低温燃料电池担载型贵金属催化剂

本文对近年来低温燃料电池用担载型金属纳米催化剂的合成及其电化学性能作了回顾;综述了不同的贵金属及其合金(如Pt, Pt-Ru等)制备方法以及新型碳纳米材料作为催化剂载体的研究进展;对该领域今后的发展作了展望。     

膨胀石墨负载纳米Pt催化剂的制备及其电催化性能

以天然鳞片石墨为基材,采用高氯酸插层氧化制备了膨胀石墨(EG),利用乙二醇液相还原法在其表面负载了Pt纳米颗粒;采用XRD、TEM、SEM及循环伏安曲线(CV)等手段对其形貌、结构及对甲醇的电催化性能进行了表征研究.结果 表明,Pt纳米颗粒的平均粒径为2.56 nm,均匀地分布在膨胀石墨载体表面,而片状结构的膨胀石墨载...     

新型纳米金修饰玻碳电极对水杨酸的电催化氧化

借助"种子媒介纳米金属生长法"制备新型的纳米金修饰玻碳电极,应用场发射扫描电镜、紫外-可见光谱分析和电化学方法等,研究该电极的表面形貌及其电化学性能.结果表明,该修饰电极对水杨酸的电化学氧化有明显的电催化作用,电极响应灵敏度是裸玻碳电极表面的1.8倍.其氧化峰电流与水杨酸浓度在5.0×10-7~8.0×10-5mol/L范围内呈良好的线性关系,可用于水中痕量水杨酸的检测.     

担载型水溶性膦铑配合物催化剂研究

烯类氢甲酰化反应包括了均相催化的某些重要应用。含贵金属和贵重配体的均相催化剂与产物的分离及制备高活性、高选择性、高稳定性催化剂,是均相催化及其多相化最活跃的研究领域之一。对于氢甲酰化催化剂多相化,在基础研究和技术上都仍存在如何解决好催化活性、反应选择性变化或金属流失等问题。将HRh(CO)[P(m-C_6H_4SO_33Na)_3]_3担载在亲水性     

贵金属纳米框架设计合成及电催化性能的研究进展

由超薄边框相互连接形成的贵金属纳米框架以负载量低、活性高等优势在多相催化领域受到了广泛关注.纳米框架独特的三维开放可及性结构不仅能够在边缘和顶点处暴露出更多的活性位点,提高贵金属活性位点利用率,还可以将反应底物限制在纳米范围内,增加底物分子碰撞的几率.本文综合评述了贵金属纳米框架材料的合成策略,总结了近年来贵金属纳米框架催化剂在电催化领域的研究进展,并对其未来发展方向和面临的挑战进行了展望.     

二氧化碳甲烷化催化剂研究1.担载型8族金属催化剂的性能

采用水溶液浸渍法制备了一系列无机氧化物担载的Ⅷ族金属催化剂，研究了它们在二氧化碳甲烷化反应中的催化性能。结果表明，催化剂性能与金属本性有关。     

钛基纳米多孔金电极对甲醛氧化的电催化活性

采用水热法制备了钛基纳米金微粒修饰电极(Au/Ti)。扫描电镜图表明纳米金颗粒粒径大约为300 nm,在钛基体表面构成三维多孔网状结构。运用循环伏安,电位阶跃和交流阻抗等电化学技术研究了碱性介质中甲醛在Au/Ti电极上的电氧化行为。循环伏安图显示,甲醛在Au/Ti上的起始氧化电位在-0.90 V左右,相对于多晶金电极提前大约0.2 V,交流阻抗测试表明,甲醛在Au/Ti电极上电氧化表现出低的电荷传递电阻。研究结果表明钛基纳米金微粒修饰电极对甲醛氧化具有良好的电催化活性。     

金纳米颗粒制备及应用研究进展

金纳米颗粒是近年研究的一种热门材料。介绍了金纳米颗粒主要的制备方法,包括化学还原法,两相法,晶种生长法以及模板法,并总结了金纳米粒子在生物医学、传感器、催化剂、电化学等领域的应用进展。     

