高指数晶面裸露的贵金属纳米晶体的合成

由于在高指数晶面上存在高密度的台阶位、扭结位原子等,高指数晶面裸露的贵金属纳米晶体一般表现出优越的物理化学性能,在催化、电化学等方面都有很重要的应用前景．近年来,研究人员围绕高指数晶面的制备进行了大量的工作并取得了一定进展．本文重点从合成制备方法的角度出发,结合本课题组的相关研究,系统总结了现有的有关制备高指数晶面裸露的贵金属纳米晶体的一些最新研究成果．从电化学方法、“帽”式试剂保护法、欠电位沉积原子层保护法、动力学调控、氧化刻蚀溶解再生长法以及模板法等几个方面对现有的高指数晶面裸露的贵金属纳米晶体的制备进行了总结．     

Ru修饰Pd二十四面体纳米晶的合成及其甲醇电催化氧化性能

表面结构控制和表面异种金属修饰是调控催化剂反应性的重要方法。因此,我们结合高指数晶面结构的高反应性与表面修饰异种金属,合成具有{730}高指数晶面的钯二十四面体纳米晶,并通过循环伏安扫描电沉积法得到Ru修饰的钯二十四面体纳米晶。电化学测试结果表明,低的Ru覆盖度(θ_(Ru)=0.08)可显著提高对碱性介质中甲醇电氧化的催化性能。电化学原位红外光谱结果表明,少量Ru的修饰没有减少CO的生成,而是促进了低电位下甲醇氧化成甲酸根。     

碳纸负载高指数晶面铂纳米粒子的制备及其在直接甲酸燃料电池中的催化性能研究

直接甲酸燃料电池(DFAFCs)是一种很有前景的可用于移动电子设备的电源. 钯对甲酸电催化氧化有很高的活性,但稳定性较差,容易失活;铂对甲酸电催化氧化的活性低于钯,但稳定性好. 前期研究表明,高指数晶面铂纳米粒子对甲酸的电催化氧化活性显著高于低指数晶面铂纳米粒子. 本文以碳纸为载体,应用方波电位法生长高指数晶面铂纳米粒子（HIF-Pt/C-paper）,通过改变方波上下限电位,合成出不同粒径的二十四面体和偏方三八面体铂纳米粒子. 进一步在碳纸上修饰一层碳黑微孔层并优化电沉积条件,制备出粒径约10 nm,载量0.069 mg•cm^-2的HIF-Pt/C-paper作为DFAFCs的阳极催化剂.在甲酸浓度为3M时,测得30℃下单电池最大功率密度10.6 mW•cm^-2,最大质量功率密度153.5 mW•mg^-1_Pt,是以1mg•cm^-2 载量的商业60 wt% Pt/C为阳极催化剂的电池的8.4倍. HIF-Pt/C-paper阳极DFAFCs在20 mA•cm^-2条件下运行50 h,电压保持率为95%,显示出很好的稳定性.     

高表面能晶面裸露的金属氧化物微纳米晶体的可控合成

表面结构是影响固体材料物理和化学性质的重要因素,由于高表面能的晶面上存在更多的表面悬挂键等,高表面能晶面裸露的微纳米晶体一般表现出很好的物理和化学活性．近年来,科研工作者针对高能面微纳米晶体材料的制备及性能调控进行了大量的研究工作并取得了一定的进展．本文重点讨论了高能面裸露的金属氧化物半导体微纳米晶体的合成制备方法．主要以本课题组近年在该领域的研究为例,分别从晶体生长过程中的静电作用法、“帽”式试剂保护法、过饱和度调控法、动力学调控法及选择性化学刻蚀法等几个方面对高表面能晶面裸露的金属氧化物微纳米晶体的制备进行了系统的总结．     

金属纳米电极的制备、表征及其在电化学测量中的应用

本文简要介绍了各种金属纳米电极的制备及表征方法。结合我们自己的工作,重点介绍了纳米电极在电化学反应动力学参数测量及扫描电化学显微镜(SECM)中的应用,并对其发展前景进行了展望。引用文献78篇。     

碳化钨催化剂电化学稳定性的研究

碳化钨(WC)催化剂在酸性体系中具有“类铂”的催化活性,且不被任何浓度的一氧化碳和几个ppm的硫化氢中毒,可以用于酸性燃料电池中的氢电极和电解合成中的活性阴极材料,也适作加氢和脱氢中的异相催化剂。作为电极材料碳化钨的电化学稳定性直接影响它的使用,但这方面的研究至今尚不多见。本文用恒电流阳极充电法研究WC粉末在酸性和碱性电解液中的电化学稳定性。     

多级树状纳米结构聚苯胺的电化学制备

建立一种无模板的恒电位电聚合方法,可在室温下制备对甲基苯磺酸（p-TSA）掺杂的多级树状纳米结构聚苯胺（PANI）.根据电聚合曲线分析了PANI的聚合机理.扫描电镜（SEM）、透射电镜（TEM）观察表明制备的PANI具有均匀的多级树状纳米结构.紫外可见吸收光谱（UV-Vis）和红外光谱（FTIR）则显示所制备的PANI为掺杂态.该电沉积方法具有简便、易操作的特点,还可应用于其他纳米结构导电聚合物的可控制备.     

