The active site for methanol synthesis on a Cu/ZnO/SiO2 catalyst

This note rectifies serious omissions from the references included in a recent paper by Fujitani et al. concerned with methanol synthesis over Cu/SiO₂ containing ZnO. This revised version was published online in July 2006 with corrections to the Cover Date.     

Carbon nanotube-supported Pd–ZnO catalyst for hydrogenation of CO2 to methanol

A type of Pd–ZnO catalysts supported on multi-walled carbon nanotubes (MWCNTs) were developed, with excellent performance for CO₂ hydrogenation to methanol. Under reaction conditions of 3.0 MPa and 523 K, the observed turnover-frequency of CO₂ hydrogenation reached 1.15 × 10⁻² s⁻¹ over the 16%Pd_0.1Zn₁/CNTs(h-type). This value was 1.17 and 1.18 times that (0.98 × 10⁻² and 0.97 × 10⁻² s⁻¹) of the 35%Pd_0.1Zn₁/AC and 20%Pd_0.1Zn₁/γ-Al₂O₃ catalysts with the respective optimal Pd_0.1Zn₁-loading. Using the MWCNTs in place of AC or γ-Al₂O₃ as the catalyst support displayed little change in the apparent activation energy for the CO₂ hydrogenation, but led to an increase of surface concentration of the Pd⁰-species in the form of PdZn alloys, a kind of catalytically active Pd⁰-species closely associated with the methanol generation. On the other hand, the MWCNT-supported Pd–ZnO catalyst could reversibly adsorb a greater amount of hydrogen at temperatures ranging from room temperature to 623 K. This unique feature would help to generate a micro-environment with higher concentration of active H-adspecies at the surface of the functioning catalyst, thus increasing the rate of surface hydrogenation reactions. In comparison with the “Parallel-type (p-type)” MWCNTs, the “Herringbone-type (h-type)” MWCNTs possess more active surface (with more dangling bonds), and thus, higher capacity for adsorbing H₂, which make their promoting action more remarkable.     

Effect of metal oxide additives on the CO hydrogenation to methanol over Rh/SiO2 and Pd/SiO2

Catalysts were prepared from ultra pure SiO₂, Pd and Rh nitrates and chlorides, and by doping with Al, Fe, Na, K or Ca nitrate. The activities and selectivities of the Pd and Rh catalysts were investigated at 553 K, H₂/CO=2 or 3 and 2.5 or 4 MPa respectively. Additives had a strong influence on the catalytic properties. The doping with alkali and alkaline earth oxides led to a strong suppression of the CO dissociation. Particularly basic additives, such as Ca, had a strong promoting effect on the methanol production. This may confirm that the formation of methanol occurs through formate intermediates.     

Partial oxidation of ethanol over Pd/CeO2 and Pd/Y2O3 catalysts

The effect of the support nature on the performance of Pd catalysts during partial oxidation of ethanol was studied. H₂, CO₂ and acetaldehyde formation was favored on Pd/CeO₂, whereas CO production was facilitated over Pd/Y₂O₃ catalyst. According to the reaction mechanism, determined by DRIFTS analyses, some reaction pathways are favored depending on the support nature, which can explain the differences observed on products distribution. On Pd/Y₂O₃ catalyst, the production of acetate species was promoted, which explain the higher CO formation, since acetate species can be decomposed to CH₄ and CO at high temperatures. On Pd/CeO₂ catalyst, the acetaldehyde preferentially desorbs and/or decomposes to H₂, CH₄ and CO. The CO formed is further oxidized to CO₂, which seems to be promoted on Pd/CeO₂ catalyst.     

Oxygen storage capacity of promoted Rh/CeC2 catalysts. Exceptional behavior of RhCu/CeO2

The effect of various additives (V, Cr, Mn, Fe, Co, Ni, Cu and Pb) on the oxygen storage capacity (OSC) of CeO₂ and Rh/CeO₂ catalysts was investigated. Copper is an excellent promoter of OSC conferring to Rh a very high resistance to sintering (900°C, 2% O₂).     

Catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

A series of MnOx–CeO₂ mixed oxide catalysts with different compositions prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of volatile organic compounds of chlorinated aromatics. MnOx–CeO₂ catalysts with different ratios of Mn/Ce + Mn were found to possess high catalytic activity in the catalytic combustion of CB, and MnOx(0.86)–CeO₂ was identified as the most active catalyst, on which the temperature of complete combustion of CB was 254 °C. Effects of systematic variation of reaction conditions, including space velocity and inlet CB concentration on the catalytic combustion of CB were investigated. Additionally, the stability and deactivation of MnOx–CeO₂ catalysts were studied by various characterization methods and other assistant experiments. MnOx–CeO₂ catalysts with high Mn/Ce + Mn ratios present a stable high activity, which is related to their high ability to remove the adsorbed Cl species and a large amount of active surface oxygen.     

