银在甲烷选择性催化还原NOx反应中不同催化行为的研究

 采用XRD,TEM和UV－Vis方法研究了Ag－HZSM－5催化剂中活性组分银的价态和结构变化,并将这种变化与其在CH4选择性催化还原NOx反应中的活性和选择性相关联．结果表明,惰性气氛下高温处理使交换到分子筛阳离子位上的Ag＋自还原为Ag0,并在热的作用下聚集成纳米尺度的银颗粒Agn．纳米银颗粒Agn的形成提高了银催化剂在CH4选择性催化还原NOx反应中的活性,但它的长大又促进了CH4和O2的直接燃烧,使CH4选择性催化还原NOx反应的选择性降低．氧气气氛下高温预处理抑制了银颗粒的长大,并且氧气的氧化作用使银颗粒带有一定电荷,形成小的荷电纳米银粒子Agy＋x．荷电纳米银粒子的形成使催化剂的活性降低,但提高了CH4选择性催化还原NOx反应的选择性．     

Solid-phase synthesis of 2-aminoquinazolinone derivatives with two- and three-point diversity

A versatile solid-phase method for the synthesis of various substituted 2-amino-4(3H)-quinazolinones with two- and three-point diversity is described. The synthesis commenced with the generation of polymer-bound S-methylisothiourea followed by N-acylation with different substituted o-nitrobenzoic acid. Finally, reduction of the nitro group triggered intramolecular cyclization via formation of guanidine to afford 2-amino-4(3H)-quinazolinone and its derivatives in high yields and purities.     

Modification of carbon nanofibres for the immobilization of metal complexes: a case study with rhodium and anthranilic acid

The immobilisation of the rhodium/anthranilic acid complex onto fishbone carbon nanofibres (CNFs) was executed by means of the following steps: 1) surface oxidation of the fibres, 2) conversion of the oxygen-containing surface groups into acid chloride groups, 3) attachment of anthranilic acid and 4) complexation of rhodium by the attached anthranilic acid. The immobilisation process was followed and the resulting surface species were characterised by IR, X-ray absorption fine structure (XAFS) and X-ray photoelectron spectroscopy (XPS), and by molecular modelling. Anthranilic acid bonds to the CNFs by an amide linkage to the carboxyl groups that are present after surface oxidation of the fibres. The immobilised anthranilic acid coordinates to rhodium through the nitrogen atom and the carboxyl group. The assynthesised RhIII complex itself is not active in the liquid-phase hydrogenation of cyclohexene. Reduction with sodium borohydride yields small particles (d = 1.5-2 nm) of rhodium metal that are highly active. The results indicate that different activation procedures for the immobilised Rh/anthranilic acid system should be applied, such as reduction with a milder reducing agent or direct complexation of the rhodium in the RhI state.     

花球状银催化材料的制备及其对4-硝基苯酚的催化加氢性能

通过室温下将硝酸银水溶液与含有硫酸亚铁和柠檬酸的水溶液直接混合,一步合成由银纳米片自组装而成的银花状球结构。结合X射线粉末衍射(XRD)、扫描电子显微镜(SEM)等结构表征手段,考察硝酸银水溶液的滴加速度、柠檬酸添加量等因素对产物形貌及尺寸的影响,并对银花状球的形成机理进行研究。实验结果表明,通过对硝酸银水溶液滴加速度的简单调控可以实现银颗粒形貌由薄片状到花球状的转变。此外,该形貌的微纳米材料在4-硝基苯酚加氢反应中呈现出优异的催化活性。     

Smart synthesis of silver nanoparticles supported in porous polybenzoxazine nanocomposites via a main-chain type benzoxazine resin

Novel silver nanoparticles immobilized on macroporous polybenzoxazine nanocomposites were prepared as catalysts for catalytic reduction reaction.     

