Studies of the hydrogen held by solids: XXII. The surface chemistry of reduced molybdenaalumina catalysts

The surface hydroxyl concentrations of a fresh molybdenaalumina catalyst (8% Mo) and of the alumina from which it was made have been determined as a function of the temperature of pretreatment. Similar data were obtained for catalysts reduced with H₂ or with CO. In all cases, the hydroxyl concentrations decreased with increasing pretreatment temperatures. The difference between the curves for the parent alumina and the molybdenaalumina preparation made from it provided a measure of the number of hydroxyl groups eliminated as the epitaxial monolayer of molybdena was grown onto the surface. The values obtained (1.7 ± 0.6 OH/Mo) showed that the surface hydroxyl groups of alumina are replaced by molybdate anions. When the catalyst was reduced with CO to about $\text{e}\text{Mo}\text{= 1.5}$ (average valence, Mo^+4.5), the curve obtained was almost identical with that for the unreduced catalyst, but when the catalyst was reduced with H₂, values for the retained hydrogen were higher than for the oxidized catalyst and approached those of the parent alumina as its evacuation temperature was increased to 550 °C. This increase in hydroxyl concentration was in agreement with earlier deductions.The hydroxyl region of the infrared spectra of similar preparations was recorded. Four distinct bands could be characterized for the parent alumina at 3780, 3740, 3705, and 3650 cm^?1 and a shoulder at 3795 cm^?1. The same bands were present on the oxidized catalyst, but with lower intensities and with altered intensity ratios; i.e., some bands were affected more than others as hydroxyl groups were replaced by molybdena species. Spectra from catalysts reduced with CO were indistinguishable in the OH region from those for the unreduced catalyst. No new bands appeared when the catalysts were reduced with H₂, but the intensities of bands attributable to alumina OH increased with the 3795 cm^?1 band strengthening noticeably more than the others. Thus, the new hydroxyl groups introduced on reduction are probably alumina OH rather than MoOH as previously supposed. A form of hydrogen which is chemisorbed but which can be removed from the catalyst as H₂ on evacuation at the reduction temperature also appeared in the OH region, mainly as a continuous contribution to the low frequency edge. From absorption coefficients derived from the present data, it was deduced that about twice as many hydrogen atoms were present in the H₂ formed than were supplied by these OH groups; i.e., the chemisorption appears heterolytic with half the atoms unseen by ir. A search was made for a band attributable to MoH, but without success. A brief study was made of this adsorption process, which was found to be slow but reversible, and to have a positive pressure dependence. When the catalyst was reduced with CO, rather than with H₂, a portion of the CO remained irreversibly chemisorbed in electronically comparable amounts. Infrared spectra of such samples contained a band at about 1585 cm^?1 attributable to a carbonate species. Data for the two reducing gases differed in that no reversibly chemisorbed CO was observed. At room temperature, CO was also chemisorbed as a linear species with the stretching frequency (2190 cm^?1) higher than that of the gaseous molecule (2143 cm^?1).     

Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.     

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods: Part 1. ATR-FTIRAS spectra of CO adsorbed on highly dispersed Pt catalyst on carbon black and carbon un-supported Pt black

