Pd/MCM-41催化水溶液中碘苯Ullmann反应的研究

以水溶剂中Ullmann反应为目标反应,设计具有纳米介孔结构的Pd/MCM-41作为其高效催化剂.与传统SiO2载体负载的Pd催化剂比较,该催化剂在以水为介质的碘苯偶合（Ullmann反应）中显示出优良的催化活性和对联苯的选择性.     

载体特性对Pd-Cu/TiO2催化剂催化脱氮性能的影响

以Pd-Cu／TiO2为催化剂，采用催化加氢技术进行脱氮研究．结果表明：TiO2载体的特性对催化活性及N2选择性有显著影响，与773K和973K温度下焙烧得到的载体相比，以573K温度下焙烧得到的TiO2为载体制备的Pd（5wt％）-Cu（1．25wt％）／TiO2催化剂可显著提高催化效率及N2选择性．     

铈锆固溶物载Pd催化剂的构造特征及其活性

以共沉淀法和滤纸作为模板剂的模板法制备铈锆固溶物(Ce／Zr=1)负载Pd催化剂,用XRD对其进行晶相分析,两种方法均形成立方萤石结构．TPR实验揭示了滤纸模板法制备的铈锆固溶物高温老化催化剂更易被还原．催化剂表面Pd的分散度和活性评价实验表明,催化剂表面贵金属的分散度在一定程度上决定催化剂的活性,载体物性影响Pd的分散度,滤纸模板法制备的铈锆固溶物负载Pd催化剂有较高的Pd分散度,表现出比共沉淀法制备的铈锆固溶物负载Pd催化剂好的三效活性．     

Enhanced performances in catalytic oxidation of <Emphasis Type="Italic">o</Emphasis>-xylene over hierarchical macro-/mesoporous silica-supported palladium catalysts

A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next loaded on the hierarchical silica supports via colloids precipitation method. Physicochemical properties of the synthesized samples were characterized by various techniques and all catalysts were tested for the total oxidation of o-xylene. Among them, the Pd/MMS-b catalyst with tetraethoxysilane/polystyrene weight ratio of 1.0 exhibited superior catalytic activity, and under a higher gas hourly space velocity (GHSV) of 70000 h^–1, the 90% conversion of o-xylene has been obtained at around 200°C. The BET and SEM results indicated that Pd/MMSb catalyst possesses high surface area and large pore volume, and well-ordered, interconnected macropores and 2D hexagonally mesopores hybrid network. This novel ordered hierarchical porous structure was highly beneficial to the dispersion of active sites Pd nanoparticles with less aggregation, and facilitates diffusion of reactants and products. Furthermore, the Pd/MMS-b catalyst possessed good stability and durability.     

全Pd三效催化剂研究涂层材料的研究

制备了作为Pd三效催化剂涂层材料组成的活性Al2O3/金属氧化物添加剂试样,用BET法、XRD法及H2－TPR法对这些涂层原材料体系进行表征。结果表明：金属氧化物添加剂提高了活性Al2O3的热稳定性;添加ZrO2改善了CeO2的热稳定性;与含Ca的试样不同,含La试样没有贮氧能力。用含有Al2O3-CeO2/ZrO2和Al2O3-La2O3/BaO的涂层材料制备的Pd催化剂有好的CO,HC和NOx同时净化的三效性能和低的起燃活性。加入0．003％（V／V）SO2降低了催化剂活性,含La2O3/BaO涂层材料的Pd催化剂上NOx反应易被SO2中毒。     

低浓CH4催化燃烧的研究

制备了陶瓷蜂窝结构贵金属和金属氧化物催化剂,研究了CH_4的氧化活性,其中金属Pd催化剂具有最佳的活性,使用Pd催化剂测定了低浓CH_4燃烧的若干基本参数,获得若干基础性的结果。     

Promoting effect of Zr on the catalytic combustion of methane over Pd/γ-Al2O3 catalyst

The effect of Zr on the catalytic performance of Pd/y-A1203 for the methane combustion was investigated. The results show that the addition of Zr can improve the activity and stability of Pd/γ-Al2O3 catalyst, which, based on the catalyst characterization （N2 adsorption, XRD, CO- Chemisorption, XPS, CHa-TPR and O2-TPO）, is ascribed to the interaction between Pd and Zr. The active phase of methane combustion over supported palladium catalyst is the Pd^0/Pd^2＋ mixture. Zr addition inhibits Pd aggregation and enhances the redox properties of active phase Pd^0/ Pd^2＋. H2 reduction could effectively reduce the oxidation degree of Pd species and regenerate the active sites （Pd^0/ pd^2＋）.     