纳米金修饰玻碳电极对甲醛的电催化氧化

利用电沉积方法制备了纳米金(nano-gold,NG)修饰玻碳电极(GCE)。在碱性介质中该电极对甲醛有较好的催化氧化作用,使甲醛在0.65 V左右出现一个氧化峰,依此测定甲醛的含量。通过实验确定了纳米金的沉积电位和沉积时间,以及纳米金对甲醛的催化氧化所需的底液。该法测定甲醛的线性范围为1~1 000μg/L,检出限为0.3 mg/L。加标回收率为98.5%~101.8%。     

Size‐Dependent Electrocatalytic Activity of Free Gold Nanoparticles for the Glucose Oxidation Reaction

Understanding the fundamental relationship between the size and the structure of electrode materials is essential to design catalysts and enhance their activity. Therefore, spherical gold nanoparticles (GNSs) with a mean diameter from 4 to 15 nm were synthesized. UV/Vis spectroscopy, transmission electron microscopy, and under‐potential deposition of lead (UPD_Pb) were used to determine the morphology, size, and surface crystallographic structure of the GNSs. The UPD_Pb revealed that their crystallographic facets are affected by their size and the growth process. The catalytic properties of these GNSs toward glucose electrooxidation were studied by cyclic voltammetry, taking into account the scan rate and temperature effects. The results clearly show the size‐dependent electrocatalytic activity for glucose oxidation reactions that are controlled by diffusion. Small GNSs with an average size of 4.2 nm exhibited high catalytic activity. This drastic increase in activity results from the high specific area and reactivity of the surface electrons induced by their small size. The reaction mechanism was investigated by in situ Fourier transform infrared reflectance spectroscopy. Gluconolactone and gluconate were identified as the intermediate and the final reaction product, respectively, of the glucose electrooxidation.     

Gold Nanoparticles Confined in Vertically Aligned Silica Nanochannels and Their Electrocatalytic Activity Toward Ascorbic Acid

A facile method of confining gold nanoparticles (AuNPs) in silica nanochannels aligned perpendicularly to an underlying electrode surface is reported. The nanochannel surface carrying a layer of (3‐aminopropyl)triethoxy silane (APTS) displays a strong electrostatic interaction with AuCl₄^?, eventually resulting in the confinement of AuNPs inside the nanochannels after chemical reduction. As‐prepared AuNPs in APTS‐modified mesoporous silica film (APTS‐MSF) are highly dispersed with a narrow size distribution. Furthermore, these AuNPs are free of protecting ligands and exhibit a good electrochemical catalytic activity toward the oxidation of ascorbic acid.     

Preparation of Au Nanoparticles on Surface of Two Supports by Adsorption Phase Synthesis

By utilizing adsorption phase synthesis (APS), Au nanoparticles were prepared on the surface of SiO₂ with or without modification by Ni(OH)₂. TEM, XRD, and UV‐vis were employed to characterize the morphology of Au particles on the surface of two kinds of supports. The results showed that the average size of Au particles on the SiO₂ surface modified by Ni(OH)₂ was less than 5 nm. Due to high surface isoelectric point, Au particles formed in the adsorption layer were prone to distribute on the surface of SiO₂ modified by Ni(OH)₂. With content of Ni(OH)₂ in samples increasing, more Au particles with small size appeared on the support surface.     

Bisthiol-Assisted Multilayers' Self-Assembly of Gold Nanoparticles: Synthesis,Characterization, Size Control and Electrocatalytic Applications

The layer-by-layer (LBL) approach has been utilized to self-assemble multilayers films of citrate-stabilized gold nanoparticles (AuNPs) on polycrystalline gold (poly-Au) substrates. 1,4-benzenedimethanethiol (BDMT) was used as a cross linker to bind every two successive AuNPs layers. The transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) techniques were employed to confirm the existence of the alternative layers of AuNPs and BDMT in the self-assembled multilayers film. The AuNPs modified poly-Au electrode showed a significant electrocatalysis towards the reduction of oxygen (a positive potential shift of about 100 mV was observed in the reduction peak potential compared to that obtained at the bare poly-Au electrode). The AuNPs tend to aggregate during their assembling to different extent which markedly depends on the substrate geometry and roughness. An effort was dedicated to understand and control the aggregation phenomenon.     

