Methanol synthesis from carbon dioxide at atmospheric pressure over Cu/ZnO catalyst. Role of methoxide species formed on ZnO support

Methanol synthesis from CO₂ and H₂ was carried out over a Cu/ZnO catalyst (Cu/Zn = 3/7) at atmospheric pressure, and the surface species formed were analyzed by diffuse reflectance FT-IR spectroscopy and temperature programmed desorption method. Two types of formate species and zinc methoxide were formed in the course of the reaction. Zinc methoxide was readily hydrolyzed to methanol. H₂O formed through the reverse water gas shift reaction was suggested to be involved in the hydrolysis of zinc methoxide.     

Creation of the active site for methanol synthesis on a Cu/SiO2 catalyst

The effect of ZnO/SiO₂ in a physical mixture of Cu/SiO₂ and ZnO/SiO₂ on methanol synthesis from CO₂ and H₂ was studied to clarify the role of ZnO in Cu/ZnO-based catalysts. An active Cu/SiO₂ was prepared by the following procedure: the Cu/SiO₂ and ZnO/SiO₂ catalysts with a different SiO₂ particle size were mixed and reduced with H₂ at 523-723 K, and the Cu/SiO₂ was then separated from the mixture using a sieve. The methanol synthesis activity of the Cu/SiO₂ catalyst increased with the reduction temperature and was in fairly good agreement with that previously obtained for the physical mixture of Cu/SiO₂ and ZnO/SiO₂. These results indicated that the active site for methanol synthesis was created on the Cu/SiO₂ upon reduction of the physical mixture with H₂. It was also found that ZnO itself had no promotional effect on the methanol synthesis activity except for the role of ZnO to create the active site. The active site created on the Cu/SiO₂ catalyst was found not to promote the formation of formate from CO₂ and H₂ on the Cu surface based on in situ FT-IR measurements. A special formate species unstable at 523 K with an OCO asymmetric peak at ~1585 cm^-1 was considered to be adsorbed on the active site. This revised version was published online in July 2006 with corrections to the Cover Date.     

Spectroscopic evidence for adsorption sites located at Cu/ZnO interfaces

FTIR spectra are reported of CO and formic acid adsorption on a series of Cu/ZnO/SiO₂ catalysts. Peaks due to linear CO adsorbed on copper diminished in intensity as the loading of ZnO was increased. This behaviour was explained in terms of ZnO island growth on the copper surface. Similarly, reduction of the copper concentration while maintaining a constant ZnO loading also resulted in further attenuation in bands ascribed to CO chemisorbed on copper. Formic acid exposure to a Cu/SiO₂ sample produced a formate species displaying a _as(COO) mode at 1585 cm^–1. Addition of a small quantity of ZnO to the catalyst resulted in substantial promotion of formate growth, which was accompanied by a shift (and broadening) of the _as(COO) vibration to 1660–1600 cm^–1. Since further ZnO incorporation poisoned formate creation it was concluded that formate species bonded to Cu and Zn sites located at interfacial positions had been formed. The role of such species in methanol synthesis is discussed.     

In situ FTIR studies of methanol adsorption and dehydrogenation over Cu/SiO2 catalyst

In situ FTIR spectroscopy was used to identify the adsorbed species and the intermediates during methanol dehydrogenation over Cu/SiO₂ catalyst, and a schematic reaction network was proposed. Methoxy species on copper, which were derived from adsorbed methanol, dehydrogenated into formaldehyde. Then several competitive pathways took place. The adsorbed formaldehyde could desorb to the gas phase, or react with another adsorbed methoxy group to form methyl formate, and/or undergo further dehydrogenation to CO and H₂. Carbon monoxide formed from the decomposition first adsorbed on high-index planes of copper, and then on low-index planes as the reaction progressed. With the increase of temperature, the concentration of formaldehyde and CO in gas phase increased, and that of methyl formate decreased.     