树脂负载α-FeOOH异相光Fenton降解水中己烷雌酚

以Amberlite200树脂为载体,在Fe(NO3)3-HNO3体系中恒温水解制备了负载型催化剂α-FeOOH/Resin,以己烷雌酚(HEX)为目标化合物,研究了α-FeOOH/Resin的异相Fenton催化性能.结果表明,α-FeOOH/Resin异相Fenton反应能够有效降解水中的HEX,紫外光和H2O2的协同作用很大程度地提高了降解效率;pH值的降低或初始H2O2浓度的提高,均能增加HEX的降解速率;在中性条件下,HEX的光Fenton降解过程中,溶出的铁元素对降解贡献不大,异相Fenton反应起主导作用;催化剂重复使用后仍具有较好的催化活性和机械强度,说明铁在其表面负载牢固,催化剂具有一定的实用性.     

Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption

In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds (vinyl polychlorides including trichloroethylene (TCE), tetrachloroethylene (PCE), and alkyl polychlorides including 1,1,1-trichloroethane (1,1,1-TCA), and 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA)) to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, k_SA, showed a systematic dependence on the electronic structure (the density of states at the Fermi level) of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first (weakest) dissociated C-Cl bond, suggesting that C-Cl bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydrodechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular (non-dissociative) adsorption on the noble metals rather than with the first C-Cl bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.     

以ZrO2为载体的金属氧化物催化剂对NO还原性能的研究

研究了负载于氧化锆载体上的多种金属氧化物在富氧条件下,以丙烯为还原剂,选择性还原NO的活性,考察了CuO和Ag的负载量与活性关系,CuO和Ag单独负载与共同负载时的催化性能,以及氧气浓度对催化剂活性影响.结果表明:在CuO,MgO,La2O3 ,CoO,Fe2O3 ,MoO3和WO3等七种金属氧化物中,CuO活性最好,NO转化率为47.5%,加入活性组分银可明显提高催化剂的NO还原能力,转化率提高到61%.单独负载银时,催化剂活性较差,NO转化率仅为22.1%.在对氧气浓度的考察中,确定在0.4%NO,0.4?H6的反应气中,氧气的最佳含量为2%.     

稀土修饰的Co/Hβ催化剂催化分解N_2O

以Hβ分子筛为载体,采用浸渍法制备了一系列以钴为主活性组分,稀土元素为助剂的CoM/Hβ（M=La、Ce、Pr、Nd）催化剂,考察了在含氧条件下直接催化分解N2O的性能.采用X射线衍射、热重-质谱联用系统、H2-TPR、NH3-TPD等方法对催化剂进行了表征.XRD结果表明,Co物种主要以Co3O4尖晶石形态存在.NH3-TPD结果表明,催化剂活性与催化剂的酸性有关.活性评价结果显示,稀土助剂的添加使催化剂活性得到改善,其中以Pr为助剂的催化剂活性最好,N2O转化率达到95%时的反应温度为398℃.     

Al_2O_3负载Pd-Cu催化剂催化1,2-二氯乙烷加氢脱氯性能

采用共浸渍法制备了一系列Al2O3负载金属Pd、Cu催化剂.通过元素分析（ICP）、氮气吸脱附（BET）、X射线粉末衍射（XRD）、透射电镜（TEM）等技术对催化剂进行了表征,并以1,2-二氯乙烷气相加氢脱氯为探针反应,考察了Pd-Cu/Al2O3催化剂的钯铜比、反应温度、反应时间等因素对催化活性以及反应产物乙烯选择性的影响.结果发现,提高Cu负载量可在催化剂中形成Pd-Cu合金,并促进催化剂对乙烯的选择性.此外,当温度为250℃,Pd、Cu负载量分别为0.78%和1.9%时的Pd-Cu/Al2O3催化剂对1,2-二氯乙烷的催化加氢脱氯效果最佳,最终产物乙烯的选择性可达到80%以上.     

