反应气中的湿度对Au/Co_3O_4室温催化氧化甲醛的影响

采用共沉淀法制备了Au/Co_3O_4催化剂,通过TG-DSC、XRD、BET、XPS等技术对其进行了表征,并考察了其室温下催化氧化甲醛的性能.结果表明,Au的负载降低了Co3O4催化氧化甲醛的反应温度,在25℃具有60%的催化去除效率(RH 0%,GHSV 80 000 h-1)和100%的CO2选择性;室内环境湿度水平的水汽能显著提高其催化活性,在25℃达到了95%以上的甲醛去除效率(RH 50%,GHSV 80 000 h~(-1))和100%的CO_2选择性,活性持续2 0 h以上未见降低.XPS结果表明,Au在Co_3O_4表面主要以金属单质形式存在,其引入提高了催化剂表面的Oads/Olatt比.原位红外(In situ DRIFTS)分析结果表明,甲酸盐和二氧亚甲基(DOM)是催化反应过程中的主要中间物种,水汽的引入有利于促进甲酸盐的生成、中间产物的氧化分解以及产物的脱附.     

Supported bimetallic catalyst Pt-Pb/SiO2 for selective conversion of nitrobenzene to p-aminophenol in pressurized CO2/H2O system

Various supported Pt-Pb bimetallic catalysts were prepared and applied for the catalytic conversion of nitrobenzene to p-aminophenol in the environmentally benign pressurized CO_2/H_2O system.Among the bimetallic catalysts prepared,Pt-Pb/SiO_2 is the best and nitrobenzene could be converted to paminophenol with a selectivity as high as 82% when the reaction was carried out using this catalyst at110 ℃ under 5 MPa CO_2 and 0.2 MPa H_2.     

Enhancement of Fe3O4/Au Composite Nanoparticles Catalyst in Oxidative Degradation of Methyl Orange Based on Synergistic Effect

Enhancement of Fe₃O₄ /Au nanoparticles (Fe₃O₄ /Au NPs ) catalyst was observed in the oxidative degradation of methyl orange by employing H₂O₂ as oxidant. To evaluate the catalytic activity of Fe₃O₄ /Au nanoparticles, different degradation conditions were investigated such as the amounts of catalyst, H₂O₂ concentration and pH value. Based on our data, methyl orange was degraded completely in a short time. The enhanced catalytic activity and increased oxidation rate constant may be ascribed to synergistic catalyst‐activated decomposition of H₂O₂ to •OH radical, which was one of the strong oxidizing species. Besides, Fe₃O₄ /Au nanoparticles have exhibited satisfying recycle performance for potential industrial application.     

Facile Synthesis of Cuprous Oxide/Gold Nanocomposites for Nonenzymatic Amperometric Sensing of Hydrogen Peroxide

In this work, a facile preparation method of cuprous oxide/gold (Cu₂O/Au) nanocomposite was successfully developed. The process consisted of one‐pot co‐reduction of HAuCl₄ and CuSO₄ using ascorbic acid (AA) as a reducing agent at room temperature under magnetic stirring. The structures and compositions of the as‐prepared products were characterized by SEM, EDS, and XRD. Cyclic voltammetry and chronopotentiometry studies revealed that the as‐prepared cubic Cu₂O/Au nanocomposites showed enhanced performance towards the non‐enzymatic catalytic reduction of hydrogen peroxide (H₂O₂) when compared to single‐component Cu₂O nanocubes. The linear range of H₂O₂ determination spanned over 4 orders of magnitude (1 μM∼16.7 mM) and the detection limit was low as 0.45 μM (S/N=3). The enhanced performance of cubic Cu₂O/Au was attributed to: i) the synergistic effect between Cu₂O and Au, ii) the increase in surface area induced by the reduced size of the nanocubes, and iii) the improved electrical conductivity due to the presence of Au in the particles. Overall, the cubic Cu₂O/Au nanocomposites prepared by the proposed method hold great promise for future practical use in H₂O₂ detection.     

Mg/Al物质的量比对Ce-La/MgAl2O4-x催化剂催化CO还原NO性能的影响

采用初始浸渍法制备了不同Mg/Al物质的量比的Ce-La/MgAl₂O₄-x催化剂,并通过低温N₂-吸附脱附、XRD、H₂-TPR和CO-TPR等手段对其进行了表征。结果表明,在Mg/Al物质的量比为0.5时,催化剂催化CO还原NO的性能最好。这主要是因为适量Mg的添加促进了CeO₂的分散和Ce-O-La固溶体的形成,从而使得表面Ce³⁺和氧空穴增加。两者的协同作用使得Ce-La/MgAl₂O₄-0.5表现出最佳的催化性能。另外,适量Mg的引入可以抑制Ce（SO₄）₂和Ce₂（SO₄）₃的形成,从而提高了Ce-La/MgAl₂O₄-0.5催化剂抗硫中毒能力。     