A new method of low-temperature methanol synthesis on Cu/ZnO/Al2O3 catalysts from CO/CO2/H2

A new synthesis method of low-temperature methanol proceeded on Cu/ZnO/Al₂O₃ catalysts from CO/CO₂/H₂ using 2-butanol as promoters. The Cu/ZnO/Al₂O₃ catalysts were prepared by co-impregnation of r-Al₂O₃ with an aqueous solution of copper nitrate and zinc nitrate. The total carbon turnover frequency (TOF), the yield and selectivity of methanol were the highest by using the Cu/ZnO/Al₂O₃ catalyst with copper loading of 5% and the Zn/Cu molar ratio of 1/1, which precursor were not calcined, and reduced at 493 K. The activity of the catalysts increased due to the presence of the CuO/ZnO phase in the oxidized form of impregnation Cu/ZnO/Al₂O₃ catalysts. The active sites of the Cu/ZnO/Al₂O₃ catalyst for methanol synthesis are not only metallic Cu but also special sites such as the Cu–Zn site, i.e. metallic Cu and the Cu–Zn site work cooperatively to catalyze the methanol synthesis reaction.     

Rideal-type reaction of formate species with alcohol: A key step in new low-temperature methanol synthesis method

In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to study the reaction mechanism of the formate adsorbed species with ethanol to form the ethyl formate on Cu/ZnO catalyst surface in a novel low-temperature methanol synthesis process. The results indicate that the formate adsorbed species were firstly formed by CO/CO₂/H₂ adsorbed on Cu/ZnO catalyst, followed by rapid reaction with ethanol to form ethyl formate. It was found that the species reacted with formate adsorbed species were ethanol in gas phase rather than adsorbed ethoxy species. The reaction of the adsorbed formate species with ethanol on Cu/ZnO catalyst surface proceeded according to Rideal-type mechanism, not Langmuir–Hinshelwood mechanism.     

Deactivation of Cu/ZnO catalyst during dehydrogenation of methanol

The deactivation of Cu/ZnO catalyst during methanol dehydrogenation to form methyl formate has been studied. The Cu/ZnO catalyst was seriously deactivated under the reaction conditions: various temperatures of 493, 523 and 553 K, atmospheric pressure and methanol GHSV of 3000 ml (STP)/g-cat h. The weight loss due to reduction of ZnO in the Cu/ ZnO catalyst was monitored by a microbalance. X-ray induced Auger spectroscopy of Zn(L₃M_4,5M_4,5) showed the increase in the concentration of metallic Zn on the catalyst surface after the reaction. Temperature-programmed reduction (TPR) of the Cu/ZnO catalyst with methanol demonstrated that the reduction of ZnO in Cu/ ZnO was suppressed by introduction of CO₂ into the stream of helium-methanol. As the concentration of CO₂ in the feed gas increased, the weight loss of the Cu/ZnO catalyst due to the reduction of ZnO decreased. The deactivation of the Cu/ZnO catalyst in the methanol dehydrogenation was also retarded by the addition of CO₂. In particular, oxygen injection into the reactant feed regenerated the Cu/ ZnO catalyst deactivated during the reaction. Based on these observations, the cause of deactivation of the Cu/ZnO catalyst has been discussed.     

On the mechanism of methanol synthesis and the water-gas shift reaction on ZnO

Zinc oxide catalyses both methanol synthesis and the forward and ‘everse water-gas shift reaction (f- and r- WGSR). Copper also catalyses both reactions, but at lower temperatures than ZnO. Presently the combination of Cu and ZnO stabilized by Al₂O₃ is the preferred catalyst for methanol synthesis and for the f- and r- WGSR. On Cu, the mechanism of methanol synthesis is by hydrogenation of an adsorbed bidentate formate [1] (the most stable adsorbed species in methanol synthesis), while the f- and r- WGSR proceeds by a redox mechanism. The f-WGSR proceeds by H₂O oxidizing the Cu and CO, reducing the adsorbed oxide and the r-WGSR proceeds by CO₂ oxidising the Cu and H₂, reducing it [2–5]. Here we show that the mechanisms of both reactions are subtly different on ZnO. While methanol is shown to be formed on ZnO through a formate intermediate, it is a monodentate formate species which is the intermediate; the f- and r-WGS reactions also proceed through a formate – a bidentate formate - in sharp contrast to the mechanism on Cu.     

Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2

The effect of zirconia promotion on Cu/SiO₂ for the hydrogenation of CO and CO₂ at 0.65 MPa has been investigated at temperatures between 473 and 573 K. With increasing zirconia loading, the rate of methanol synthesis is greatly enhanced for both CO and CO₂ hydrogenation, but more significantly for CO hydrogenation. For example, at 533 K the methanol synthesis activity of 30.5 wt% zirconia-promoted Cu/SiO₂ is 84 and 25 times that of unpromoted Cu/SiO₂ for CO and CO₂ hydrogenation, respectively. For all catalysts, the rate of methanol synthesis from CO₂/H₂ is higher than that from CO/H₂. The apparent activation energy for methanol synthesis from CO decreases from 22.5 to 17.5 kcal/mol with zirconia addition, suggesting that zirconia alters the reaction pathway. For CO₂ hydrogenation, the apparent activation energies (~12 kcal/mol) for methanol synthesis and the reverse water-gas shift (RWGS) reaction are not significantly affected by zirconia addition. While zirconia addition greatly increases the methanol synthesis rate for CO₂ hydrogenation, the effect on the RWGS reaction activity is comparatively small. The observed effects of zirconia are interpreted in terms of a mechanism which zirconia serves to adsorb either CO or CO₂, whereas Cu serves to adsorb H₂. It is proposed that methanol is formed by the hydrogenation of the species adsorbed on zirconia.     

The promoting effect of alcohols in a new process of low-temperature synthesis of methanol from CO/CO2/H2

The catalytic promoting effects of eleven different alcohols, as reaction medium, on the synthesis of methanol from feed gas of CO/CO₂/H₂ on Cu/ZnO solid catalyst were investigated. Added alcohol altered the reaction route to realize a low-temperature synthesis method where formate was an intermediate. Many alcohols showed catalytic promoting effect for methanol formation at temperature as low as 443 K, remarkably lower than that in the present industrial ICI process.     

Isotope Effects in Methanol Synthesis and the Reactivity of Copper Formates on a Cu/SiO2 Catalyst

Here we investigate isotope effects on the catalytic methanol synthesis reaction and the reactivity of copper-bound formate species in CO₂–H₂ atmospheres on Cu/SiO₂ catalysts by simultaneous IR and MS measurements, both steady-state and transient. Studies of isotopic variants (H/D, ¹²C/¹³C) reveal that bidentate formate dominates the copper surface at steady state. The steady-state formate coverages of HCOO (in 6 bar 3:1 H₂:CO₂) and DCOO (in D₂:CO₂) are similar and the steady-state formate coverages in both systems decrease by ~80% from 350 K to 550 K. Over the temperature range 413 K–553 K, the steady-state methanol synthesis rate shows a weak H/D isotope effect (1.05 ± 0.05) with somewhat higher activation energies in H₂:CO₂ (79 kJ/mole) than D₂:CO₂ (71 kJ/mole) over the range 473 K–553 K. The reverse water gas shift (RWGS) rates are higher than methanol synthesis and also shows a weak positive H/D isotope effect with higher activation energy for H₂/CO₂ than D₂/CO₂ (108 vs. and 102 kJ/mole) The reactivity of the resulting formate species in 6 bar H₂, 6 bar D₂ and 6 bar Ar is strongly dominated by decomposition back to CO₂ and H₂. H₂ and D₂ exposure compared to Ar do not enhance the formate decomposition rate. The decomposition profiles on the supported catalyst deviate from first order decay, indicating distributed surface reactivity. The average decomposition rates are similar to values previously reported on single crystals. The average activation energies for formate decomposition are 90 ± 17 kJ/mole for HCOO and 119 ± 11 kJ/mole for DCOO. By contrast to the catalytic reaction rates, the formate decomposition rate shows a strong H/D kinetic isotope effect (H/D ~8 at 413 K), similar to previously observed values on Cu(110).     

