形貌可控的钯纳米粒子的电化学制备及电催化性质

以NaPdCl4为前驱体, 以柠檬酸钠为包裹剂, 通过两步恒电势法在氧化铟锡(ITO)导电玻璃基底上沉积得到不同形貌的钯纳米粒子(PdNPs). 通过调节晶种沉积电势和粒子生长电势、柠檬酸根和溴离子的浓度及反应温度等因素, 可以控制PdNPs的形貌、尺寸及在ITO基底上的生长密度; 制备出了钯纳米锥阵列及球形、花状和多面体形的PdNPs. 研究结果表明, 钯纳米锥阵列与其它形状的PdNPs相比, 在单位面积ITO基底上具有更大的表面积, 表现出对甲醇更强的电化学氧化能力.     

多孔碳纳米纤维负载Pd纳米颗粒用于增强电催化氧还原性能

采用溶剂热法合成了以锆为金属核心、2-氨基为配体的锆基金属有机骨架(UiO-66)纳米材料,通过静电纺丝技术制备出UiO-66自由分散的聚丙烯腈(PAN/UiO-66)纤维,可控热解得到多孔碳纳米纤维(porous carbon nanofibers,PCNFs),结合湿化学还原法在PCNFs表面沉积Pd纳米颗粒,得到PCNFs@Pd复合材料。通过扫描电子显微镜、透射电子显微镜、X射线衍射技术对其形貌、组成、结构进行表征;采用电化学工作站分别测试了PCNFs@Pd在0.1 mol·L^-1KOH和0.1 mol·L^-1HClO₄电解质中氧还原性能(oxygen reduction reaction,ORR)。结果表明,在PAN纤维中添加UiO-66显著提高了PCNFs@Pd(Pd负载量为0.34%)复合材料的ORR性能。相比40%Pt/C,在碱性电解质中,PCNFs@Pd复合材料展示出更低的Tafel斜率、更优异的循环稳定性和耐甲醇中毒性。在酸性电解质中也表现出类似20%Pt/C的催化活性和循环稳定性。     

刺状Pd纳米粒子的室温合成及其对乙醇氧化的电催化性能

室温下以氯化胆碱为稳定剂,用化学还原法合成了刺状Pd纳米粒子(Pdtnh0o0r0n).透射电子显微镜和电化学循环伏安研究结果表明Pdtnh0o0r0n具有较高密度的台阶位,与商业Pd黑催化剂相比较,Pdtnh0o0r0n对乙醇氧化的电催化活性显著提高,氧化电流密度是商业Pd黑催化剂的1.2倍(-0.40--0.30V)-1.5倍(-0.65--0.40V),起始氧化电位和峰电位均负移50mV.相同电流密度下,Pdtnh0o0r0n催化剂对乙醇的氧化电位均更低.     

纳米Pd上H2O2的电催化还原反应

利用纳米Pd颗粒修饰的Au旋转圆盘电极, 通过强制对流条件下的线性电势扫描伏安法, 研究了酸性介质中H2O2在纳米Pd催化剂上的电还原反应. 动力学研究结果表明, H2O2在纳米Pd上电还原反应的表观活化能为27.6 kJ·mol-1, 反应为2电子转移过程, 电解质的阴离子类型显著影响纳米Pd对H2O2电化学还原反应的催化性能. 根据动力学电流与H2O2浓度及与H+浓度的关系, 提出了Pd催化H2O2电还原反应可能的速率控制步骤, 并讨论了其可能的反应机理.     

低维纳米材料的增强红外吸收与异常红外效应

由低维纳米材料组成的表面体系在电催化、磁学、储能、传感等领域得到广泛研究和应用.增强红外吸收与异常红外效应是其特殊的红外光学性能.作者综述了近年来他们在研究低维纳米材料的特殊红外光学性能方面的主要进展,包括系统研制和构筑各种具有特殊红外性能的低维纳米材料和纳米结构表面体系,发展表面组合电化学研究方法等.研究工作对揭示低维纳米材料的结构与性能之间的本质关系,发展相关的基础和理论具有重要意义.     

