In situ observation of methoxide hydrogenation on the Ni(111) surface

The surface chemistry of methoxide (CH₃O-) on the Ni(111) surface has been studied in the presence of hydrogen pressures up to 2 Torr. During heating in vacuum methoxide decomposes to H₂ and CO, which desorb at 380 and 445 K, respectively. The CH₃O-decomposition process is rate limited by CH bond breaking and exhibits a strong deuterium kinetic isotope effect in CD₃O-. In the presence of ambient hydrogen pressures of 0.02–2.0 Torr both CH₃O- and CD₃O-are hydrogenated directly to methanol at 310 K. Methoxide is hydrogenated by adsorbed hydrogen, which nearly saturates the surface at these pressures and temperatures.     

CO oxidation on a Cu(100) catalyst

The oxidation of carbon monoxide by molecular oxygen on a single crystal Cu(100) catalyst was studied at 458 K using reactant gas mixtures with CO/O₂ ratios of 2/1, 10/1 and 25/1 at a total pressure of 10 Torr. The catalytic activities were found to be strongly dependent upon the CO/O₂ ratio. Under stoichiometric reaction conditions (CO/O₂ = 2), the initial CO oxidation activity decreased sharply; with a highly reducing reaction mixture (CO/O₂ = 25), the initial activity gradually increased. These changes in catalytic activities with reactant gas mixture composition correlate with changes in surface composition, namely an increase in the surface oxygen coverage. Post-reaction TPD revealed the presence of a carbonate-like species which decomposed at ca. 630 K.     

Methane activation on clean and oxidized Ni(100)

The activation of methane was investigated on a clean and oxidized Ni(100) surface in the pressure range of 0.05–1.0 Torr. The results are most consistent with a precursor mediated mechanism being primarily responsible for the reactive sticking of methane on the clean Ni(100) surface. This contrasts with the Ni(111) surface where dissociative adsorption has been determined to occur predominantly through the direct mechanism. The reaction probability of methane on the NiO films was significantly lower than that observed for the clean Ni(100) surface and exhibited an apparent activation energy of 8.8±1.1 kcal/mol. The results suggest that methane activation on NiO occurs on defect metallic nickel sites.     

Promotion through gas phase induced surface segregation: methanol synthesis from CO, CO2 and H2 over Ni/Cu(100)

We have studied the rate of methanol formation over Cu(100) and Ni/Cu(100) from various mixtures of CO, CO₂ and H₂. It is found that the presence of submonolayer quantities of Ni leads to a strong increase in the rate of methanol formation from mixtures containing all three components whereas Ni does not influence the rate from mixtures of CO₂/H₂ and CO/H₂, respectively. The influence of the partial pressures of CO and CO₂ on the rate indicates that the role of CO is strictly promoting. From temperature-programmed desorption spectra it follows that the surface concentration of Ni depends strongly on the partial pressure of CO. In this way the increase in reactivity is interpreted as a CO-induced structural promotion introduced by the stronger bonding of CO to Ni as compared to Cu. It is suggested that this type of promotional behavior will be of general importance in existent catalysts and perhaps even more relevant in the development of new or improved bimetallic catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

CO oxidation on a model Cu/Rh(100) catalyst

The reaction between carbon monoxide and molecular oxygen on a model Cu/Rh(100) bimetallic catalyst was studied at 455 K using a CO/O₂ = 2 reactant gas mixture at a total pressure of 10.0 Torr. A maximum in the initial activity was observed at a Cu coverage of 1.3 monolayers. However, the Cu overlayers were found to be unstable at the reaction conditions employed in that the Cu films interact strongly with surface oxygen to form three-dimensional CuO_x clusters. The morphological modifications were found to influence markedly the catalytic properties of the surface. However, the initial catalytic activity and surface morphology of the Cu films could be restored by flashing the sample to > 750 K.     