Isoprene formation from CO and H2 over CeO2 catalysts

The CO-H₂ reaction over CeO₂ catalysts at around 623 K and 67 kPa forms isoprene with about 20% and 70% selectivities in total and C₅ hydrocarbons, respectively. The formation of dienes may be due to the low and high activity of CeO₂ for alkene and CO hydrogenation, respectively.     

Structural change of palladium particles supported on cerium oxide in catalytic methanol synthesis

Ultrafine palladium particles supported on cerium oxide by the coprecipitation method effectively catalyzes the methanol synthesis from carbon monoxide and hydrogen, while the catalytic activity increases in the initial stage. The Pd K-edge EXAFS (extended X-ray absorption fine structure) of the catalyst shows that a small part of palladium is still oxidized after the pretreatment with hydrogen at 573 K for 1 h. During the reaction the palladium particles in the catalyst are further oxidized due to the formation of Pd–O–Ce bonding which may stabilize the cationic palladium species being active to the reaction.     

Deactivation of CeO2 catalyst in the hydrogenation of benzoic acid to benzaldehyde

The CeO₂ catalyst has been investigated for hydrogenation of benzoic acid to benzaldehyde and shows little deactivation in stability test. BET results indicate that no significant sinter was observed on the used catalyst. SEM images show few changes taking place in surface feature of the used catalyst. Element analysis confirms that some coke is formed which leads to catalyst deactivation. XRD analysis reveals that crystalline size of catalyst is not relevant to the catalytic behavior in the range from 14.3 nm to 18.4 nm.     

Pt-CeO2/C anode catalyst for direct methanol fuel cells

In order to develop a cheaper and durable catalyst for methanol electrooxidation reaction, ceria (CeO₂) as a co-catalytic material with Pt on carbon was investigated with an aim of replacing Ru in PtRu/C which is considered as prominent anode catalyst till date. A series of Pt-CeO₂/C catalysts with various compositions of ceria, viz. 40 wt% Pt-3–12 wt% CeO₂/C and PtRu/C were synthesized by wet impregnation method. Electrocatalytic activities of these catalysts for methanol oxidation were examined by cyclic voltammetry and chronoamperometry techniques and it is found that 40 wt% Pt-9 wt% CeO₂/C catalyst exhibited a better activity and stability than did the unmodified Pt/C catalyst. Hence, we explore the possibility of employing Pt-CeO₂ as an electrocatalyst for methanol oxidation. The physicochemical characterizations of the catalysts were carried out by using Brunauer Emmett Teller (BET) surface area and pore size distribution (PSD) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques. A tentative mechanism is proposed for a possible role of ceria as a co-catalyst in Pt/C system for methanol electrooxidation.     

Deactivation mechanism of Pd supported on ordered and non-ordered mesoporous silica in the direct H2O2 synthesis using CO2-expanded methanol

The deactivation mechanism of Pd supported on silica and mesoporous silica (SBA-15) using CO₂-expanded methanol as solvent was studied in the direct synthesis of H₂O₂ in batch and semi-continuous batch reactor tests as well as its hydrogenolysis. Fresh and used catalysts were characterized by TPR and CO chemisorption. The results evidence the presence of deactivation, which can be correlated to the loss of accessible active metal surface area due to sintering of Pd, but there is also an effect of the presence of the ordered mesoporous structure and of the reaction conditions. The higher concentration of H₂ in solution in semi-continuous batch reactor tests with respect to batch reactor tests leads to a more relevant deactivation in Pd-SiO₂ with respect to Pd-SBA-15, but a higher initial activity, due to the fact that H₂ accelerates the reduction of the Pd species which are less reducible in Pd-SiO₂ than in Pd-SBA-15. Pd-SBA-15 shows a higher H₂O₂ selectivity and productivity with respect to Pd-SiO₂ in batch reactor tests, related to the presence of easier reducible Pd species. Another difference is related to the different mechanism of sintering. On the SBA-15 support, due to the presence of the ordered mesoporosity, the Pd particles migrate into the SBA-15 channels forming elongated 1D-type particles. In Pd-SiO₂ catalyst, instead, the sintering of the Pd particles leads to large aggregates of Pd particles in the range of 20-25 nm.     