A Pt-Bi bimetallic nanoparticle catalyst for direct electrooxidation of formic acid in fuel cells

Direct formic acid fuel cells are a promising portable power-generating device, and the development of efficient anodic catalysts is essential for such a fuel cell. In this work Pt-Bi nanoparticles supported on micro-fabricated gold wire array substrate were synthesized using an electrochemical deposition method for formic acid oxidation in fuel cells. The surface morphology and element components of the Pt-Bi/Au nanoparticles were characterized, and the catalytic activities of the three Pt-Bi/Au nanoparticle electrodes with different Pt/Bi ratios for formic acid oxidation were evaluated. It was found that Pt₄Bi₉₆/Au had a much higher catalytic activity than Pt₁₁Bi₈₉/Au and Pt₁₃Bi₈₇/Au, and Pt₄Bi₉₆/Au exhibited a current density of 2.7 mA·cm^-2, which was 27-times greater than that of Pt/Au. The electro-catalytic activity of the Pt-Bi/Au electrode for formic acid oxidation increased with the increasing Bi content, suggesting that it would be possible to achieve an efficient formic acid oxidation on the low Pt-loading. Therefore, the Pt-Bi/Au electrode offers a promising catalyst with a high activity for direct oxidation of formic acid in fuel cells.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Synthesis, physicochemical characterizations and catalytic performance of Pd/carbon-zeolite and Pd/carbon-CeO2 nanocatalysts used for total oxidation of xylene at low temperatures

In this work, xylene removal from waste gas streams was investigated via catalytic oxidation over Pd/carbon-zeolite and Pd/carbon-CeO₂ nanocatalysts. Activated carbon was obtained from pine cone chemically activated using ZnCl₂ and modified by H₃PO₄. Natural zeolite of clinoptilolite was modified by acid treatment with HCl, while nano-ceria was synthesized via redox method. Mixed supports of carbon-zeolite and carbonceria were prepared and palladium was dispersed over them via impregnation method. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller surface area (BET), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) techniques. Characterization of nanocatalysts revealed a good morphology with an average particle size in a nano range, and confirmed the formation of nano-ceria with an average crystallite size below 60 nm. BET analysis indicated a considerable surface area for catalysts (～1000 m²·g^?1). FTIR patterns demonstrated that the surface groups of synthesized catalysts are in good agreement with the patterns of materials applied in catalyst synthesis. The performance of catalysts was assessed in a low-pressure catalytic oxidation pilot in the temperature range of 100° C-250°C. According to the reaction data, the synthesized catalysts have been shown to be so advantageous in the removal of volatile organic compounds (VOCs), representing high catalytic performance of 98% for the abatement of xylene at 250°C. Furthermore, a reaction network is proposed for catalytic oxidation of xylene over nanocatalysts.     

Pd nanoparticles entrapped in TiO<Subscript>2</Subscript> nanotubes for complete butane catalytic combustion at 130 °C

Air pollution by volatile organic compounds is a major health issue due to increasing industrialization and urbanization, notably in the developing countries. Cleaning organic pollutants by catalytic combustion is a potential solution, but actual methods require relatively high temperatures, thus increasing remediation costs. There is therefore a need for methods that operate at mild temperatures. Here we prepared a novel catalyst made of Pd nanoparticles entrapped in TiO₂ nanotubes by vacuum-assisted impregnation. Then, we tested this catalyst for butane combustion. The catalyst was characterized by N₂ adsorption–desorption isotherms, transmission electronic microscopy, energy-dispersive X-ray analysis coupled with a scanning transmission electron microscope, X-ray photoelectron spectroscopy and temperature programmed oxidation. Results show a complete combustion of butane at 130 °C, which is about 20 °C lower than temperatures required by actual catalysts made of Pd nanoparticles deposited on the exterior surface of TiO₂ nanotubes. Structure characterization suggests that this higher performance at lower temperature is explained by the confinement of TiO₂ nanotubes. Such a confinement could hinder the metal sintering and, in turn, facilitate the formation of PdO during oxidation on the entrapped Pd nanoparticles.     