Theoretical investigation of ethylene adsorbed on Ni(100) surface by the multiple-scattering cluster method

In this paper the carbon K-edge near edge X-ray absorption fine structure spectra (NEXAFS) of adsorption system C₂H₄/Ni(100) are calculated using the multiple-scattering cluster method. By a comparison between the theoretical results and experimental spectra, the chemisorption geometry of this system has been determined. The result shows that the molecule is adsorbed on the perpendicular bridge site, and the distance between the C atom and the nearest Ni atom is 1.70 Å, while the molecular plane tilting to the surface is 50°. It is found that the interaction between hydrogen atom and Ni substrate plays an important role in the formation of the adsorption structure. The above results are supported by other evidences.     

Methanol synthesis on Cu(100) from a binary gas mixture of CO2 and H2

The rate of methanol synthesis over a Cu(100) single crystal from a 1 1 mixture of CO₂ and H₂ has been measured at a total pressure of 2 bar and a temperature range of 483–563 K. At these conditions the apparent activation energy is determined to be 69 kJ mol^–1, and at 543 K the turnover rate is 2.7 × 10^–4 (site s)^–1. A kinetic model for the methanol synthesis is presented. Predictions from this model are in good agreement with the rates of methanol synthesis observed on real catalysts at industrial conditions.     

Catalytic properties of partially reduced cobalt wire in CO hydrogenation

The reaction rate and the ethylene/ethane product ratio in CO hydrogenation increase when cobalt wire, used as a catalyst for the reaction, is reduced to lower extents. The kinetic results obtained with the poorly reduced wire correlate well with temperature-programmed surface reaction (TPSR) and H₂ chemisorption results, and are interpreted to be due to electronic modification of the cobalt surface by the unreduced sub-surface cobalt oxide. It has been concluded that the extent of metal reduction is an important variable in determining the catalytic property of cobalt.     

镍基催化剂加氢还原氯代硝基苯时脱氯机制的研究

Ni-B/SiO2非晶态合金对一系列氯代芳烃硝基化合物进行加氢,脱氯顺序依次为:2-氯-5-硝基甲苯>邻氯硝基苯>间氯硝基苯=对氯硝基苯>2,5-二氯硝基苯。将Ni-B/SiO2非晶态合金和Raney Ni催化加氢邻氯硝基苯进行了对比,发现在—NO2转化成—NH2的反应终了之前,用非晶态镍催化剂的脱氯速度小于用Raney Ni催化剂的脱氯速度,但加氢反应终了之后,在非晶态镍催化剂上的脱氯速度大于Raney Ni催化剂上的脱氯速度。镍基催化剂的软硬度是催化剂选择性好坏的主要原因,镍基催化剂软度大有利于催化剂选择性的提高。     

Poisoning effect of CO on ethylene polymerization with Ni(II)-diimine/MAO

CO was not a comonomer but an inhibitor in ethylene polymerization catalyzed over [1,2-bis(2,6-diisopropylphenylimino)]acenaphthene nickel(II) dibromide (1)/MAO. The average number of active sites, , and the average rate constant for chain propagation, of the (1)/MAO system was determined using CO inhibition method based on the assumption that two molecules of CO coordinate to each active center. At 0 °C, the average number of active centers, , was increased with the Al/Ni ratio, and , was not influenced by the Al/Ni ratio. Up to Al/Ni ratio of 3000, the average number of active sites was saturated. Single active site was present at the high ratio of Al/Ni and its reactivity with CO is uniform at 0 °C. The maximum average activity was 5262.07 (kg-PE/mol-Ni/atm/hr) and 65.7% of (1) was converted to form active cation complexes at 0 °C and Al/Ni molar ratio of 5000, while 36.5% of (1) was activated at the Al/Ni molar ratio of 250. Above 30 °C, the complicated CO poisoning behavior was observed because the reactivity and stoichiometry of active centers with CO were not uniform and their thermal stability was very poor.     