Study on the Mechanism of CO Formation in Reverse Water Gas Shift Reaction Over Cu/SiO2 Catalyst by Pulse Reaction, TPD and TPR

The mechanism of reverse water gas shift reaction over Cu catalyst was studied by pulse reaction with QMS monitoring, temperature programmed desorption (TPD) and temperature programmed reduction (TPR) of Cu/SiO₂ catalyst. The reduced and/or oxidized copper offered low catalytic activity for the dissociation of CO₂ to CO in the pulse reaction study with 1 ml volume of He/CO₂, but the rate of CO formation was significantly enhanced with H₂ participating in the reaction. The TPD spectra of CO₂ obtained by feeding H₂/CO₂ over copper at 773 K provided strong evidence of the formation of formate at high temperature. The formate derived from the association of H₂ and CO₂ is proposed to be the key intermediate for CO production. The formate dissociation mechanism is the major reaction route for CO production.     

Methanol synthesis over Cu/SiO2 catalysts

The rates of CO and CO/CO₂ hydrogenation at 4.2 MPa and 523 K are reported for a series of Cu/SiO₂ catalysts containing 2 to 88 wt.% Cu. These catalysts were prepared on a variety of silica sources using several different Cu deposition techniques. In CO/CO₂ hydrogenation, the rate of methanol formation is proportional to the exposed Cu surface area of the reduced catalyst precursor, as determined by N₂O frontal chromatography. The observed rate, 4.2×10^–3 mole CH₃OH/Cu site-sec, is within a factor of three of the rates reported by others over Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts under comparable conditions. These results suggest that the ZnO component is only a moderate promoter in methanol synthesis. Hydrogenation of CO over these catalysts also gives methanol with high selectivity, but the synthesis rate is not proportional to the Cu surface area. This implies that another type of site, either alone or in cooperation with Cu, is involved in the synthesis of methanol from CO.     

CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared via a route of solid-state reaction

Cu/ZnO/ZrO₂ catalysts were prepared by a route of solid-state reaction and tested for the synthesis of methanol from CO₂ hydrogenation. The effects of calcination temperature on the physicochemical properties of as-prepared catalysts were investigated by N₂ adsorption, XRD, TEM, N₂O titration and H₂-TPR techniques. The results show that the dispersion of copper species decreases with the increase in calcination temperature. Meanwhile, the phase transformation of zirconia from tetragonal to monoclinic was observed. The highest activity was achieved over the catalyst calcined at 400 °C. This method is a promising alternative for the preparation of highly efficient Cu/ZnO/ZrO₂ catalysts.     

Methanol synthesis over Cu/ZnO catalysts prepared by ball milling

Cu/ZnO catalysts (with a Cu/Zn atomic ratio of 30/70) have been prepared by high intensity mechanical mixing of copper and zinc oxide powder in air and under vacuum. During milling in vacuum gradual amorphisation of the constituents occurs, as evidenced by broadening of the Cu⁰ and ZnO diffraction peaks in XRD, but the two original phases remain. The result of such treatment is a catalyst with low BET area and low Cu metal surface area. Consequently, the activity of the vacuum milled samples in batch methanol production from synthesis gas (CO/CO₂/H₂=20/5/75) at 50 bar and 250°C is low. Milling in air leads to oxidation of the copper metal phase and much higher BET surface area and, after reduction, Cu metal surface area. Prolonged milling times in air result in more than 90% Cu²⁺ formation as evidenced by TPR. Activity in methanol synthesis for the air milled samples is comparable to a conventional Cu/ZnO catalyst prepared by coprecipitation. It is concluded that high intensity ball milling at ambient conditions is a promising method to prepare mixed oxide catalysts or catalyst precursors. This revised version was published online in July 2006 with corrections to the Cover Date.     