SELECTIVE CARBON MONOXIDE OXIDATION IN H2-RICH GAS STREAM OVER Co3O4/CeO2/ZrO2, Ag/CeO2/ZrO2, AND MnO2/CeO2/ZrO2 CATALYSTS

Activity and selectivity of selective CO oxidation in an H₂-rich gas stream over Co₃O₄/CeO₂/ZrO₂, Ag/CeO₂/ZrO₂, and MnO₂/CeO₂/ZrO₂ catalysts were studied. Effects of the metaloxide types and metaloxide molar ratios were investigated. XRD, SEM, and N₂ physisorption techniques were used to characterize the catalysts. All catalysts showed mesoporous structure. The best activity was obtained from 80/10/10 Co₃O₄/CeO₂/ZrO₂ catalyst, which resulted in 90% CO conversion at 200°C and selectivity greater than 80% at 125°C. Activity of the Co₃O₄/CeO₂/ZrO₂ catalyst increased with increase in Co₃O₄ molar ratio.     

Activity and stability of Cu/ZnO/Al2O3 catalyst promoted with B2O3 for methanol synthesis

The addition of B₂O₃ to a Cu/ZnO/Al₂O₃ catalyst increased the activity of the catalyst for methanol synthesis after an induction period during the reaction. The stability of the B₂O₃-containing Cu/ZnO/Al₂O₃ catalyst was greatly improved by the addition of a small amount of colloidal silica to the catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Electron Microscopy (HREM, EELS) Study of the Reoxidation Conditions for Recovery of NM/CeO2 (NM: Rh, Pt) Catalysts from Decoration or Alloying Phenomena

The reversibility of metal–support interaction effects in NM/CeO₂ catalysts (NM: Rh, Pt) is investigated using high-resolution electron microscopy and electron energy loss spectroscopy. Reoxidation treatments at 773 K followed by a mild reduction at 473 K are not effective in recovering ceria-based systems from the decorated or alloyed states observed upon high-temperature reduction (T_red>973 K).     

Synergistic Effect of MgO and CeO2 as a Support for Ruthenium Catalysts in Ammonia Synthesis

Nanocomposite materials in MgO–CeO₂ (Ce=0–100 mol%) system were prepared as the support materials for Ru-based ammonia synthesis catalysts, so that the resultant catalytic activity was enhanced by mixing them together compared with that of the MgO or CeO₂ component was solely used as a support. Such high catalytic activity was due to two effects: electrodonating property of partially reduced CeO_2-δ to Ru metal and strong metal-support interaction derived from the unique catalyst morphology in this study.     

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.     

Effect of starting salt on catalytic behaviour of Cu-ZrO2 catalysts in methanol synthesis from carbon dioxide

Starting salts used in the co-precipitation of Cu-ZrO₂ precursors had marked influence on both activity and selectivity of resulting catalysts for methanol synthesis: chlorides increased the selectivity, suggesting the structure sensitivity of methanol formation reaction, while sulfates much enhanced the activity by affecting the dispersion of Zr species. A simultaneous use of copper chloride and zirconium sulfate greatly improved the activity and selectivity of the catalyst for methanol formation.     

Nanocrystalline CeO2 in SBA-15: Performance of Pt/CeO2/SBA-15 Catalyst for Water-gas-shift Reaction

CeO₂ particles confined within the pores of an SBA-15 mesoporous silica host were prepared by incipient wetness impregnation (IMP) and deposition precipitation (DP) methods. The materials were characterized by XRD, N₂-adsorption and temperature programmed reduction (TPR) to evaluate the structure, texture, and redox properties. The preparation procedure had significant impact on the assembling mode of CeO₂ inside the SBA-15 mesopores. A high dispersion of CeO₂ particles was achieved via DP, whereas the dispersion of CeO₂ prepared by IMP was found to be inhomogeneous and CeO₂ partially blocked the pores. The CO conversion in the water-gas-shift reaction was enhanced over 1 wt% Pt supported on CeO₂-modified SBA-15 obtained by DP.     

Low-temperature water-gas shift reaction on Au/CeO2 catalysts – the influence of catalyst pre-treatment on the activity and deactivation in idealized reformate

The effect of the pre-treatment temperature and atmosphere on the surface composition and on the activity and stability of well defined Au/CeO₂ catalysts in the low-temperature water-gas shift reaction in dilute water gas was investigated by X-ray photoelectron spectroscopy, kinetic measurements and in-situ IR spectroscopic (DRIFTS) measurements, comparing different reductive and oxidative conditioning procedures. Reductive conditioning at 200 °C yields the most active catalyst. Physical origin and consequences of the resulting differences in the reaction behavior are discussed.