PDMS-Au复合基底上多环芳烃分子的表面增强拉曼光谱

利用聚二甲基硅氧烷(PDMS)对有机物的富集功能,通过在金纳米粒子单层膜(Au MLF)表面旋涂薄层PDMS膜制备PDMS-Au MLF复合表面增强拉曼光谱(SERS)基底.研究了SERS增强性能与旋涂液浓度及稀释溶剂间的关系,考察了复合基底增强活性的均匀性.研究发现,采用叔丁醇为稀释溶剂,浓度为2%(质量分数)的旋涂液时所得复合基底表面多环芳烃(PAHs)的SERS信号强度最高,且此基底SERS信号强度偏差小于10%.分别以PDMS-Au MLF复合材料和Au MLF作为基底,对比研究了对萘、蒽、菲和芘4种多环芳烃的SERS检测能力.结果表明,PDMS-Au MLF复合基底对以上4种有机物的检出限分别为10~(-6),10~(-7),10~(-8)及10~(-7)mol/L,相比于单一Au MLF基底,其检测限至少降低了1个数量级,这主要源自于PDMS对PAHs的富集作用,且此类复合基底可用于多种多环芳烃混合物的特征识别.     

Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

Polymerization of optically active disubstituted acetylene monomers by Pd catalyst bearing bulky phosphine ligand

Chloro- and aryl-substituted acetylene monomers having an optically active group were polymerized by a Pd catalyst [(^tBu₃P)PdMeCl] bearing a bulky phosphine ligand, and by MoCl₅ for comparison. The corresponding disubstituted acetylene polymers with M_n's = 2000–19,500 and 6900–10,800 were obtained in 29–83% and 11–62% yields when the Pd and Mo catalysts were used, respectively. The formation of polyacetylenes, poly[(R)- 1p ], poly[(R)- 1m ], and poly[(S)- 2p ] were confirmed by SEC and the presence of a Raman scattering peak based on the alternating double bonds of the main chain. Pd-based poly[(R)- 1m ] exhibited CD signals around 350 nm assignable to a certain secondary structure, while Mo-based poly[(R)- 1m ] did not. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3011–3016     

四氯化碳液相催化加氢制氯仿多元金属催化剂的制备及其催化性能

以贵金属M(=Pd,Pt)为主要活性成分,掺加过渡金属Fe和Ni作为助剂,采取浸渍和氢气还原法制备了椰壳活性炭(ACcs)负载的单元金属(M/ACcs)、二元金属(M-Ni/ACcs、M-Fe/ACcs)和三元金属(M-Ni-Fe/ACcs)系列催化剂;通过CC_l4液相催化加氢制氯仿反应考察了这些催化剂的催化活性和选择性。结果表明,Pd基催化剂的催化活性明显高于Pt基催化剂,但后者对氯仿的选择性优于前者;在前5 h加氢反应时段,两系列催化剂的活性顺序为:Pd-Ni-Fe/ACcsPd-Fe/ACcsPd/ACcsPd-Ni/ACcs和Pt/ACcs≈Pt-Fe/ACcsPt-Ni/ACcsPt-Ni-Fe/ACcs;总体上,引入Fe对于催化性能的改善效果要优于Ni,Ni的单独引入则会不同程度地降低催化活性。综合考量成本、活性和选择性等因素,优选Pd-Ni-Fe/ACcs作为催化剂,在393 K下反应5 h,可实现CC_l497.6%的转化率以及接近100%氯仿的选择性。     

Zn/SiO_2气相催化裂解1,1,2-三氯乙烷脱HCl:酸性与失活

用浸渍法制备了一系列SiO_2负载的过渡金属催化剂M/SiO_2(M为第Ⅳ周期过渡金属),用于气相催化裂解1,1,2-三氯乙烷(TCE)脱HCl的反应。研究发现,在M/SiO_2催化剂中,Zn/SiO_2催化性能最好,TCE转化率能达到98%,顺-1,2-二氯乙烯(cis-DCE)的选择性为82%。随着Zn负载量的增加,Zn/SiO_2催化剂上TCE转化率逐渐增加,与催化剂上总酸量变化一致。将总酸量以Zn负载量归一化得到比酸量,则比酸量越大,Zn/SiO_2催化剂比活性越高,表明Zn/SiO_2催化剂表面酸性中心是TCE脱氯反应的活性中心。Zn/SiO_2催化剂在TCE脱HCl反应中存在一定的失活现象,归因于反应过程中催化剂表面积炭。低Zn负载量催化剂上会产生较多积炭,归因于其具有较多强酸性中心,表明催化剂表面强酸中心是导致催化剂积炭和失活的主要原因。