羧酸酯加氢金属催化剂研究进展

羧酸酯通过催化加氢可以制备高附加值的醇、醛和酸,该类反应得到了广泛地研究.回顾了羧酸酯催化加氢所使用的金属催化剂,重点讨论了铜基催化剂、锰氧化物催化剂、贵金属铑、钌、铂和钯催化剂在羧酸酯加氢反应中的应用,并对羧酸酯加氢反应中环境友好的新型催化剂进行了展望.     

Seeding approach to noble metal decorated conducting polymer nanofiber network

Metal displacement reactions between conducting polymers-"synthetic metals"-and noble metals (Pt, Au and Ag) have been demonstrated using a seeding polymerization technique, to produce a synthetic metal nanofiber network decorated with noble metal nanoparticles, in one-step.     

选择性催化加氢合成氯代苯胺最新进展

如何抑制脱氯氢解副反应是实现高效绿色合成氯代芳胺的核心问题。依据氯代硝基苯催化加氢合成氯代苯胺反应的抑制脱氯方法,选择性加氢催化剂设计思路可分为调变催化剂金属组分与载体的相互作用,制备双/多金属催化剂、非晶态合金催化剂、聚合物稳定的贵金属催化剂和杂原子修饰的贵金属催化剂等。本文分别综述了近年来各类抑制脱氯方法的研究进展及抑制脱氯机理,并进一步分析比较了不同反应介质对催化反应性能的影响。现有研究表明,杂原子修饰的贵金属催化剂表现出更好的催化性能,无溶剂条件下合成氯代苯胺彰显了绿色友好化工理念。两者有望成为今后的研究热点。     

挥发性有机物燃烧催化剂的研究进展

挥发性有机物（VOCs）是主要大气污染物质,也是形成PM_2.5和臭氧的重要前体。强化挥发性有机物控制,是改善大气环境的重要途径。催化燃烧（氧化）被认为是去除VOCs最有效的方式之一,本文综述了VOCs催化燃烧常用的贵金属催化剂、非贵金属催化剂。其中,贵金属催化剂主要包括基于Pd、Pt、Ru等的催化剂,非贵金属催化剂主要包括Mn、Co、Ce、Zr等的氧化物,通常贵金属催化剂具有比非贵金属更高的氧化活性和稳定性,但对于含氮VOCs非贵金属催化剂（Mn、Cu）具有更好的氮气选择性,Cr基催化剂对于含氯VOCs燃烧具有更好的效果。此外,还重点讨论了载体、分散度、催化剂制备方法对贵金属催化剂性能的影响,并对发展VOCs氧化催化剂的研究提出了展望。     

基于表面等离子体共振效应的Ag(Au)/半导体纳米复合光催化剂的研究进展

由具有表面等离子体共振(surface plasmon resonance,SPR)效应的贵金属(Ag、Au等)纳米粒子和半导体纳米结构组成的纳米复合光催化剂具有优异的可见光光催化活性,成为新型光催化材料的研究热点之一。本文综述了Ag(Au)/半导体纳米复合光催化剂的制备方法、基本性质以及光催化应用方面的一些重要研究进展;重点介绍了Ag(Au)等纳米粒子的表面等离子共振增强可见光催化活性的机理,以及Ag(Au)纳米粒子与不同类型半导体复合的光催化剂的光催化性能,其中所涉及的半导体包括金属氧化物、硫化物和其他一些半导体;本领域未来几年的研究热点将集中于新型高效的Ag(Au)/半导体纳米复合光催化剂的微结构调控及其用于可见光驱动有机反应的机理研究。本文为基于SPR效应构建Ag(Au)/半导体纳米复合光催化剂的研究提供了有力的参考依据,并且指出Ag(Au)/半导体纳米复合光催化剂的研究是发展可见光高效光催化剂的重要方向。     

Development of a transient kinetic model for the CO oxidation by O2 over a Pt/Rh/CeO2/γ-Al2O3 three-way catalyst

