配体保护下的Au_(20)团簇吸附和活化CO的理论研究

用密度泛函理论方法计算了CO分子吸附在有机配体聚乙烯吡咯烷酮poly(N-vinyl-2-pyrrolidone)(PVP)保护下的Au20团簇上的稳定构型的结构和性质。配体PVP通过物理吸附主要作用于Au20团簇的顶点位置。与Au20比较,配体的存在有利于CO的吸附和活化,其根本原因是PVP和CO在Au20表面分别作为供电子和吸电子基团产生的协同效应。中性及阴离子Au20团簇对配体和CO的吸附强度不同,前者对PVP吸附作用较强,后者对CO的吸附和活化作用较强。     

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.     

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.     

Superparamagnetic POT/Fe3O4 nanoparticle composites with supported Au nanoparticles as recyclable high-performance nanocatalysts

A novel method has been developed to successfully synthesize Fe₃O₄ nanoparticles with tunable size and morphology supported on shells of poly(o-Toluidine)(POT) hollow microspheres. The as-prepared POT/Fe₃O₄ nanoparticle composites can be used as novel and magnetic-responsive catalyst supports to produce highly efficient and recyclable noble metal catalysts. The size of Fe₃O₄ nanoparticles supported on shells of POT hollow microspheres can be tuned from 4 to 12 nm by changing the concentration of Fe ions. The roles of the doping acid of POT and Zeta potentials of Fe₃O₄ nanoparticles and POT in the formation of the POT/Fe₃O₄ nanoparticle composites were discussed. Furthermore, gold nanoparticles that were supported on the as-synthesized POT/Fe₃O₄ nanoparticle composites have been achieved by utilizing the reactivity of POT towards Au ions. The size of gold nanoparticles can be tuned by altering the concentration of HAuCl₄. Finally, the catalytic activity of the obtained POT/Fe₃O₄/Au composites for 4-nitrophenol (4NP) reduction is investigated. The results demonstrate that such magnetic-responsive polymer-supported gold nanoparticles can be easily recovered and reused five times still remains high catalytic performance, which indicate their potential applications in the field of catalysis.     

金—稀土合金电刷丝的磨损机理研究

采用扫描电子显微镜、微区电子探针及 X射线光电子能谱等分析测试技术考察了金 -稀土合金电刷丝摩擦副的磨损机理 .结果表明 :该摩擦副的摩擦磨损机理为轻微粘着磨损 ;合金中稀土元素发生偏聚 ;在摩擦升温过程中 ,稀土元素向合金表面扩散富集 ,摩擦副接触表面氧化层不断生成和磨损 ,从而降低电刷丝的表面能 ,使摩擦副的接触表面粘着能降低 ,从而改善其摩擦磨损     

Nanospherical Surface‐Supported Seeded Growth of Au Nanowires: Investigation on a New Growth Mechanism and High‐Performance Hydrogen Peroxide Sensors

In this paper, a novel strategy with a new growth mechanism for fast and large‐scale growth of Au long nanowires on high‐curvature SiO₂ nanospherical surfaces has been developed. The synthesis includes three steps, i.e., amino modification of SiO₂ nanospheres, Au seed loading on aminated SiO₂ nanospheres and subsequently, Au seed‐mediated nanowire growth on SiO₂ nanospheres. The prepared Au nanowires (Au NWs) (exhibit long length, high aspect ratio, and good flexibility, and can naturally form the dense nanowire film, which is promising as a stable conductive electrode. In addition, the effect of synthetic conditions such as reactant feeding order, Au seeds and SiO₂@Au seeds on the morphology of Au nanostructures (nanowires, nanoteeth, and nanoflowers) has been investigated. It is found that Au seeds and high‐curvature SiO₂ nanospherical surfaces are necessary conditions for the successful preparation of Au NWs and nanowire films. The different growth mechanisms for Au NWs and nanoteeth have been proposed and discussed. Moreover, the novel nonenzymatic H₂O₂ sensor based on Au NWs exhibits much enhanced performance such as higher sensitivity, stability, and selectivity, wider linear range and lower detection limit, compared with that of Au nanoparticles‐based H₂O₂ sensor.     

A novel enzyme-mimic nanosensor based on quantum dot-Au nanoparticle@silica mesoporous microsphere for the detection of glucose

QD-Au NP@silica mesoporous microspheres have been fabricated as a novel enzyme-mimic nanosensor. CdTe quantum dots (QDs) were loaded into the core, and Au nanoparticles (NPs) were encapsulated in the outer mesoporous shell. QDs and Au NPs were separated in the different space of the nanosensor, which prevent the potential energy or electron transfer process between QDs and Au NPs. As biomimetic catalyst, Au NPs in the mesoporous silica shell can catalytically oxidize glucose as glucose oxidase (GOx)-mimicking. The resultant hydrogen peroxide can quench the photoluminescence (PL) signal of QDs in the microsphere core. Therefore the nanosensor based on the decrease of the PL intensity of QDs was established for the glucose detection. The linear range for glucose was in the range of 5–200 μM with a detection limit (3σ) of 1.32 μM.     

AuNPs/Sol-gel复合膜法固定乙酰胆碱酯酶生物传感器检测有机磷农药

基于有机磷农药对乙酰胆碱酯酶(Acetylcholinesterase,AChE)的抑制作用,用金纳米粒子(Au nanoparticles,AuNPs)与壳聚糖/SiO2杂化溶胶-凝胶构成复合固酶基质,将AChE固定于玻碳电极表面,制备了电流型AChE生物传感器选用久效磷进行实验,以氯化硫代乙酰胆碱为底物,建立了电化...