crystallite size in the x%Pd/y%Co/Al₂O₃ catalysts depend on the incorporated amount of PdO and cobalt oxide. Pd dispersion in the 1%Pd/Al₂O₃ catalyst increases from 4% to 20% upon deposition of 14 wt.% Co₃O₄ (by mass Al₂O₃) onto the Al₂O₃ surface (1%Pd/0.3%Co/Al₂O₃). This increase in Pd dispersion influence the increase in the activity of the 1%Pd/Al₂O₃ catalyst. On the surface of the 0.5%Pd/5%Co₃O₄–Al₂O₃ catalyst Pd occurs mainly in the form of PdO and displays considerable mobility under conditions of temperature variations—cyclically undergoing reduction and oxidation. At 500 °C, in vacuo, the reduction was irreversible and parallelled by the agglomeration of metallic Pd crystallites. At room temperature, cobalt occurred on the catalyst surface in the form of Co⁺² ions (CoAl₂O₄) and was reduced to Co⁰ at 500 °C (in vacuo). Up to 500 °C, the reduction of Co was reversible.     

Characterization of Fischer–Tropsch Cobalt-Based Catalytic Systems (Co/SiO<Subscript>2</Subscript> and Co/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) by X-ray Diffraction and Magnetic Measurements

Results of the characterization of six Co-based Fischer–Tropsch (FT) catalysts, with 15% Co loading and supported on SiO₂ and Al₂O₃, are presented. Room temperature X-ray diffraction (XRD), temperature and magnetic field (H) variation of the magnetization (M), and low-temperature (5 K) electron magnetic resonance (EMR) are used for determining the electronic states (Co⁰, CoO, Co₃O₄, Co²⁺) of cobalt. Performance of these catalysts for FT synthesis is tested at reaction temperature of 240 °C and pressure of 20 bars. Under these conditions, 15% Co/SiO₂ catalysts yield higher CO and syngas conversions with higher methane selectivity than 15% Co/Al₂O₃ catalysts. Conversely the Al₂O₃ supported catalysts gave much higher selectivity towards olefins than Co/SiO₂. These results yield the correlation that the presence of Co₃O₄ yield higher methane selectivity whereas the presence of Co²⁺ species yields lower methane selectivity but higher olefin selectivity. The activities and selectivities are found to be stable for 55 h on-stream.     

Supported Nano-Gold Catalysts for Epoxidation of Styrene and Oxidation of Benzyl Alcohol to Benzaldehyde

Nano-gold particles supported on different alkaline earth oxides (viz. MgO, CaO, BaO and SrO), Gr. IIIa metal oxides (viz. Al₂O_3, Ga₂O_3, In₂O₃ and Tl₂O₃), transition metal oxides (viz. TiO_2, Cr₂O_3, MnO_2, Fe₂O_3, CoO_x, NiO, CuO, ZnO, Y₂O₃ and ZrO₂), rare earth metal oxides (viz. La₂O_3, Ce₂O_3, Nd₂O_3, Sm₂O_3, Eu₂O_3, Tb₂O_3, Er₂O₃ and Yb₂O₃) and U₃O₈ [all prepared by depositing gold on corresponding metal oxide support by deposition precipitation (DP) and/or homogeneous deposition precipitation (HDP) method] were evaluated for their catalytic performance in the liquid phase epoxidation of styrene by tert-butyl hydroperoxide (TBHP) to styrene oxide and also in the solvent-free benzyl alcohol-to-benzaldehyde oxidation (by molecular oxygen or TBHP) reactions. For the epoxidation, the catalytic performance (styrene oxide yield) of the most promising nano-gold catalysts prepared by the HDP method was in the following order: Au/MgO > Au/Tl₂O₃ > Au/Yb₂O₃ > Au/Tb₂O₃ > Au/CaO (or TiO₂). However, for the oxidation of benzyl alcohol to benzaldehyde by molecular oxygen, the order of choice for the most promising catalysts (based on benzaldehyde yield) was Au/U₃O₈ > Au/Al₂O₃ > Au/ZrO₂ > Au/MgO. Whereas, when TBHP was used as an oxidizing agent for the benzyl alcohol oxidation, the order of choice for the most promising catalysts was Au/U₃O₈ > Au/MgO > Au/TiO₂ > Au/ZrO₂ > Au/Al₂O₃. The catalytic performance of a particular supported nano-gold catalyst was thus found to depend on the reaction catalysed by them. Moreover, it is strongly influenced by a number of catalyst parameters, such as the metal oxide support, the method of gold depositon on the support, the gold loading and also on the catalyst calcination temperature. Nano-gold particles-support interactions seem to play an important role in controlling the deposition of gold (amount of gold deposited and size and morphology of gold particles), formation of different surface gold species (Au⁰, Au¹⁺ and Au³⁺) and electronic properties of gold particles and, consequently, control the catalytic performance (both the activity and selectivity) of the supported nano-gold catalysts in the reactions. The nano-gold catalysts prepared by the HDP method showed much better catalytic performance than those prepared by the DP, coprecipitation or impregnation method; in general, the HDP method provided supported gold catalysts with much higher gold loading and/or smaller size gold particles than that achieved by the DP and other methods.     