On the Issue of the Active Site and the Role of ZnO in Cu/ZnO Methanol Synthesis Catalysts

The problem concerning the active site and the role of ZnO in Cu/ZnO-based methanol synthesis catalysts can be consistently explained based on the literature results by distinguishing CO₂ and CO hydrogenations. Although only metallic copper has some activities for methanol synthesis by the hydrogenation of CO₂, Cu-Zn alloying in Cu particles is responsible for the major promotional role of ZnO in industrial Cu/ZnO-based catalysts. The morphology effect reported in the literature will probably appear for the system of highly dispersed Cu particles supported on ZnO. As for the hydrogenation of CO, Cu⁺ species or Cu-O-Zn sites are the active sites for methanol synthesis. The spillover effect of the Cu-ZnO system is not significant compared to the effect of ZnO on the creation of the Cu-O-Zn site.     

CO2 Hydrogenation to Methanol Over Cu/ZnO/Al2O3 Catalysts Prepared by a Novel Gel-Network-Coprecipitation Method

A novel gel-network-coprecipitation process has been developed to prepare ultrafine Cu/ZnO/Al₂O₃ catalysts for methanol synthesis from CO₂ hydrogenation. It is demonstrated that the gel-network-coprecipitation method can allow the preparation of the ultrafine Cu/ZnO/Al₂O₃ catalysts by homogeneous coprecipitation of the metal nitrate salts in the gel network formed by gelatin solution, which makes the metallic copper in the reduced catalyst exist in much smaller crystallite size and exhibit a much higher metallic copper-specific surface area. The effect of the gel concentration of gelatin on the structure, morphology and catalytic properties of the Cu/ZnO/Al₂O₃ catalysts for methanol synthesis from hydrogenation of carbon dioxide was investigated. The Cu/ZnO/Al₂O₃ catalysts prepared by the gel-network-coprecipitation method exhibit a high catalytic activity and selectivity in CO₂ hydrogenation to methanol.     

Influence of titania on zirconia promoted Cu/SiO2 catalysts for methanol synthesis from CO/H2 and CO2/H2

The effects of adding mixtures of titania and zirconia on the methanol synthesis activity and selectivity of Cu/SiO₂ were investigated. The synthesis of methanol from both CO/H₂ and CO₂/H₂ mixtures was examined at 0.65 MPa and temperatures between 448 and 573 K. For CO hydrogenation, the addition of ZrO₂ alone increased the methanol synthesis activity of Cu/SiO₂ by up to three-fold. Substitution of a portion of the ZrO₂ by TiO₂ decreased the methanol synthesis activity of the catalyst relative to that observed when only ZrO₂ is added. ZrO₂ addition also enhanced the methane synthesis activity by as much as seven fold. In the case of CO₂ hydrogenation, the maximum methanol synthesis activity is achieved when a 50/50 wt% mixture of ZrO₂ and TiO₂ is added to Cu/SiO₂. Neither the presence of the oxide additive nor its composition had any effect on the activity of the reverse water–gas-shift reaction, which suggests that this reaction proceeds only on Cu. The observed effects of ZrO₂ and TiO₂ on the catalytic activity of methanol synthesis from CO and CO₂, and methane synthesis from CO, are interpreted in terms of the strength and concentration of acidic and basic groups on the surface of the dispersed oxide.     

A highly efficient Cu/ZnO/Al2O3 catalyst via gel-coprecipitation of oxalate precursors for low-temperature steam reforming of methanol

The impact of preparation methods on the structure and catalytic behavior of Cu/ZnO/Al₂O₃ catalysts for H₂ production from steam reforming of methanol (SRM) has been reported. The results show that the nanostructured Cu/ZnO/Al₂O₃ catalyst obtained by a novel gel-coprecipitation of oxalate precursors has a high specific surface area and high component dispersion, exhibiting much higher activity in the SRM reaction as compared to the catalysts prepared by conventional coprecipitation techniques. It is suggested that the superior catalytic performance of the oxalate gel-coprecipitation-derived Cu/ZnO/Al₂O₃ catalyst could be attributed to the generation of “catalytically active” copper material with a much higher metallic copper specific surface as well as a stronger Cu–Zn interaction due to an easier incorporation of zinc species into CuC₂O₄ · x H₂O precursors as a consequence of isomorphous substitution between copper and zinc in the oxalate gel-precursors.     

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.