Elecrochemical ATR-FTIRAS measurements were conducted for the first time to investigate nature of CO adsorbed under potential control on a highly dispersed Pt catalyst with average particle size of 2.6 nm supported on carbon black (Pt/C) and carbon un-supported Pt black catalyst (Pt-B). Each catalyst was uniformly dispersed by 10 μg Pt/cm² and fixed by Nafion^® film of 0.05 μm thick on a gold film chemically deposited on a Si ATR prism window. Adsorption of CO was conducted at 0.05 V on the catalysts in 1 and 100% CO atmospheres, for which CO coverage, θ_CO, was 0.69 and 1, respectively. Two well-defined ν(CO) bands free from band anomalies assigned to atop CO (CO(L)) and symmetrically bridge bonded CO (CO(B)_sym.) were observed. It was newly found that the CO(L) band was spitted into two well-defined peaks, particularly in 1% CO, from very early stage of adsorption, which was interpreted in terms of simultaneous occupation of terrace and step-edge sites, denoted as CO(L)_terrace and CO(L)_edge, respectively. This simultaneous occupation was commonly observed in our work both on Pt/C and Pt-B. A new band was also observed around 1950 cm⁻¹ in addition to the bands of CO(L) and CO(B)_sym., which was assigned to asymmetric bridge CO, CO(B)_asym., adsorbed on (1 0 0) terraces, based on our previous ECSTM observation of CO adsorption structures on (1 0 0) facet. The CO(B)_asym. on the Pt/C, particularly in 100% CO atmosphere, results in growth of a sharp band at 3650 cm⁻¹ accompanied by a concomitant development of a band around 3500 cm⁻¹. The former and the latter are assigned to ν(OH) vibrations of non-hydrogen bonded and hydrogen bonded water molecules adsorbed on Pt, respectively, interpreted in term of results from a bond scission of the existing hydrogen bonded networks by CO(L)s and from a promotion of new hydrogen bonding among water molecules presumably by CO(B)_asym..It was found that the frequency ν(CO) of CO(L) both on Pt/C and Pt-B is lower than that on bulky polycrystalline electrode Pt(poly) or different crystal planes of Pt single-crystal electrodes by 30-40 cm⁻¹ at corresponding potentials, which implies a stronger electronic interaction between CO and Pt nano-particles and/or an increased contribution of step-edge sites on the particles. Determination of the band intensities of CO(L), CO(B)_asym. and CO(B)_sym. has led us to conclude a much higher bridged occupation of sites at Pt nano-particles than Pt(poly) electrodes.     

液相合成甲醇催化剂活性的研究

The effects of reduction procedure, reaction temperature and composition of feed gas on the activity of a CuO-ZnO-Al2O3 catalyst for liquid phase methanol synthesis were studied. An optimized procedure different from conventional ones was developed to obtain higher activity and better stability of the catalyst. Both CO and CO2 in the feed gas were found to be necessary to maintain the activity of catalyst in the synthesis process. Reaction temperature was limited up to 523K, otherwise the catalyst will be deactivated rapidly. Experimental results show that the catalyst deactivation is caused by sintering and fouling, and the effects of CO and CO2 on the catalyst activity are also investigated. The experimental results indicate that the formation of water in the methanol synthesis is negligible when the feed gas contains both CO and CO2. The mechanism for liquid-phase methanol synthesis was discussed and it differed slightly from that for gas-phase synthesis.     

DRIFT Studies of Adsorbed CO Over Sulfided K–Rh–Mo/Al2O3 Catalysts: Detection of Rh–Mo–S Phase

Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was used to study the nature of active species in K–Rh–Co–MoS₂/Al₂O₃ catalyst by means of probing with CO molecule. The effects of K addition to Rh and interaction between Mo and Rh were studied with varying K and Mo loadings over 1 wt% Rh/Al₂O₃ catalyst. In sulfided Rh–Mo/Al₂O₃, the formation of Rh–Mo–S phase was evidenced first time by a band at 2,095 cm^?1. The introduction of Co to K–Rh–MoS₂/Al₂O₃ catalyst showed the existence of both Rh and Co promoted MoS₂ sites, but the CO absorption frequencies in DRIFT spectra are significantly at lower side compared to Co free Rh–Mo catalyst. The stabilities of CO band from Rh and Co promoted and unpromoted MoS₂ sites are studied at different temperatures. When activated carbon used as support, bands for both promoted and unpromoted MoS₂ sites were appeared, but the intensity of these bands were decreased largely compared to alumina based catalyst, resulted from the coverage of added K not only on the support surface but also on the active metal components due to the neutral nature of activated carbon.     

CO adsorption and correlation between CO surface coverage and activity/selectivity of preferential CO oxidation over supported Ag catalyst: an in situ FTIR study

In situ IR measurements for CO adsorption and preferential CO oxidation in H₂-rich gases over Ag/SiO₂ catalysts are presented in this paper. CO adsorbed on the Ag/SiO₂ pretreated with oxygen shows a band centered around 2169 cm^–1, which is assigned to CO linearly bonded to Ag⁺ sites. The amount of adsorbed CO on the silver particles (manifested by an IR band at 2169 cm^–1) depends strongly on the CO partial pressure and the temperature. The steady-state coverage on the Ag surface is shown to be significantly below saturation, and the oxidation of CO with surface oxygen species is probably via a non-competitive Langmuir–Hinshelwood mechanism on the silver catalyst which occurs in the high-rate branch on a surface covered with CO below saturation. A low reactant concentration on the Ag surface indicates that the reaction order with respect to Pco is positive, and the selectivity towards CO₂ decreases with the decrease of Pco. On the other hand, the decrease of the selectivity with the reaction temperature also reflects the higher apparent activation energy for H₂ oxidation than that for CO oxidation.     