A transient kinetic model was developed for the CO oxidation by O₂ over a Pt/Rh/CeO₂/γ-Al₂O₃ three-way catalyst. The experiments which were modelled consisted of periodically switching between a feed stream containing 0.5 mol% CO in helium and a feed stream containing 0.5 mol% O₂ in helium, with a frequency from 0.1 to 0.25 Hz, in the temperature range 393–433 K. These temperatures are representative for cold start conditions. The transient experiments yield information about the reaction mechanism. A transient kinetic model based on elementary reaction steps was developed which describes the experimental data in the above mentioned range of experimental conditions adequately. The kinetic model consists of two monofunctional and one bifunctional contribution. The first monofunctional reaction path comprises competitive adsorption of CO and O₂ on the noble metal surface followed by a surface reaction. The second monofunctional reaction path consists of CO adsorption on an oxygen atom adsorbed on the noble metal surface, followed by a reaction to CO₂. The bifunctional reaction path involves a reaction between CO adsorbed on the noble metal surface and oxygen from ceria at the noble metal/ceria interface. Also, reversible adsorption of carbon dioxide on the support is taken into account. The kinetic parameters, i.e. preexponential factors and activation energies for the different elementary reaction steps, and the oxygen storage capacity were estimated using multi-response non-linear regression analysis of the oxygen, carbon monoxide and carbon dioxide outlet concentrations.     

Rapid preparation of noble metal nanocrystals via facile coreduction with graphene oxide and their enhanced catalytic properties

We present the facile preparation results of noble metal nanostructures induced by graphene via rapid coreduction by Ti(3+) at room temperature. Such a reduction of graphene oxide (GO) can be readily performed in solutions or on various substrates within seconds. High quality noble metal nanocrystals can be prepared by using graphene as the controlling agent at room temperature, including Rh, Au and Rh-Pt nanodendrites and Pd nanoparticles, showing the roles of graphene on tuning the growth behaviors of nanostructures. These surface clean Pd nanoparticles show high catalytic activity and selectivity in Suzuki and Heck coupling reactions.     

有机废气催化燃烧过程中多尺度效应和催化剂设计

有机废气是重要的空气污染物,基于负载型贵金属催化剂的催化燃烧技术因效率高、无二次污染等特点而被广泛研究和应用。但目前催化燃烧技术仍存在高耗能和高成本等缺点。有机废气多相催化燃烧效率均与催化剂一定尺度范围内的结构密切相关。在有机废气催化氧化反应体系内存在从活性中心到高性能催化剂与过程的多尺度效应。依据不同尺度范围内催化剂的功能,对催化剂进行相应的设计和功能强化,是提高催化剂净化效率的有效方式。总结了近年国内外研究者在有机废气催化燃烧贵金属催化剂不同尺度范围内的设计理念和效果,并对有机废气催化燃烧催化剂的未来发展方向进行展望。     

贵金属纳米簇的独特性能及其制备方法

贵金属纳米金属簇因其独特的性能，在催化领域受到广泛的关注。对贵金属纳米簇的性能、抗团聚的稳定机制和制备方法等进行了系统的介绍。展望了金属纳米簇在催化中的应用前景。     

State of arts on the bio-synthesis of noble metal nanoparticles and their biological application

Nanomaterials are materials in which at least one of the dimensions of the particles is 100 nm and below. There are many types of nanomaterials, but noble metal nanoparticles are of interest due to their uniquely large surface-to-volume ratio, high surface area, optical and electronic properties, high stability, easy synthesis, and tunable surface functionalization. More importantly, noble metal nanoparticles are known to have excellent compatibility with bio-materials, which is why they are widely used in biological applications. The synthesis method of noble metal nanoparticles conventionally involves the reduction of the noble metal salt precursor by toxic reaction agents such as NaBH₄, hydrazine, and formaldehyde. This is a major drawback for researchers involved in biological application researches. Hence, the bio-synthesis of noble metal nanoparticles (NPs) by bio-materials via bio-reduction provides an alternative method to synthesize noble metal nanoparticles which are potentially non-toxic and safer for biological application. In this review, the bio-synthesis of noble metal nanoparticle including gold nanoparticle (AuNPs), silver nanoparticle (AgNPs), platinum nanoparticle (PtNPs), and palladium nanoparticle (PdNPs) are first discussed. This is followed by a discussion of these biosynthesized noble metal in biological applications including antimicrobial, wound healing, anticancer drug, and bioimaging. Based on these, it can be concluded that the study on bio-synthesized noble metal nanoparticles will expand further involving bio-reduction by unexplored bio-materials. However, many questions remain on the feasibility of bio-synthesized noble metal nanoparticles to replace existing methods on various biological applications. Nevertheless, the current development of the biological application by bio-synthesized noble metal NPs is still intensively ongoing, and will eventually reach the goal of full commercialization.     