Electronic,chemisorption and catalytic properties of Pd overlayers on Ru(100) probed by CO and O2 adsorption and reaction

We have employed UHV surface sensitive techniques together with CO and oxygen adsorption and reaction to link the chemical, electronic and structural properties of ultra-thin Pd films vapour-deposited on Ru(100). At low Pd coverage the properties of the Pd overlayer are considerably modified relative to the bulk-like properties exhibited by thick Pd films. A Pd coverage of 6 ML seems to mark a critical transition to bulk-like Pd behaviour. The strongest modifications in the Pd overlayer occur for coverages up to 2 ML and are exemplified by a reduction in the CO desorption temperature, a low DOS at Fermi level,E _f, and a lower activity toward CO oxidation.     

Stability of Pt-Co bimetallic particles: effect of the support induced morphology on reactivity in CO hydrogenation

The structure and the stability of bimetallic particles are controlled by their interaction with surface oxide species on support or by support geometry. Location and size of the bimetallic particles estimated by XRD and XPS, depends on the environment and treatment. Thus, the Pt-Co bimetallic particles entrapped in NaY zeolite cages become unstable upon mild oxidation by O₂ and/or reaction with surface protons causing the Co²⁺ ions formed to migrate irreversibly from the supercages into the sodalite cages as determined by TPR and TPD. Differences in the selectivity pattern observed for the CO hydrogenation over alumina and NaY zeolite supported Pt-Co catalysts, can be interpreted by the interaction between bimetallic particles with surface cobalt oxide species and the zeolite cage wall, respectively.On leave from Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China.     

The hydrogenation of acetylene in a pulsed system over Ni and Ir catalysts

In order to detect possible effects of deposited carbonaceous layers on the hydrogenation of acetylene, a pulse flow reactor was used to study this reaction. Silica supported Ni and Ir catalysts were used to study the effect of variations in the particle size and of combining the active metal with an inactive component (Au).     

分子筛在双功能催化剂中催化CO/CO2加氢研究进展

双功能催化剂可将CO/CO_2加氢直接合成低碳烯烃、芳烃和汽油等,具有工艺流程短、能耗低的优势。双功能催化剂由金属氧化物和分子筛两部分组成,分子筛特定的腔体结构、酸性质及与金属氧化物的结合方式等均可显著影响其催化性能。该文综述了近年来分子筛在双功能催化剂中用于CO/CO_2加氢反应的研究进展,简述了分子筛的类型、酸性质、形貌及颗粒尺寸、金属改性、分子筛与金属氧化物的结合方式等对双功能催化剂催化性能的影响规律,展望了双功能催化剂中分子筛的发展趋势。     

核壳纳米材料制备及其在CO/CO2热催化加氢中的应用

采用多种包覆方法制备的核壳纳米材料具有许多优于单一材料的性能,其独特的核壳结构可产生出色的协同作用和新特性,现在已经广泛用于催化、吸附、储能与转化、药物传递和光学等领域。在CO/CO₂热催化加氢反应过程中,壳层包覆可对核体粒子表面进行修饰,如改变核体的表面电荷、官能团和反应特性等,从而提高核体的稳定性与分散性。核壳催化剂可形成封闭的内部微环境以富集反应物,提高反应速率和催化活性。部分核壳催化剂甚至还能实现接力催化,并提高体系内的能量利用率。主要介绍了核壳纳米材料的常用制备方法,不同类型壳层包覆的核壳催化剂在CO/CO₂热催化加氢中的应用进展,并对该领域的未来发展进行了展望。     

Selective coordination activation regulating the selectivity for photocatalytic hydrogenation of α, β-unsaturated aldehyde over Pd/MIL-100(FeaCub)

Here, the mixed metal nodes MOFs, Pd/MIL-100(Fe_aCu_b), were constructed as photocatalysts for hydrogenation of α, β-unsaturated aldehyde (UAL) under visible light. 1 wt% Pd/MIL-100(Fe_0.81Cu_0.19) can convert a range of UAL to saturated aldehydes (SAL) with a high efficiency (≈ 100 %) and selectivity (≈ 98 %). The results of XPS and in situ DRIFTS reveal that UAL can be selectively activated via a coordination of -CC- on Cu²⁺ sites, determining the high selectivity of the photocatalytic reaction. The mixed metal nodes and Pd clusters can improve the transformation and separation of photogenerated electrons-holes. EPR result suggests that photogenerated carriers can facilitate the generation of H·on Pd/MIL-100(Fe_0.81Cu_0.19), enhancing the catalytic activity. A possible mechanism is proposed for elucidating the catalytic processes at the molecular level. This work provides a valuable strategy for tailoring the selectivity of photocatalytic hydrogenation via selective coordination activation.     