Restructuring and redispersion of silver on SiO2 under oxidizing/reducing atmospheres and its activity toward CO oxidation

The effects of oxygen-hydrogen pretreatments of nanosilver catalysts in cycle mode on the structure and particle size of silver particles, and subsequently the activity of the catalyst toward CO oxidation (or CO selective oxidation in the presence of H2), are reported in this paper. Ag/SiO2 catalyst with silver particle sizes of ca. 6 approximately 8 nm shows relatively high activity in the present reaction system. The adopting of a cycle of oxidation/reduction pretreatment has a marked influence on the activity of the catalyst. Oxygen pretreatment at 500 degrees C results in the formation of subsurface oxygen and activates the catalyst. As evidenced by in-situ XRD and TEM, the following H2 treatment at low temperatures (100 approximately 300 degrees C) causes surface faceting and redispersing of the silver particles without destroying the subsurface oxygen species. The subsequent in-situ FTIR and catalytic reaction results show that CO oxidation occurs at -75 degrees C and complete CO conversion can be obtained at 40 degrees C over such a nanosilver catalyst pretreated with oxygen at 500 degrees C followed by H2 at 100 degrees C. However, prolonged hydrogen treatment at high temperatures (>300 degrees C) after oxygen pretreatment at 500 degrees C induces the aggregation of silver particles and also depletes so much subsurface oxygen species that the pathway of CO oxidation by the subsurface oxygen species is inhibited. Meanwhile, the ability of the catalyst to adsorb reactants is greatly depressed, resulting in a 20 approximately 30% decrease in the activity toward CO oxidation. However, the activity of the catalyst pretreated with oxygen at 500 degrees C followed by hydrogen treatment at high temperatures (>300 degrees C) is still higher than that directly pretreated with H2. This kind of catalytic behavior of silver catalyst is associated with physical changes in the silver crystallites because of surface restructuring and crystallite redispersion during the course of oxygen-hydrogen pretreatment steps.     

花球状银催化材料的制备及其对4-硝基苯酚的催化加氢性能

通过室温下将硝酸银水溶液与含有硫酸亚铁和柠檬酸的水溶液直接混合,一步合成由银纳米片自组装而成的银花状球结构。结合X射线粉末衍射（XRD）、扫描电子显微镜（SEM）等结构表征手段,考察硝酸银水溶液的滴加速度、柠檬酸添加量等因素对产物形貌及尺寸的影响,并对银花状球的形成机理进行研究。实验结果表明,通过对硝酸银水溶液滴加速度的简单调控可以实现银颗粒形貌由薄片状到花球状的转变。此外,该形貌的微纳米材料在4-硝基苯酚加氢反应中呈现出优异的催化活性。     

A traceless approach for the parallel solid-phase synthesis of 2-(arylamino)quinazolinones

A traceless approach for the parallel solid-phase synthesis of 2-arylamino-substituted quinazolinones is described. Acylation of MBHA resin with o-nitrobenzoic acid derivatives, followed by reduction of the nitro group with tin chloride, generated a resin-bound o-anilino derivative. Reaction of resin-bound o-anilino derivative with arylisothiocyanates yielded resin-bound thioureas, which reacted with amines in the present of Mukaiyama's reagent (2-chloro-1-methylpyridinium iodide) to afford resin-bound guanidines. Following intramolecular cyclization of the resin-bound guanidines during cleavage from the resin by HF/anisole (95/5) for 1.5 h at 0 degrees C, the desired products were obtained in good yield and purity.     

聚苯乙烯邻氨基苯甲酸负载钯催化剂的加氢性能研究

含有双配位基的聚苯乙烯邻氨基苯甲酸与钯络合物反应制得螫合的配位高分子钯催化剂。用甲醇-水(pH=12)还原可得晶粒分布均匀的胶态钯催化剂,它们对烯烃的加氢具有良好的催化作用。研究表明,钯络合物上原有配体的给予性常数(E_n)与负载后络合催化剂的加氢活性具有良好的线性关系,金属粒径为40—50A的催化剂对己烯-1的加氢活性最高。本文还研究了溶剂极性,载体孔结构及底物对催化剂活性的影响。     

Catalytic activity and complexation-iv 2,2'-Bipyridyl as activator for the catalytic ultramicro determination of silver

The activation of the catalytic persulphate oxidation of sulphanilic acid when the catalyst, silver(I), is suitably complexed, is discussed. 2,2'-Bipyridyl is proposed as activator as it accelerates the rate-determining step of the process-the oxidation of silver(I) to silver(II). The mechanism of activation is investigated and discussed in detail. On the basis of these investigations a catalytic method has been developed for the determination of silver(I), with a sensitivity of 4 x 10(-4)mug ml and +/-7.6% relative error.     