钛基氧化物电极的分形维数和电催化性能

分形几何学是近十几年来发展起来的新的数学理论,它对研究自然科学中的不规则几何行为具有独特的优势,尤其对材料的表面结构与性能研究有着重要的理论和实际意义。多相催化反应的一个显著特征就是在整个反应的一个显著特征就是在整个反应过程中都存在着反应界面,而界面的结构性质对反应过程有重要的影响。十几年前,有关这类界面的研究几乎都基于欧氏几何模型,在简单情况下视之为平面,在较复杂的情况下视之为曲面,即总是把表面视为二维面,但在很多情况下,这种做法与实际情况并不相符,例如,催化剂是多孔的,表面极不规则,存在各种晶体缺陷,而这些缺陷一般又是活性中心的集中处,面对这类粗糙的表面,经典的夫整几何学已显得无能为力,近年来,由Mandelbrot建立起来的分形几何学给人们解决诸多粗糙表面的复杂问题提供了新的途径和思路,本文计算了几种电极材料的表面分形维数,并对其催化性能进行了讨论。     

磁性纳米粒子负载钯催化有机合成反应研究进展

磁性纳米粒子负载钯催化的有机合成反应,由于具有催化活性高,催化剂在外加磁场作用下即可快速分离和重复使用等特点,已引起了人们的广泛关注.综述了近年来磁性纳米粒子负载钯催化有机合成反应的研究进展,载体包括Fe3O4纳米粒子、有机小分子修饰的磁性纳米粒子、SiO2包覆的磁性纳米粒子、碳修饰磁性纳米粒子、羟基磷灰石包覆的磁性纳米粒子和有机高分子修饰的磁性纳米粒子等.     

Thiol‐Assisted Synthesis of Carbon‐Supported Metal Nanoparticles for Efficient Electrocatalytic CO2 Reduction

The typical preparation route of carbon‐supported metallic catalyst is complex and uneconomical. Herein, we reported a thiol‐assisted one‐pot method by using 3‐mercaptopropionic acid (MPA) to synthesize carbon‐supported metal nanoparticles catalysts for efficient electrocatalytic reduction of carbon dioxide (CO₂RR). We found that the synthesized Au?MPA/C catalyst achieves a maximum CO faradaic efficiency (FE) of 96.2% with its partial current density of ?11.4 mA/cm², which is much higher than that over Au foil or MPA‐free carbon‐supported Au (Au/C). The performance improvement in CO₂RR over the catalyst is probably derived from the good dispersion of Au nanoparticles and the surface modification of the catalyst caused by the specific interaction between Au nanoparticles and MPA. This thiol‐assisted method can be also extended to synthesize Ag?MPA/C with enhanced CO₂RR performance.     

Preparation and Electrocatalytic Performance of Functionalized Copper‐Based Nanoparticles Supported on the Gold Surface

Copper nanoparticles (CuNPs) encapsulated by polymeric stabilizer of polyvinylpyrrolidone (PVP) (noted as PVP‐CuNPs) were simply prepared and used to construct an enzymeless glucose sensor on a solid substrate. Sensing and assay performance of the CuNPs‐based sensor to glucose were evaluated in detail. Cyclic voltammetry (CV), chronoamperometry (I–t) and flow injection amperometry (FIA) revealed a high sensitivity, excellent stability, and good reproducibility in the glucose determination at +0.45 V, which was 200 mV more negative than those in former reports. A detection limit as low as 1.0×10^?8 M (signal‐to‐noise=3) and a linear range of 1.0×10^?7 M to 5.0×10^?3 M were obtained in this study.     

Uniform Functionalization of High-Quality Graphene with Platinum Nanoparticles for Electrocatalytic Water Reduction

Graphene–metal composites have potential as novel catalysts due to their unique electrical properties. Here, we report the synthesis of a composite material comprised of monodispersed platinum nanoparticles on high-quality graphene obtained by using two different exfoliation techniques. The material, prepared via an easy, low-cost and reproducible procedure, was evaluated as an electrocatalyst for the hydrogen evolution reaction. The turnover frequency at zero overpotential (TOF₀ in 0.1 m phosphate buffer, pH 6.8) was determined to be approximately 4600 h⁻¹. This remarkably high value is likely due to the optimal dispersion of the platinum nanoparticles on the graphene substrate, which enables the material to be loaded with only very small amounts of the noble metal (i.e., Pt) despite the very highly active surface. This study provides a new outlook on the design of novel materials for the development of robust and scalable water-splitting devices.