High surface area-activated carbon from Glycyrrhiza glabra residue by ZnCl2 activation for removal of Pb(II) and Ni(II) from water samples

A high-surface-area activated carbon was prepared by chemical activation of Glycyrrhiza glabra residue with ZnCl₂ as active agent. Then, the adsorption behavior of Pb(II) and Ni(II) ion onto produced activated carbon has been studied. The experimental data were fitted to various isotherm models. According to Langmuir model, the maximum adsorption capacity of Pb(II) and Ni(II) ions were found to be 200 and 166.7 mg g⁻¹, respectively, at room temperature. Kinetic studies showed the adsorption process followed pseudo second-order rate model. High values of intra-particle rate constants calculated shows the high tendency of activated carbon for removal of Pb(II) and Ni(II) ions.     

Ni/W比对NiWCx催化剂加氢性能的影响

过渡金属碳化物具有类似贵金属的电子结构和加氢性能。采用等体积浸渍法制备了不同Ni/W比的NiW/γ-Al₂O₃催化剂,以程序升温碳化法转化为NiW碳化物后对芳烃模型化合物和低温煤焦油中分离所得芳烃组分进行加氢处理。催化剂的N₂吸附、XRD、H₂-TPR和SEM表征表明,Ni的添加促进了载体表面WO₃物种的分散和还原,抑制了WO₃晶体的团聚和大晶粒的生成。萘的加氢实验表明,Ni/W原子比为0.6时催化剂的活性最佳,而添加苯酚和吡啶后的模型油加氢过程中萘的转化率和十氢萘的产率均明显下降,Ni/W原子比为0.47和0.6的催化剂性能相近,煤焦油中芳烃组分加氢后Ni/W原子比为0.47的催化剂性能更优。结果表明,Ni和W均具有良好的加氢活性,但Ni耐杂原子性能较差,二者存在一个最佳的配比以使加氢性能更优。有杂原子化合物存在时,如煤基芳烃组分的加氢,Ni/W原子比为0.47的NiW碳化物催化剂具有更好的加氢性能。     

Hydrogenation of CO and CO2 on carbon black-supported Ru catalysts

The activity and selectivity of both unsupported Ru and carbon black-supported Ru catalysts toward the hydrogenation of CO and CO₂ have been investigated in order to learn about the effect of metal particle size on both reactions. The specific activity for both reactions decreases with metal particle size and the product distribution obtained in the hydrogenation of CO (the hydrogenation of CO₂ only yields methane) is also a function of metal dispersion; thus, the proportion of methane produced increases and the olefin/paraffin decreases with decreasing Ru particle size. This behaviour is attributed to changes in the electronic properties of the Ru crystallites in close contact with the graphitised carbon black used as support.     

Methanol synthesis on a Cu(100) catalyst

The synthesis of methanol on a Cu(100) single crystal surface was studied between 500–550 K and at pressures between 44–102 kPa using a gas mixture of CO₂/CO/H₂ = 1/2/12. The specific reaction rates found for methanol synthesis were approximately an order of magnitude lower than those rates previously reported for silica supported, Cu-based catalysts. Furthermore the rates observed for the Cu(100) catalyst are estimated to be several orders of magnitude smaller than those rates found for ZnO supported Cu catalysts at comparable reaction conditions. The very low concentration of ionic copper species on the surface is thought to be responsible for the low activity of the Cu(100) catalyst.