Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

介孔-大孔结构无定形硅-铝催化剂的核磁共振研究

合成了具有介孔-大孔双模型分级结构的无定形硅-铝催化剂,利用硅和铝核的固体魔角核磁共振谱,考察了合成样品中硅和铝结构上的原子特征.     

金属掺杂中孔分子筛的合成及其研究

以十二烷二胺(DADD)为模板剂,TEOS为硅源,通过水热合成法制备出了具有高金属含量的中孔分子筛Zr-MSU-V和Nd-MSU-V,采用XRD、TG-DTA和TEM等对合成的分子筛进行了表征.XRD结果表明,即使当Si/Zr或Si/Nd的摩尔比达到5或20时,获得的两种分子筛Zr-MSU-V和Nd-MSU-V均能保持良好的结晶度,TEM图清楚地展示了Zr-MSU-V具有有序的层状结构;TG-DTA的结果显示,903 K焙烧脱除模板剂不会破坏金属嵌入分子筛的结构,说明其具有良好的热稳定性;通过48 h水热处理后的分子筛仍保持其结构有序性,说明其具有优良的水热稳定性.     

介孔氧化铁对正辛醇乙氧基化反应的催化性能

以十二烷基磺酸钠为模板剂、乙二胺为碱性介质,将水热法合成的氧化铁/十二烷基磺酸钠复合中孔材料在550℃、空气气氛中煅烧10h,除去模板剂,得到介孔氧化铁。通过X射线衍射、氮气吸附-脱附方法对介孔氧化铁的晶体结构和表面物性进行表征。表征结果显示,煅烧后的介孔氧化铁具有典型的六方介孔的结构特征,平均孔径为5.4nm。将介孔氧化铁用于催化正辛醇乙氧基化反应,研究结果表明,升高反应温度和初始压力、增加催化剂用量,可加快环氧乙烷的反应速率,同时产物的相对分子质量分布较窄。当平均聚合度为6.5时,正辛醇聚氧乙烯醚相对分子质量分布的选择性系数达到21.1。     

Selective catalytic reduction of nitric oxide by propane over vanadia-titania aerogels

An investigation has been carried out of the effect of vanadia loading on the activity and selectivity ofV₂O₅TiO₂ aerogel catalysts, prepared by a two-step procedure, for the reduction of NO by propane. The structure of catalysts have been characterized by laser Raman spectroscopy and XRD measurements. At vanadia loading levels below ca. 4.4 wt%, the vanadia is present in the form of coordinated polymeric species, whereas crystallites of V₂O₅ are formed at higher vanadia contents. At this critical level of 4.4 wt% V₂O₅, the kinetic measurements showed also a maximum in the activity per mass of catalyst which very likely indicated that the coordinated polymeric surface species are more active than crystalline V₂O₅. The selectivity towards the formation of dinitrogen decreased as the loading increased, presumably because of the formation of larger polymeric species and V₂O₅ crystallites, below and above the critical loading level, respectively. For the reduction of NO by propane, titania supported vanadia aerogel catalysts are significantly more active, per mass of catalyst, and more selective towards N₂ formation than conventionalV₂O₅TiO₂ and V₂O₅Al₂O₃ aerogel catalysts, at vanadia loading levels below ca. 11 wt%.     

The role of carbon deposition on precious metal catalyst activity during dry reforming of biogas

Gold and palladium were supported on a mesoporous TiO₂ for total oxidation of volatile organic compounds (VOCs). Mesoporous high surface area titania support was synthesised using of Ti(OC₂H₅)₂ in the presence of CTMABr surfactant. After removing the surfactant molecules, 0.5 or 1.5 wt% of palladium and 1 wt% of gold were precipitated on the support by, respectively, wet impregnation and deposition–precipitation methods. The activity for toluene and propene total oxidation of the prereduced samples follows the same order: 0.5%Pd-1%Au/TiO₂ > 1.5%Pd/TiO₂ > 0.5%Pd/TiO₂ > 1%Au-0.5%Pd/TiO₂ > 1%Au/TiO₂ > TiO₂. Moreover, a catalytic comparison with samples based on a conventional TiO₂, shows the catalytic advantage of the mesoporous TiO₂ support. The promotional effect of gold added to palladium could be partly explained by small metallic particles (TEM), but meanly by metallic particles made up of Au-rich core with a Pd-rich shell. Moreover, the hydrogen TPR profile of 0.5%Pd-1%Au/TiO₂ shows only the signal attributed to small PdO particles. Gold also implies a protecting effect of the support under reduction atmosphere. Operando diffuse reflectance infrared fourier transform (DRIFT) spectroscopy was carried on and allowed to follow the VOCs oxidation and the formation of coke molecules, but also a metallic electrodonor effect to the adsorbed molecule which increases in the same order as the activity for oxidation reaction. The presence of coke after test was also shown by DTA–TGA by exothermic signals between 300 and 500 °C and by EPR (g = 2.003).     

臭氧氧化-光催化降解水中的五氯酚

利用臭氧氧化-光催化技术降解水中的有机污染物五氯酚(PCP)。对比了紫外光照射、臭氧氧化、光催化、臭氧氧化-光催化4种方法降解PCP的情况。考察了臭氧氧化-光催化体系中臭氧流量、臭氧产量、PCP初始质量浓度、pH和CO23-等因素对PCP降解率的影响。实验结果表明,臭氧氧化-光催化法比单独使用紫外光照射、臭氧氧化、光催化法更能有效的去除PCP;增加臭氧流量和臭氧产量有利于提高PCP的降解率;降低PCP的初始浓度,PCP的降解率显著提高;pH对PCP的降解效果影响不明显;CO23-的存在显著降低了PCP的降解率。在臭氧氧化-光催化体系中,除臭氧直接氧化降解PCP外,臭氧与TiO2协同作用产生的.OH对PCP的降解也起到了重要作用。