高指数晶面和梯度组成的PtCu3@Pt3Cu@Pt纳米枝晶氧还原电催化剂性能

燃料电池作为一种清洁、高效的能量转换装置,其大规模应用受到阴极氧还原反应(ORR)动力学缓慢以及铂资源稀缺和价格高昂等的极大制约.尽管研究人员在过去几十年中付出了巨大努力,但研制高效、耐用的低Pt合金催化剂仍亟待突破.近年的研究表明,Pt的一些高指数晶面能够表现出比Pt(111)晶面更高的ORR活性,尤其是Pt(332...     

高熵纳米合金在电化学催化中的应用

The implementation of clean energy techniques, including clean hydrogen generation, use of solar-driven photovoltaic hybrid systems, photochemical heat generation as well as thermoelectric conversion, is crucial for the sustainable development of our society. Among these promising techniques, electrocatalysis has received significant attention for its ability to facilitate clean energy conversion because it promotes a higher rate of reaction and efficiency for the associated chemical transformations. Noble-metal-based electrocatalysts typically show high activity for electrochemical conversion processes. However, their scarcity and high cost limit their applications in electrocatalytic devices. To overcome this limitation, binary catalysts prepared by alloying with transition metals can be used. However, optimization of the activity of the binary catalysts is considerably limited because of the presence of the miscibility gap in the phase diagram of binary alloys. The activity of binary electrocatalysts can be attributed to the adsorption energy of molecules and intermediates on the surface. High-entropy alloys (HEAs), which consist of diverse elements in a single NP, typically exhibit better physical and/or chemical properties than their single-element counterparts, because of their tunable composition and inherent surface complexity. Further, HEAs can improve the performance of binary electrocatalysts because they exhibit a near-continuous distribution of adsorption energy. Recently, HEAs have gained considerable attention for their application in electrocatalytic reactions. This review summarizes recent research advances in HEA nanostructures and their application in the field of electrocatalysis. First, we introduce the concept, structure, and four core effects of HEAs. We believe that this part will provide the basic information about HEAs. Next, we discuss the reported top-down and bottom-up synthesis strategies, emphasizing on the carbothermal shock method, nanodroplet-mediated electrodeposition, fast moving bed pyrolysis, polyol process, and dealloying. Other methods such as combinatorial co-sputtering, ultrashort-pulsed laser ablation, ultrasonication-assisted wet chemistry, and scanning-probe block copolymer lithography are also highlighted. Among these methods, wet chemistry has been reported to be effective for the formation of nano-scale HEAs because it facilitates the concurrent reduction of all metal precursors to form solid-solution alloys. Next, we present the theoretical investigation of HEA nanocatalysts, including their thermodynamics, kinetic stability, and adsorption energy tuning for optimizing their catalytic activity and selectivity. To elucidate the structure–property relationship in HEAs, we summarize the research progress related to electrocatalytic reactions promoted by HEA nanocatalysts, including the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, methanol oxidation reaction, and CO₂ reduction reaction. Finally, we discuss the challenges and various strategies toward the development of HEAs.     

Anion Modulation of Pt-Group Metals and Electrocatalysis Applications

Pt-group metal (PGM) electrocatalysts with unique electronic structures and irreplaceable comprehensive properties play crucial roles in electrocatalysis. Anion engineering can create a series of PGM compounds (such as RuP₂, IrP₂, PtP₂, RuB₂, Ru₂B₃, RuS₂, etc.) that provide a promising prospect for improving the electrocatalytic performance and use of Pt-group noble metals. This review seeks the electrochemical activity origin of anion-modulated PGM compounds, and systematically analyzes and summarizes their synthetic strategies and energy-relevant applications in electrocatalysis. Orientation towards the sustainable development of nonfossil resources has stimulated a blossoming interest in the design of advanced electrocatalysts for clean energy conversion. The anion-modulated strategy for Pt-group metals (PGMs) by means of anion engineering possesses high flexibility to regulate the electronic structure, providing a promising prospect for constructing electrocatalysts with superior activity and stability to satisfy a future green electrochemical energy conversion system. Based on the previous work of our group and others, this review summarizes the up-to-date progress on anion-modulated PGM compounds (such as RuP₂, IrP₂, PtP₂, RuB₂, Ru₂B₃, RuS₂, etc.) in energy-related electrocatalysis from the origin of their activity and synthetic strategies to electrochemical applications including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), N₂ reduction reaction (NRR), and CO₂ reduction reaction (CO₂RR). At the end, the key problems, countermeasures and future development orientations of anion-modulated PGM compounds toward electrocatalytic applications are proposed.     