核-壳结构Au-Pt纳米粒子的光谱表征和电催化性能

用化学还原法合成了核-壳结构Au-Pt纳米粒子.紫外可见光谱(UV-Vis)、电化学循环伏安(CV)和透射电子显微镜(TEM)表征结果指出，所合成的核-壳结构Au-Pt纳米粒子为球形，平均直径为27 nm.以CO为分子探针，结合透射红外光谱研究，发现CO以孪生吸附态形式(COT)吸附在Au-Pt纳米粒子上，在2110 cm－1和2063 cm－1附近分别给出对称和反对称红外吸收峰. CV研究结果指出Au-Pt/GC电极对CO的氧化有较高的催化活性，起始氧化电位较本体Pt电极提前了0.45 V，峰电位提前了0.11 V.     

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.     

团聚铂纳米粒子电极在甲醇氧化中的电催化特性

用H2还原法并以Nafion作为稳定剂合成团聚的Pt纳米粒子，附载于玻碳表面制备电催化剂.透射电子显微镜（TEM）和扫描电子显微镜（SEM）表征结果指出,团聚Pt纳米粒子的平均尺寸约为400 nm.运用电化学循环伏安法(CV)和原位傅立叶变换红外反射光谱（in situ FTIRS）研究甲醇的氧化过程，发现团聚Pt纳米粒子电极具有较高的电催化活性.原位FTIRS研究结果检测到甲醇在所制备的电催化剂上氧化的中间体为线型吸附态CO物种，其红外吸收给出异常红外效应的光谱特征.     

担载型纳米金的制备参数优化及电催化性能探索

纳米尺度的金由于常表现出有趣的尺寸效应和物理化学特性而被大量应用于催化反应中,但是其在电催化反应中的应用却十分有限. 本文以水为溶剂、HAuCl₄为前驱体、十二烷基聚乙二醇醚（Brij 35）等为软模板剂、NaBH₄为还原剂、活性炭或石墨烯为载体,在温和反应条件下获得担载型金纳米电催化剂. 本文考察并优化了关键制备参数和样品纯化方法,最终确定NaBH₄的最佳浓度区间为5 ~ 10mmol•L^-1,Brij 35的最佳浓度约为1 mmol•L^-1,在3 ~ 16 ^oC下金纳米颗粒的尺寸容易控制,石墨烯和活性炭（EC600）是金纳米颗粒的良好载体. 在优化的反应条件下,金纳米颗粒的粒径可以被控制在1 ~ 4 nm. 热处理法可以有效去除表面活性剂,纯化后的担载型纳米金电催化剂在醇类小分子的氧化反应中表现出良好的性能.     

Observation of Single Pt Nanoparticle Collisions: Enhanced Electrocatalytic Activity on a Pd Ultramicroelectrode

Single Pt nanoparticle (NP) collisions on an electrode surface were detected by using an electrocatalytic amplification method with a Pd ultramicroelectrode (UME). Pd is not a preferred material for UMEs for the detection of single Pt NP collisions, because Pd shows similar electrocatalytic activity compared with Pt for hydrazine oxidation, thus resulting in a high background current level. However, a Pt NP colliding on the Pd UME shows greatly enhanced activity compared with a Pt NP on an inert UME, such as a Au UME, which is usually used for the detection of single Pt NP collisions. The use of an electroactive UME material instead of an inert one facilitated the study of single‐NP activity on the various solid supports, which is important in many NP applications.     