前驱体对Ru/CeO_2-ZrO_2-Al_2O_3催化剂CO选择性甲烷化的影响

以CeO_2-ZrO_2-Al_2O_3复合氧化物为载体,采用分步等体积浸渍法制备了不同Ru负载量及不同Ru前驱体的催化剂,并考察了这些因素对催化剂CO选择性甲烷化活性及为燃料电池供氢操作温度窗口的影响。结果表明,Ru负载量为1%的催化剂具有较好的CO选择性甲烷化活性及最宽的操作温度窗口;以Ru(NO)(NO_3)_3为前驱体制备的催化剂,Ru金属分散度较差,低温CO甲烷化活性较低,高温CO甲烷化选择性较差,操作温度窗口仅为15℃;以RuCl_3·xH_2O为前驱体制备的催化剂具有良好的CO选择性、甲烷化活性及60℃操作温度窗口,且水洗除氯操作对催化剂性能影响不明显。     

Low temperature CO pulse adsorption for the determination of Pt particle size in a Pt/cerium-based oxide catalyst

Unexpectedly large amounts of CO adsorption have resulted from a pulse adsorption experiment at 323 K, giving about 300% Pt dispersion in a Pt/cerium-based oxide catalyst. An in situ diffuse reflectance infrared Fourier transform spectroscopic investigation on a Pt/cerium-based oxide during CO adsorption has revealed that carbonate species on the cerium oxide surface are responsible for the unrealistically large CO adsorption at 323 K, as a result of CO spillover. Lowering the temperature to 195 K considerably diminished the amount of CO adsorption. The size of the Pt particles in the Pt/cerium-based oxide catalyst was determined by CO pulse adsorption at 195 K and showed good agreement with the particle size determined by X-ray diffraction and low energy ion scattering. This indicates that CO pulse adsorption at 195 K is a useful technique to reliably estimate the Pt particle size in a Pt/cerium-based oxide catalyst.     

醋酸液相氧化燃烧反应动力学

以醋酸钴、醋酸锰为主催化剂，溴化钾为促进剂，乙酸钾为助催化剂，在半连续搅拌釜式钛材反应器中通过测定尾气中CO2和CO的生成量，对醋酸的液相催化氧化动力学进行了研究. 分别考察了空气流量、温度、催化剂总浓度、[Co]/[Mn]比、溴离子浓度、水含量等因素对醋酸燃烧损失速率的影响. 实验结果表明，增加催化剂总浓度和[Co]/[Mn]比能明显加快CO2和CO的生成速率常数，提高溴离子浓度和降低反应温度可显著抑制醋酸的燃烧损失，同时根据实验结果得出CO2和CO的反应活化能分别为88.11和127.31 kJ/mol.     

多孔材料在催化CO2与环氧化物环加成反应中的研究进展

以CO2为原料与环氧化物合成环状碳酸酯是实现CO2资源利用最为有效的途径之一，也是缓解温室效应的有效方式之一。在该反应中催化剂的选择至关重要，多孔材料由于具有相对密度低、强度高、比表面积大、稳定性好、合成方法多样等优点而被广泛应用于催化CO2环加成。重点综述了近年来无机多孔材料、多孔有机聚合物材料、金属有机骨架材料在催化CO2与环氧化物合成环状碳酸酯中的研究进展，介绍了各催化剂的优缺点并对未来多孔材料的发展进行了展望。     

The promotion of CO electro-oxidation on platinum-bismuth as a model for surface mediated oxygen transfer