Cu2O光催化剂综述

介绍Cu_2O光催化降解机理,禁带宽度,光生载流子利用率和溶液pH影响Cu_2O光催化降解活性,通过掺杂,负载贵金属,碳材料修饰和半导体复合可提高Cu_2O光催化性能。     

Effects of Noble Metal Promoters on In Situ Reduced Low Loading Ni Catalysts for Methane Activation

The commercial potential for a given catalytic process may be influenced by requirements on metal loading, in particular where noble metals are used. In an effort to substantially decrease the amount of catalyst material used for methane activation and catalytic partial oxidation (CPO), the effect of 0.005 wt% noble metal (Rh, Ru, Pd or Pt) on 0.5 wt% Ni/γ-Al₂O ₃ catalysts have been studied at temperatures below 1,173 K and 1 atm. The successful catalysts were activated directly by in situ reduction, without a calcination step, to promote formation of a highly dispersed (supported) metal phase from nitrate precursors. The obtained metal particles were not observable by XRD (size <  2–3 nm). This activation procedure had a decisive effect on catalyst activity, as compared to a catalyst which was calcined ex situ before in situ reduction. Adding a noble metal caused a significant drop in the ignition temperature during temperature programmed catalytic partial oxidation (TPCPO). The ignition temperature for partial oxidation coincides well with the temperature for methane dissociation, and is likely correlated to the reducibility of the noble metal oxide. Methane partial oxidation over 0.5 wt% Ni catalysts, both with and without promoter, yielded high selectivity to synthesis gas (>93%) and stable performance for continued operation, but synthesis gas production at temperatures below 1,073 K required a promoter when the catalyst was ignited by TPCPO. Ignition of the CPO reactions by introducing the feed at a high furnace temperature (1,073 K) also enabled formation of synthesis gas, but the reaction was then less stable than obtained with the TPCPO procedure. A dual bed concept attempted to beneficially use the activation and combustion properties of the noble metal followed by the reforming properties of Ni. However, it was concluded that co-impregnated catalysts yielded as high, or even higher conversion of methane and selectivity to synthesis gas.     

Environmentally benign multiphase catalysis with dense phase carbon dioxide

Environmental concerns stemming from the use of conventional solvents and from hazardous waste generation have propelled research efforts aimed at developing benign chemical processing techniques that either eliminate or significantly mitigate pollution at the source. This paper provides an overview of heterogeneous and homogeneous catalysis in dense phase CO₂, considered a green solvent. In addition to solvent replacement, the demonstrated advantages of using dense phase CO₂ include the enhanced miscibility of reactants, such as O₂ and H₂ which eliminate interphase transport limitations, and the chemical inertness of CO₂. Further, the physicochemical properties of CO₂-based reaction media can be pressure-tuned to obtain unique fluid properties (e.g. gas-like transport properties, liquid-like solvent power and heat capacities). The advantages of CO₂-based reaction media for optimizing catalyst activity and product selectivity are highlighted for a variety of reactions including alkylation on solid-acid catalysts, hydrogenation on supported noble metal catalysts and a broad range of homogeneous oxidations with transition metal catalysts and dioxygen as an oxidant. Through these examples, the need is emphasized for a systematic approach to research and development of supercritical carbon dioxide based processes, taking into account conventional multiphase reaction engineering principles, catalytic chemistry and phase behavior.     

An in situ reduction approach for bio-oil hydroprocessing

An in situ reduction treatment, combination of reduction and esterification, was investigated to refine bio-oil. Over Raney Ni and zeolites-supported noble metal (Pd and Ru) catalysts, the reductant formic acid decomposed into hydrogen and carbon dioxide, and then hydrogen reduced the bio-oil while compressible CO₂ dissolved in methanol to form a CO₂-CH₃OH expanded liquid. The results showed that Raney Ni and zeolites-supported Ru were highly active in this heterogeneous catalytic system. The reactions preformed at 150-230 °C for 5-7 h would give a better upgraded bio-oil with a high yield of 80-90 wt.%. The unsaturated components in bio-oil were reduced substantially without obvious coke formation, and the oxygen content was lowered by ca. 5 wt.%. Organic acids were converted into esters through the esterification with methanol, and the properties of hydrogenated bio-oil were improved: the pH value increased from 2.17 to ca. 4.5; the higher heating value approached to 22 MJ/kg, and the viscosity decreased from 5.31 to ca. 4.0 mm²/s.     