Ce0.7Zr0.3O2纳米棒的制备及其对柴油车尾气碳颗粒的催化净化性能

本研究以硝酸铈、硝酸锆为原料使用溶剂热合成法,制备了CeO₂-ZrO₂纳米棒催化剂(Ce_0.7Zr_0.3O₂(NR)),并用于柴油车尾气碳颗粒催化净化.催化活性检测证实:Ce_0.7Zr_0.3O₂(NR)纳米棒催化剂可有效净化柴油车尾气碳烟颗粒.在Ce_0.7Zr_0.3O₂(NR)存在下,碳颗粒净化率为10%、50%和90%时,所需温度分别仅为375℃、414℃和455℃,比商用Ce_0.7Zr_0.3O₂和Ce0.3Zr0.7O2催化剂性能更优.采用氮吸附-脱附、X射线光电子能谱(XPS)、H2程序升温还原(H₂-TPR)、X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术对催化剂进行表征.XRD和Raman结果证实,Ce_0.7Zr_0.3O₂(NR)主要由立方相CeO₂构成,并掺杂了少量四方相氧化锆.SEM和TEM结果则显示,Ce_0.7Zr_0.3O₂(NR)催化剂颗粒明显由纳米棒堆积而成,特定的纳米形貌会影响其对碳颗粒的催化氧化活性.XPS结果证明Ce_0.7Zr_0.3O₂(NR)催化剂主要具有晶格氧、化学氧和表面吸附氧等氧物种;晶格氧是碳颗粒氧化的活性氧物种,其溢流到催化剂表面可与碳颗粒接触从而提高反应活性;化学氧和表面吸附氧均为表面氧物种,极易与表面固体碳颗粒直接接触,从而可在较低温度下促进碳颗粒的净化.H₂-TPR结果进一步证实了XPS结果,Ce_0.7Zr_0.3O₂(NR)催化剂的低温还原温度比商用Ce_0.7Zr_0.3O₂催化剂更低,且含有更多的易还原氧物种,这些低温易还原氧物种可以在较低温度下参与催化反应,促进柴油车尾气颗粒物的低温催化净化.     

A novel proton-gradient-transfer acid complexes as an efficient and reusable catalyst for fatty acid esterification

In this work, a series of novel proton-gradient-transfer acid complexes (PGTACs) were developed. Their physicochemical properties, including thermal stability, melting point, and Hammett acidity, were measured. The effects of catalyst loading, reaction temperature, and substrate expansion on the catalytic performance were systematically studied. It is found that the combination of bidentate N-heterocycle and H2SO4 (1:2 M ratio) could form simultaneously N–H covalent bond and N…H hydrogen bond, which makes the PGTACs excellent catalysts integrate the advantages of strong acids (high catalytic activity) and ionic liquids (phase separation) in the esterification reaction. Moreover, these PGTACs can be reused by convenient phase separation without obvious diminution of catalytic activity. It is concluded that these PGTACs are potential alternative candidates for esterification reaction in the process of industrial catalysis.     

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

含氮有机物在Pt／HM,Pd／HM和CuO／HM催化剂上的氧化降解

本文考虑了乙腈、硝基甲烷和乙二胺在Ｐｔ／ＨＭ，Ｐｄ／ＨＭ和ＣｕＯ／ＨＭ催化剂上氧化降解产物随反应温度的变化。在实验温度范围内，含氮产物在Ｎ２，Ｎ２Ｏ和ＮＯ２。随着反应温度的升高，硝基甲烷氧化降解的Ｎ２选择性呈单调下降；而乙腈和乙二胺的Ｎ２选择性出现极小值；高温时Ｎ２选择性升高可能是氧化生成的ＮＯ在高温时更在利于和ＣＮ基或ＮＨ２基相互反应生成Ｎ２的缘故。对于乙腈和乙二胺的催化氧化降解活性为：Ｐｔ／Ｈ