Synthesis of Pd-Based Bimetallic Nanoparticles and Their Effective Electrocatalytic Properties

In this work, we developed a simple and effective one-pot method to synthesize the Pd-based bimetallic nanoparticles (NPs) in the presence of polyvinylpyrrolidone (PVP). By using high-resolution transmission electron microscopy (HRTEM), energy-dispersive spectrometry (EDS) mapping and X-ray diffraction (XRD), the morphologies and compositions of the as-prepared bimetallic NPs were investigated in detail. Furthermore, this approach was also used to achieve the highly dispersive Pd-based bimetallic NPs directly on the carbon black. Significantly, the as-obtained carbon-supported Pd-based bimetallic NPs showed excellent electrocatalytic activity for the methanol oxidation. Among the Pd-based bimetallic NPs and the commercial Pd–C, the PdPt–C displayed the best electrocatalytic activity and stability, which may be mainly attributed to the specific nanostructure and the synergetic effect between Pt and Pd atoms.

     

Facile Fabrication of Nanoparticles Confined in Graphene Films and Their Electrochemical Properties

The development of novel nanostructured electrode materials with high performance and based on abundant elements is a key element in the societal pursuit of sustainable energy. Graphene‐based structures with rich macroporosity and high conductive networks are promising components to develop novel electrode materials. Herein, we described a facile procedure to confine Ni(OH)₂ particles in a graphene film, leading to a new sandwich‐like hybrid structure. The hybrid film offers simultaneously ordered ion diffusion channels and high electrical conductivity, which facilitate the improvement of both electrode kinetics and electrochemical stability, thus leading to high capacitance, fast rate capability, and stable cycle life as supercapacitor materials. This work provides a facile pathway for optimized structures for electrode materials, and represents a benefit for the global issues of energy shortage and environmental pollution.     

单分散PtNi纳米粒子特殊的红外光学性能

采用电位置换反应以及化学还原法制备了单分散PtNi 纳米粒子,循环伏安结果显示该纳米粒子在0.1mol·L^-1硫酸介质中对CO的氧化表现出比本体Pt 电极更好的电催化活性. 以CO为探针分子,采用电化学原位红外光谱研究了PtNi 纳米粒子上的特殊红外光学性能. 结果表明,PtNi 纳米粒子无论是在玻碳电极还是在金电极上,均表现出对称的双极谱峰,同时给出很强的增强效应. 论文研究结果有助于进一步了解低维纳米材料特殊红外性能的本质.     

单分散PtNi纳米粒子特殊的红外光学性能(英文)

采用电位置换反应以及化学还原法制备了单分散PtNi纳米粒子,循环伏安结果显示该纳米粒子在0.1mol·L-1硫酸介质中对CO的氧化表现出比本体Pt电极更好的电催化活性.以CO为探针分子,采用电化学原位红外光谱研究了PtNi纳米粒子上的特殊红外光学性能.结果表明,PtNi纳米粒子无论是在玻碳电极还是在金电极上,均表现出对称的双极谱峰,同时给出很强的增强效应.论文研究结果有助于进一步了解低维纳米材料特殊红外性能的本质.     

嵌入Y型分子筛中钯簇合成与结构的研究

经微波交换-焙烧-氢还原等过程制备了嵌入Y型分子筛中的钯簇化合物（Pd0Y）应用径向电子分布函数法（RedialElectronDistributionFunction），就其钯原子簇化合物进行了结构的研究．结果说明，嵌入Y型分子筛中的钯原子以A1型密堆积方式排列，聚集成约12大小的原子簇，嵌在Y型分子筛超笼之中．分子筛骨架的作用使族之间分立存在．它在超笼之中的占有率仅为0.06因此Pd0Y化合物既有纳米级金属钯的性能，又有分子筛固有的孔道结构特征．如此含有钯簇的分子筛化合物对一氧化碳完全氧化的反应具有超常的催化活性．     