The results of electrochemical studies of CO oxidation on clean and bismuth modified Pt(1 1 0)-(1×2) and Pt(1 1 1) surfaces and a supported platinum catalyst are compared. The effect of sub-monolayers of bismuth is to increase the CO oxidation potential on Pt(1 1 0)-(1×2), and decrease it on Pt(1 1 1). This primarily reflects the rather low potential for CO oxidation characteristic of the more open packed Pt(1 1 0)-(1×2) surface, and the higher potential characteristic of the close packed Pt(1 1 1) face. The oxidation potential of CO in the intermixed CO/Bi phases on the single crystals is very similar. The effect of bismuth on the supported platinum catalyst is to increase the CO oxidation potential by a similar amount to that found for Pt(1 1 0)-(1×2). In addition, modification by bismuth results in a concomitant reduction in the CO tolerance of the commercial catalyst. CO oxidation on the catalyst exhibits poisoning by bismuth in a similar fashion to Pt(1 1 0)-(1×2), and the bismuth redox couple on the catalyst is the same as that found on Pt(1 1 0)-(1×2). High coverages of bismuth on the catalyst do not appear to reduce its activity for hydrogen oxidation. These results are discussed in the context of the requirement for surface mediated oxygen transfer during CO electro-oxidation.     

Effect of halogen anion on hexane aromatization activity of Pt/KL catalysts

Potassium salts were added to the catalyst prepared by ion exchange of KL with [Pt(NH3)₄]Cl₂ and the effect of their counter anion on the activity and selectivity for hexane aromatization was studied. The catalyst to which KF was added showed the highest activity and selectivity for benzene formation; methylcyclopentane and hydroisomerization products were negligible. Although the catalyst with KCl added also exhibited excellent performance, the catalysts with KBr or KI added gave rise to low hexane conversion and benzene yield. Infra-red spectra of adsorbed CO revealed that the presence of the low frequency C-O stretching band is closely related to catalytic performance of the Pt/KL series catalysts. The electron-rich Pt site formed through the interaction with KF or KCl may be responsible for the high activity and selectivity for hexane aromatization.     

Ion-dipole interactions between adsorbed CO and support cations in Pt/K-LTL

The adsorption of carbon monoxide on a non-acidic Pt/K-LTL catalyst has been studied by diffuse reflectance and transmission IR spectroscopy. The CO spectrum is strongly dependent on the experimental conditions. Adsorption on the small Pt clusters in the presence of water gives linear-CO bands between 2060 and 1990 cm^–1 and a bridging-CO band around 1800 cm^–1. In the absence of water, the linear bands are red shifted to about 1940 and 1720 cm^–1, respectively. The frequency shift is attributed to an ion-dipole interaction between adsorbed CO and support cations. The ion-dipole interaction is screened by the adsorbed water leading to a smaller red shift in the CO stretching frequency.     

The heterogeneous catalytic reduction of NO and N2O mixture by carbon monoxide

Kinetics of the simultaneous reduction N₂O and NO by CO on CuCo₂O₄ has been studied. The reactants are adsorbed onto the coordination-unsaturated cations of the catalyst. The studies showed that the reactions of N₂O and CO and of NO and CO occur between the adsorbed reactants on the catalyst surface; the catalyst surface is partially reduced during both these reactions. It was found that NO inhibits the reaction between N₂O and CO, because N₂O and NO compete for the active surface sites. The adsorption capacity of the catalyst is significantly higher for NO than for N₂O and hence NO displaces N₂Oads from the surface. The inhibition occurs on strongly localized sites and does not affect on the behaviour of the remaining free sites. At such blockage, the N₂O reduction rate decreases in direct proportion to the amount of adsorbed NO.     

Cu-Zn-Al-Zr催化剂在CO_2加氢制甲醇反应中的性能研究

采用共沉淀法制备了Cu-Zn-Al-Zr复合氧化物催化剂用于CO2加氢制甲醇反应。与工业用Cu-Zn-Al催化剂进行了比较,同时进行了Cu-Zn-Al-Zr催化剂稳定性试验和试验前后样品的物化表征。结果表明:在相同的反应条件下,用Cu-Zn-Al-Zr催化剂的甲醇收率较用Cu-Zn-Al催化剂得到显著提高;在200 h的稳定性试验中,Cu-Zn-Al-Zr催化剂显示较好的催化稳定性;催化剂诱导期性能的下降归因于金属Cu晶粒的长大和表面沉积物的形成,而催化剂中的微孔分布对反应影响不显著。     

生物质合成气合成二甲醚的研究

在加压固定床反应装置上进行了生物质合成气合成二甲醚(DME)的研究.采用机械混合法制备二甲醚合成双功能催化剂.考察了组成为V(H_2):V(CO):V(CO_2):V(CH_4)=52:24:23:1的生物质合成气在不同反应温度、空速、压力下对合成二甲醚反应的影响.同时进行了102 h的催化剂的稳定性实验.结果表明,在260-300℃范围内,随反应温度的升高,CO转化率和二甲醚的选择性均先增大后减小;随反应压力的升高,CO转化率和二甲醚选择性都随之升高;原料气中高浓度的CO_2可导致铜基催化剂较快的失活.     