金属氮化物/碳化物催化剂加氢性能研究进展

介绍了过渡金属氮化物/碳化物独特的晶体结构和电子性能及其与催化性能的内在联系。综述了过渡金属氮化物/碳化物在涉氢反应中催化加氢机理的研究进展,以及过渡金属氮化物/碳化物在加氢脱硫(HDS)、加氢脱氮(HDN)和其他涉氢反应中的应用。与传统的过渡金属硫化物催化剂相比,过渡金属氮化物/碳化物具有更加优异的氢吸附、活化和转移能力。     

Hydrodeoxygenation of guaiacol on noble metal catalysts

Hydrodeoxygenation (HDO) performed at high temperatures and pressures is one alternative for upgrading of pyrolysis oils from biomass. Studies on zirconia-supported mono- and bimetallic noble metal (Rh, Pd, Pt) catalysts showed these catalysts to be active and selective in the hydrogenation of guaiacol (GUA) at 100 °C and in the HDO of GUA at 300 °C. GUA was used as model compound for wood-based pyrolysis oil. At the temperatures tested, the performance of the noble metal catalysts, especially the Rh-containing catalysts was similar or better than that of the conventional sulfided CoMo/Al₂O₃ catalyst. The carbon deposition on the noble metal catalysts was lower than that on the sulfided CoMo/Al₂O₃ catalyst. The performance of the Rh-containing catalysts in the reactions of GUA at the tested conditions demonstrates their potential in the upgrading of wood-based pyrolysis oils.     

羰基化合物直接还原胺化合成伯胺催化剂研究进展

胺类化合物是一类重要的化工原料和中间体,在农药、医药、染料、高分子聚合物等领域有着广泛的应用。通过羰基化合物（醛或酮类）的还原胺化来制备胺类化合物是当前的研究热点。研究表明,贵金属基和非贵金属基的多相和均相催化剂均能够高效催化醛或酮类的还原胺化反应。本文对近年来羰基化合物直接还原胺化（或一锅法）合成伯胺的研究现状进行了综述,包括还原胺化反应、催化剂、反应条件、底物适用范围和催化作用机制等,其中重点阐述了直接还原胺化催化剂的研究进展。文章指出：通常多相催化剂具有活性高以及可重复使用等优点,而均相催化剂的优势在于催化效率高,伯胺选择性高;另一方面,以Pd、Rh、Ru等为代表的贵金属催化剂催化性能优异,但价格昂贵,因此可采用Co、Ni等性能同样优异但价格相对低廉的非贵金属催化剂以降低成本。文中提出,催化效率高、反应条件温和、普适性高的羰基化合物还原胺化催化剂应成为未来重点研究方向。     

Improved electrode systems for reverse electro-dialysis and electro-dialysis

Reverse Electro-Dialysis, RED, is an electrochemical technique to extract work by mixing aqueous solutions of different salinities. Electro-Dialysis, ED, is an electrochemical technique to extract potable water from seawater. Both RED and ED typically employs noble metal oxide catalysts in the conversion between electronic current and ionic current. By testing several different electrode materials and red-ox salts, this paper demonstrates that these electrochemical reactions are controlled by mass transfer in the electrolyte rather than by the electrocatalytic properties of the electrode material. By comparing two different carbon materials and standard noble metal oxides, we show, for two red-ox salts, that the electrochemical performances of the inexpensive and expensive materials are similar. Relatively inexpensive graphite along with environmentally benign FeCl₂ and FeCl₃ in moderate concentrations was demonstrated to lower the electrode concentration overpotential.     

Effectiveness and performance of a catalyst pellet with bimodal kinetics

A theoretical analysis of the performance of a bimodal catalyst pellet which contains two different active components exhibiting different kinetics is presented in this paper. The isothermal interphase-intraphase effectiveness of such bimodal catalysts with a bimolecular Langmir type kinetics (i.e. noble metal) and a first order kinetics (i.e. base metal oxide) is coupled with the continuity equation for a fixed bed reactor and a continuously stirred tank catalytic reactor. The catalysts with mixed mode kinetics exhibit a behaviour that is less affected by concentration changes than the single component catalyst. Reactor performance depends on the noble metal fraction but not in direct proportion. Thus in some cases conversion reaches high levels at fractional values of noble metal loadings which would in theory allow for equivalent performance with savings in noble metal component.