嵌入Y型分子筛中钯簇合成与结构的研究

Pd clusters encaged in Y-zeolite (Pd0Y) have been prepared by means of exchanging zeolite HY with [Pd(NH3)4]2+ under microwave radiation. The product formed was deaminized by heating, washed sufficiently with de-ionized water and reduced with hydrogen. The crystal phase diffraction of Pd was not found in the XRD spectrogram of Pd0y. According to polycrystal X-ray diffraction data. Radial Electron Distribution Function (REDF) of Pd0Y was calculated to elucidate the structure of Pd cluster. The results show that the Pd clusters are of the Al type closely packed arrangement. The dimension of them is about 12 Å. They are encaged in the supercage of zeolite Y. Their occupancy on the supercage is as small as 0.06 so that the framework structure of zeolite Y is unchanged. Therefore, the high dispersing Pd cluster aggregating in supercage exhibit strong catalytic effect. The CO-conversion of Pd0Y with Pd 0.72% and 6.13% (in mass fraction) is 67 % and 100 % (in volume fraction) respectively. Evaluation conditions:
mixed gas containing 0.02% CO and air,
space velocity 3000 h-1,
reaction temperature 0 ℃.     

ZnS纳米粒子的固相合成及其光学性能

将不同的添加剂引入到低温固相反应中，快速合成了不同尺寸的ZnS纳米粒子。利用TEM表征了产物形貌，利用XRD研究了不同的添加剂、同一添加剂下不同的反应温度、不同反应时间对纳米粒子尺寸的影响。结果表明，不同的添加剂对粒子的尺寸影响较大，其中，十二烷基胺以其特殊的反应方式在较高温度下获得了较小的纳米粒子。另外，在PEG400存在条件下，反应温度和反应时间对粒子尺寸均有一定的影响。同时，对不同条件下所得产物的紫外-可见光吸收性能也进行了测试。     

Sonochemical Synthesis of Three-dimensional Aggregates of Pd Nanoparticles with High Electrocatalytic Activity Towards Ethanol Oxidation

Flower-like aggregates composed of （4.0±0.8） nm palladium（Pd） nanoparticles were prepared via ultrasonics in the palladium（Ⅱ） chloride（PdCl2） H2O/EtOH（5/1,volume ratio） solution with the addition of a quantity of poly（vinyl pyrrolidone）（PVP） and sodium dodecyl sulfonate（SDS）.The morphologies,crystal structures and the optical properties of the flower-like Pd nanostructures were characterized by X-ray diffraction（XRD）,X-ray photoelectron spectroscopy（XPS）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,selected area electron diffraction（SAED） and UV-visible absorption spectroscopy,respectively.The mechanism of sonochemical reduction of Pd（Ⅱ） ions was also investigated.The results show that the molar ratio of PVP to SDS affected the formation of the flower-like aggregates of Pd nanoparticles.Moreover,the electrocatalytic properties of Pd aggregates modified glassy carbon electrode for ethanol oxidation were also investigated by cyclic voltammetry（CV）.This material exhibits remarkable electrocatalytic activity for ethanol oxidation in 1 mol/L KOH and appears as a promising candidate to be applied in direct ethanol fuel cells.     

Assembly of SnSe Nanoparticles Confined in Graphene for Enhanced Sodium‐Ion Storage Performance

Sodium‐ion batteries (SIBs) have attracted much interest as a low‐cost and environmentally benign energy storage system, but more attention is justifiably required to address the major technical issues relating to the anode materials to deliver high reversible capacity, superior rate capability, and stable cyclability. A SnSe/reduced graphene oxide (RGO) nanocomposite has been prepared by a facile ball‐milling method, and its structural, morphological, and electrochemical properties have been characterized and compared with those of the bare SnSe material. Although the redox behavior of SnSe remains nearly unchanged upon the incorporation of RGO, its electrochemical performance is significantly enhanced, as reflected by a high specific capacity of 590 mA h g^?1 at 0.050 A g^?1, a rate capability of 260 mA h g^?1 at 10 A g^?1, and long‐term stability over 120 cycles. This improvement may be attributed to the high electronic conductivity of RGO, which also serves as a matrix to buffer changes in volume and maintain the mechanical integrity of the electrode during (de)sodiation processes. In view of its excellent Na⁺ storage performance, this SnSe/RGO nanocomposite has potential as an anode material for SIBs.