CO铜基变换催化剂氰化氢中毒机理热力学研究

为了掌握CO变换催化剂在高炉煤气气氛下的中毒机理,文中采用热力学非均相反应体系中的Gibbs自由能最小原理,从理论上分析了CO变换催化剂在高炉煤气气氛下,HCN中毒可能发生的化学反应及产物。对各个反应的吉布斯自由能及化学反应平衡常数进行了对比分析,结果表明:氰化氢(HCN)对于铁基高温变换催化剂在其活性温度下的中毒作用很小,而对于铜基低温变换催化剂在100—300℃的活性温度下,主要的中毒产物为CuCN,CuO,Cu2O,Cu(OH)2,C,且高炉煤气自身的主要气体混合也是使催化剂中毒的原因之一。此外,氧气的存在会加快催化剂的中毒反应。其中低温变换催化剂的活性物质Cu微晶与CO和O2反应的吉布斯自由能小于0,且绝对值最大,热力学平衡常数最大。这个反应是竞争能力最强的主导反应。     

H2对CO气相催化偶联制草酸二乙酯反应的失活机理

重点研究了氢气（H₂）对一氧化碳（CO）催化偶联反应制草酸二乙酯的影响,分别考察了不同H₂浓度、不同温度和不同空时条件下加入H₂对CO偶联反应的影响,结果发现H₂的加入使反应过程中CO转化率、草酸二乙酯选择性和空时收率明显下降,且在实验条件范围内,通入H₂浓度越高、反应温度越高,催化剂活性下降越快.研究得出,H₂气氛下CO偶联反应失活动力学方程为：-da/dt=k_dc^0.65_H2.进一步分析失活动力学方程可知,加氢反应过程中,H₂和CO吸附在同一个活性中心上,H₂在活性中心上的吸附抑制了CO在催化剂上的吸附,从而使得CO催化偶联反应生成草酸二乙酯的速率下降,导致加氢后CO转化率、草酸二乙酯选择性和空时收率降低.     

Performance evaluation of porous electrocatalysts via normalization of the active surface

When comparing the rate of electrochemical processes at different porous electrocatalysts a surface normalization should be used. It is shown for the case of methanol oxidation at PtRu layers electrodeposited on gold substrates that substantially different data are obtained for current, mass spectrometry signals and integrated IR band intensities of the products, with and without normalization of the catalyst surface used. Using stripping of saturated CO coverage as a normalization tool, cyclic voltammograms, on line MS and in situ FTIR spectroscopy give reasonable agreement of catalytic activity towards methanol oxidation.On leave from: Departamento de Química, Universidade Federal do Pará, Rua Augusto Correa S/N, Belém, Pará, Brazil     

改性TiO_2纳米粒子用于可见光催化反应

采用原位溶胶-凝胶法合成氧化钛,同时对大环配合物进行改性,得到粒径为10.89 nm的纳米级钴酞菁改性氧化钛（CoPc/TiO2）光催化剂,用于可见光下、水溶液中CO2的还原反应,可得HCHO、CH3OH、HCOOH等产物。结果表明,由于金属酞菁的存在导致TiO2粒径减小,相转变温度降低,CoPc以单体形式均匀分散于TiO2凝胶基质中,其二聚及多聚倾向大大减弱。钴酞菁固载的催化剂给电子能力较强,极大地提高了光还原效率。光反应的最佳条件为：在0.1 mol/L的NaOH溶液中,0.15 g CoPc/TiO2催化剂,三乙胺和三乙醇胺作为电子供体催化效果较好,在可见光照反应10 h后,还原产物中总有机碳最高可达2 965.3μmol/g-cat。在还原过程中CO2主要以HCO3-的形式被还原而非碳酸根离子,而且HCO3-的浓度在0.2 mol/L时还原产物量最大。