Catalytic properties of silver nanoparticles supported on silica spheres

In this work, we investigate the catalytic properties of silver nanoparticles supported on silica spheres. The technique to support silver particles on silica spheres effectively avoids flocculation of nanosized colloidal metal particles during a catalytic process in the solution, which allows one to carry out the successful catalytic reduction of dyes. The effects of electrolytes and surfactants on the catalytic properties of silver particles on silica have been investigated. It is found that the presence of surfactants depresses the catalytic activity of the silver particles to some extent by inhibiting the adsorption of reactants onto the surface of the particles. Electrolytes either increase the migration rate of reactants in the solution resulting in an increase in the catalytic reaction rate or inhibit the adsorption of reactants onto the surface of the silver particles leading to a loss in the activity of the metal particles.     

Amphiphilic NaY zeolite particles loaded with niobic acid: Materials with applications for catalysis in immiscible liquid-liquid system

The catalytic potential of catalysts for acid-catalyzed reactions has been demonstrated by NaY zeolite loaded with alkylsilane-covered niobic acid in the liquid phase hydration of 1,2-epoxyoctane with water. The catalytic activity of the catalysts was correlated to the amphiphilic character of the solid catalyst particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Ag-ZSM-5 Catalyst for the Catalytic Decomposition of NO

noxides(mainlyNO)aremajorairpollutantsthatcausephotochemicalsmogandacidrain.Therefore,thereisaworldwideefforttodiscoverimprovedsolutionsfortheeffectiveremovalofNO.emissionsl.UntilnoW,nosuitablecatalystthatcaneffectivelyconvertNOintoN,andO:althoughthe...     

Highly stable,active and recyclable solid acid catalyst based on polymer-coated magnetic composite particles

Sulfonic acid-functionalized polymer-coated magnetic composite particles were prepared and applied as highly stable, active and recyclable magnetic solid acid catalyst for biodiesel preparation and biomass transformation.     

Highly stable,active and recyclable solid acid catalyst based on polymer-coated magnetic composite particles

A facile approach has been adopted for coating cross-linked polystyrene(PS) shells on the surface of Fe304 magnetic clusters using reflux-precipitation polymerization(RPP).Treating the PS shell with chlorosulfonic acid yields magnetic composite particles with acid functionality.By adjusting the amount and proportion of monomers(styrene and divinylbenzene),the obtained magnetic composite particle solid acid(MPM-5 S) exhibits a saturation magnetization value of 18 emu/g,a specific surface area of 243 m~2/g and an acid density of 2.113 mmol/g.The MPM-5 S magnetic solid acid catalyst was evaluated for esterification of oleic acid with methanol to prepare biodiesel.Under mild conditions,the conversion of oleic acid reached 91%,which was much higher than the catalytic activity of Amberlyst-15 and close to the catalytic activity of concentrated H_2 SO_4.The solid acid catalyst can be recovered by magnetic separation and reused three times maintaining over 95% of its initial catalytic activity.Additionally,the solid acid can be used to catalyze the dehydration of fructose to 5-hydroxymethylfurfural.     