Synthesis of NiO Crystals Exposing Stable High-Index Facets

Metal oxides exposing high-index facets are potentially impactful in catalysis and adsorption processes owing to under-coordinated ions and polarities that alter their interfacial properties compared to low-index facets. Here, we report molten-salt syntheses of NiO particles exposing a variety of crystal facets. We show that for a given anion (nitrate or chloride), the alkali cation has a notable impact on the formation of crystals exposing {311}, {611}, {100}, and {111} faces. Based on a parametric analysis of synthesis conditions, we postulate that the crystallization mechanism is governed by the formation of growth units consisting of Ni^II complexes whose coordination numbers are determined by temperature and the selection of anion (associated to the coordination sphere) and alkali cation (associated with the outer coordination sphere). Notably, our findings reveal that high-index facets are particularly favored in chloride media and are stable under prolonged periods of catalysis and steaming.     

Performance of Pt—TiO2 Electrocatalyst for CO Oxidation in the Electrochemical Gas Sensor

It is reported for the first time that the Pt/TiO2 electrocatalyst was successfully used for the electrocatalytic oxidation of CO in the electrochemical gas sensor with a controlled potential mode. The stability of electrocatalytic activity of the Pt-TiO2 electrocatalyst for the CO oxidation is better than that of Pt.     

Deposition of SnO2 on the Anatase TiO2 {105} Facets with High Photocatalytic Performance

Anatase TiO2 as a promising photocatalyst has been widely employed in the decontamination treatment of polluted water, air purification and water splitting. Coupling TiO2 with other semiconductor materials could further enhance the photocatalytic activity. Here, we successfully synthesized the SnOz/TiO2 catalyst by depositing SnO2 particles on the anatase TiO2 {105} facets through a gas phase oxidation process. The SnOz/TiO2 catalyst shows higher photocatalytic activity for decomposition of MB than that of the pure YiO2 catalyst. The enhanced photo- catalytic activity can be attributed to the efficient charge separation since TiO2 and SnO2 catalyst have staggered energy level.     

Electrochemical Approaches to Carbonylative Coupling Reactions

The carbonylation reaction is an effective way to introduce CO or other carbonyl groups into organic compounds, and widely used in the preparation of aldehydes, ketones, amides, and esters. The replacement of conventional reaction approaches by greener electrochemical methods is appealing with great synthetic potential as well as inherent safety, owing to the avoidance of external oxidants or reductants and a more facile control in product selectivity. In this minireview, we give a summary of the recent development of carbonylation reactions via the electrochemical approach.     

Synthesis of polyhedral iron oxide nanocrystals bound by high-index facets

High surface energy of high-index facets endows nanocrystals with high activities and thus promotes potential applications such as highly efficient catalysts,special optical,electrical and magnetic devices.But the high surface energy of the high-index facets usually drives them to grow faster than the other facets and finally disappear during the crystal growth,which leads the synthesis of nanocrystals with high-indexed facets exposed to be a great challenge.Herein,we introduced two routes to control the synthesis of-Fe2O3polyhedrons with different sets of high-index facets,one using different metal ions(Ni2+,Cu2+or Zn2+)as structure-directing agents and the other applying polymer surfactant sodium carboxymethyl cellulose(CMC)as additive.The growth process of high-index-Fe2O3polyhedrons was also discussed and possible growth mechanism was proposed.     

分子印迹电化学传感器的制备及其对啶虫脒的响应特性

应用恒电位沉积法制备了以壳聚糖为功能基体,啶虫脒为模板分子、戊二醛为交联剂的印迹膜电极,并构建印迹传感器。借助阳离子指示探针Ru(NH3)6Cl3,研究该印迹传感器的电化学响应特性及其对模板分子啶虫脒的分子识别性能。结果表明,印迹传感器具有良好的印迹效果,相较于结构类似物如吡虫啉等,对啶虫脒有较高的结合速率和特异性识别能力,且在啶虫脒浓度为1.0 × 10-7 ~ 2.0 × 10-5 mol/L范围内呈线性响应,为农药残留物中啶虫脒的选择性分析提供新的思路。     

重金属自产电能的电化学处理

重金属污染是最受关注的环境问题之一. 电化学处理快速、高效,因而备受关注,发展快速. 本文从重金属离子在阴极接受电子完成电化学还原的原电池和燃料电池系统角度考虑,阐述重金属离子的产电原理,结合实例介绍了重金属在阴极的还原方式,讨论了重金属自产电能处理技术的优势和存在的问题. 污染物自身产能的电化学处理是一种崭新的技术,以期早日付之实用.     

纳米粒子在电化学DNA生物传感器研究中的应用

简要介绍了电化学DNA生物传感器的原理和分类,对纳米粒子在电化学DNA生物传感器研究中的应用进行了详细评述.     

水热法合成过渡金属氧化物纳米材料及其在食品安全检测传感器中的应用进展

以Fe,Co,Mn,Zn等过渡金属制备的氧化物纳米材料具有制备简单、形貌可控以及电化学活性高等特点,且可以固定在电极表面,在电化学传感器的应用中显示了广阔前景。该文重点介绍了过渡金属氧化物水热合成方法的研究进展,并简要阐述了基于过渡金属氧化物纳米材料的新型电化学传感器在食品安全快速检测领域的应用进展。