Reduction of oxygen by hydroxylammonium salt or hydroxylamine over supported Au nanoparticles for in situ generation of hydrogen peroxide in aqueous or non-aqueous medium

Reaction of O₂ with hydroxylamine or its salts over a number of supported gold catalysts containing Au nanoparticles (at 10–70 °C) has been studied at atmospheric pressure for the in situ generation of H₂O₂ (required for organic oxidation reactions in the synthesis of fine/specialty chemicals) in aqueous (water) or non-aqueous medium. Hydrogen peroxide in high yields with harmless by-products (viz. water and nitrogen) can be generated in situ by the reduction of O₂ by hydroxylammonium sulfate (or chloride) or hydroxylamine using the supported gold catalysts particularly Au/Gd₂O₃, Au/La₂O₃ and Au/MgO, in aqueous (water) or non-aqueous (viz. methanol) medium at close to ambient conditions. The reduction of O₂ by hydroxylammonium salt to H₂O₂, however, requires preneutralization of the salt by alkali; in the absence of the neutralization, only water is formed in the reaction.     

Photocatalytic reduction of Ag2SO4 by the Dawson anion α-[P2W18O62] and tetracobalt sandwich complexes

The photocatalytic behaviours of the Dawson salt α-K₆[P₂W₁₈O₆₂] and two isomers of the tetracobalt Dawson-derived sandwich complexes, αββα-Na₁₇[Co₄(H₂O)(OH)(P₂W₁₅O₅₆)₂]·51H₂O·2NaCl and ααβα-Na₁₆[Co₄(H₂O)₂(P₂W₁₅O₅₆)₂]·51H₂O (abbreviated ββ-{Co₄P₄W₃₀} and αβ-{Co₄P₄W₃₀}, respectively), are described and compared.The direct photochemical excitation of the polyoxometalates (POM) in the presence of propan-2-ol as electron donor leads to their reduction. With polyoxometalates as photocatalyst and propan-2-ol as sacrificial electron donor, the reduction of Ag^I₂SO₄ from aqueous solutions is observed leading to metallic Ag_n⁰ clusters and colloidal metal nanoparticles stabilized by POM.In the case of both {Co₄P₄W₃₀}, TEM experiments reveal that most of the Ag_n particles obtained with a slight excess of Ag⁺ are spherical with a quite large distribution in size between 10 and 100 nm.     

Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes

Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NO_x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH₄NO₃ above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO₂, a product of the reduction, can dimerize and then dissociate in molten NH₄NO₃ to NO⁺ + NO₃⁻, and may be stabilized within the melt as either an adduct or as HNO₂ formed from the hydrolysis of NO⁺ or N₂O₄. The other product of reduction, NH₄NO₂, readily decomposes at ≤100 °C to N₂ and H₂O, the desired end products of DeNO_x catalysis. A mechanism for the acid catalyzed reduction of NH₄NO₃ by NO is proposed, with HNO₃ as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO_x systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).     

A thermogravimetric study of the partial oxidation of methanol for hydrogen production over a Cu/ZnO/Al2O3 catalyst

The partial oxidation of methanol for the production of hydrogen was investigated in both a fixed-bed microreactor and in a thermogravimetric analyzer (TG-FTIR) from 180 °C to 250 °C using a commercial Cu/ZnO/Al₂O₃ catalyst. In the microreactor, a hot spot in the undiluted catalyst bed of 4 K and 32 K was observed at 180 °C and 220 °C, respectively. Methanol conversion was strongly accelerated between 180 °C and 220 °C. In the TG-FTIR experiments, the reduced copper was completely oxidized to cuprite, Cu₂O, with increasing time-on-stream in the presence of oxygen and methanol (O₂/MeOH = 0.5) at 180 °C. The selectivity to formaldehyde increased in the same manner as the catalyst was oxidized to cuprite. In contrast, at 250 °C the catalyst remained completely reduced for the same O₂/MeOH ratio. Two main reaction pathways are proposed explaining the influence of the copper oxidation state on the product distribution.