Hydrogenation of phenylpyruvic acid to phenylalanine catalyzed by Ni-B/SiO2

Phenylalanine （Phe） is a significant amino acid that cannot be synthesized by human themselves but must be taken from environment. It was initially found that the nanosized amorphous Ni-B/SiO2 alloy prepared by the chemical reduction method was an effective catalyst for the preparation of Phe from phenylpyruvic acid （PPA） by amination and hydrogenation. It has been found that the amorphous Ni-B/SiO2 alloy catalyst exhibits superior activity and selectivity to the traditional catalysts Raney Ni and Urushibara nickel. The effects of reaction time, amounts of catalysts and ammonia solution, reaction temperature, and H2 pressure on the reaction have been investigated systematically. The results indicated that the yield of Phe was 97.9%, and the selectivity for Phe reached 98.9% when the reaction was carried out for 3 h at 333 K and 2.0 MPa of H2 with m（Cat.） ： m（PPA） = 0.6 ： 1.0 and n（NH3） ： n（PPA） = 3 ： 1. The catalysts were characterized by XRD, AAS, XPS, BET, and TEM, and the relationship between the catalyst structure and the catalytic activity was discussed in detail. It was found that the reason why Ni-B/SiO2 amorphous alloy catalyst was much more active for the preparation of Phe could be accounted for by the presence of electron-rich Ni due to electron donation from alloying B; the smaller size of Ni-B particles, the larger specific surface area of Ni-B/SiO2.     

A bio-oriented anthranilic acid catalyzed synthesis of quinazolin-8 (4H)-one derivatives: Evaluation by green chemistry metrics

An environmental friendly synthetic route has been investigated for the synthesis of quinazolin-8 (4H)-one derivatives in the presence of anthranilic acid as a catalyst. The zwitter ion formed in course of reaction may a play key role in the desired transformations leading good to excellent yields. Evaluation of the present protocol by green chemistry metrics demonstrated that it is highly efficient and eco-compatible.     

邻苯二甲酸和酞嗪对干法制备银纳米粒子形貌的影响

以硬脂酸银为前驱体,采用干式热还原方法制备银纳米粒子,并研究了邻苯二甲酸(Phthalic acid, H₂PA)和酞嗪(Phthalazine,PHZ)对银粒子形貌的影响.结果表明:H₂PA在直接热显影(Thermograhic, TG)模拟体系及光敏热成像(Photothermographic,PTG)体系中均促进颗粒状银纳米粒子的形成,而PHZ在TG模拟体系及PTG体系中分别促进颗粒状银粒子及丝状银的形成.调色剂的添加顺序对显影银形貌有很大影响.调色剂组合及光敏催化剂的协同作用是PTG体系中产生"树枝状"银的关键因素,探讨了不同形貌银纳米粒子的形成机理.     

Photochemical deposition of SERS active silver nanoparticles on silica gel and their application as catalysts for the reduction of aromatic nitro compounds

We report an impregnation technique for immobilization of silver(I) gelatin complex on silica gel. Subsequent UV exposure of the dry impregnated silica gel deposited silver nanoparticles on the solid matrix. Conventional techniques (UV-visible spectroscopy, TEM, EDAX, and thermal analysis) have been used to identify and characterize silver particles on silica surfaces. The photoproduced silver particles have shown unique SERS activity that authenticates the presence of silver nanoclusters in the silica matrix. Hence, the surface of the silica matrix remains SERS-active for months. This surface activity of the silica matrix inspired us to successfully study the catalytic reduction of nitro-compounds in aqueous, organic, and three different micellar media. Different thermodynamic parameters for the reduction processes have also been evaluated. Catalytic activity of the particles in micelles is explained in the light of hydrophobic and electrostatic interactions between the substrate and the micelles.     

石墨烯量子点负载银纳米粒子制备及氧还原电催化活性

银基氧还原电催化剂具有较高的电催化活性且价格相对低廉,因而受到广泛关注. 本文采用简单、预先合成的石墨烯量子点作为载体和还原剂,制得了负载于石墨烯量子点、且无保护剂和表面活性剂的表面洁净银纳米粒子（Ag NPs/GQDs）. 电化学研究表明,Ag NPs/GQDs复合电催化剂的氧还原有较高的电催化活性,氧在碱性溶液中可经4电子途径还原为水. 与商业铂碳电极（Pt/C）相比,AgNPs/GQDs电极具有高催化电流密度、良好稳定性和极佳抗甲醇性能. 该银纳米粒子对开发高性能和低成本的非铂氧还原电催化剂有潜在的应用前景.