金属纳米团簇在电化学领域的应用研究进展

尺寸小于2nm的金属纳米团簇是由几个到几百个原子组成的纳米结构材料.对于金属纳米团簇,由于其大部分甚至所有金属原子可能暴露于表面而具有高的表面原子比例,该独特的原子堆积结构使其具有高的表面活性,因此其在催化反应中具有重要应用价值.同时,其明确的原子排列和堆积结构使其可作为模型催化剂,用于研究纳米结构-性能之间的关系.笔者简要总结了近年来金属纳米团簇的研究进展和现状,重点总结了其在电化学领域的应用,包括电催化和电化学传感,最后对其未来在电催化和电分析领域的应用前景进行了展望.     

Electrocatalytic dechlorination of 2,4,5-trichlorobiphenyl using an aligned carbon nanotubes electrode deposited with palladium nanoparticles

Palladium loaded carbon nanotubes cathode with well-aligned nanotubes array was successfully fabricated on a titanium foil (Pd/CNTs/Ti) using a chemical vapor deposition technique and subsequent electrochemical deposition method. Pd particles were well dispersed on CNTs wall surfaces with average sizes no more than 20 nm, in most cases around 10 nm. Experiments for dechlorination of 2,4,5-trichlorobiphenyl (PCB 29) in methanol/water solution were carried out for the first time using Pd/CNTs/Ti cathode for investigation of its performance in electrocatalytic dechlorination of PCBs. Results show that Pd/CNTs/Ti presented better dechlorination efficiency (up to 90% in 6 h) than Pd/Ti and Pd/graphite cathodes owing to unique properties owned by CNTs, which benefited enhanced dechlorination of PCB 29. Complete dechlorination for PCB 29 was observed and biphenyl was identified to be final dechlorination product. The amount of Pd loading, cathode potential, and electrolytes were found to be key factors influencing dechlorination performance.     

碱性介质中钯离子注铁电极上硝基苯的电化学行为

本文研究了Ｆｅ及Ｐｄ／Ｆｅ电极在０．１ｍｏｌ／ＬＮａＯＨ溶液中的阴极极化行为，通过循环伏安法研究了硝基苯（ＮＢ）在Ｆｅ及Ｐｄ／Ｆｅ电极上的电化学行为，ＮＢ在注钯剂量较大的Ｐｄ／Ｆｅ电极上还原效果较好，最后提出了碱性溶液中ＮＢ在Ｐｄ／Ｆｅ电极上电还原的机理．     

羟丙基-β-环糊精修饰纳米碳管载钯催化剂的制备及其甲酸氧化性能

以羟丙基-β-环糊精(HP-β-CD)为添加剂修饰碳纳米管为复合载体,常温常压下,成功合成了Pd纳米簇状结构,并用于甲酸的电催化氧化.XRD及TEM结果表明,制备出的Pd纳米簇状结构由粒径均匀,约为3.6nm的纳米颗粒组成,且高度分散沉积在载体表面.循环伏安测试结果表明,催化剂Pd/HP-β-CD-MWCNTs对甲酸氧化表现出了较高的催化活性和电化学比表面积.研究表明,在HP-β-CD存在条件下,将Pd纳米簇沉积在未作处理的碳纳米管上制备的催化剂适合应用于甲酸燃料电池.     

TiO2-C纳米复合材料负载钯催化剂的制备及其对甲酸的电催化氧化

通过将TiO2和三聚氰胺的混合物高温煅烧制备出TiO2-C纳米复合材料,并将其用作载体合成出Pd/TiO2-C催化剂.采用XRD,TEM,HR-TEM和EDS等手段对催化剂进行了表征分析,并考察了它们对甲酸氧化反应的催化性能.结果表明,Pd负载于碳与TiO2的界面,平均粒径为5nm,与Pd/XC-72和Pd/TiO2相比,Pd/TiO2-C催化剂具有更强的催化活性和稳定性,这归因于TiO2-C载体的特性和Pd/TiO2-C独特的异质结构.     

Synthesis,characterization and electrocatalytic studies of palladium–manganese oxyhydroxide nanocomposite towards direct ethylene glycol fuel cell

The palladium nanoparticle grafted manganese oxyhydroxide nanorod （MON） electrocatalyst has been synthesized and tested for the electrooxidation of ethylene glycol （EG） in an alkaline medium. The MON was prepared using the hydrothermal method and the Pd nano- particles were coated on the MON using an in situ reduction method. The nanocatalyst thus prepared was characterized by powder X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectroscopy and electrochemical methods. The microscopic studies confirm the formation of MON and reveal that the Pd nanoparticles were grafted uniformly on the MON. In the voltammetric studies, the Pd/MON catalyst exhibited a six-fold improved peak current for ethylene glycol electrooxidation compared with the C/Pd. The EG electrooxidation reaction performances of the Pd/MON nanocatalyst in the alkaline solutions containing different quantities of EG were tested through cyclic voltammetry. The catalytic removal of the poisonous intermediates formed during electrooxidation of EG was explained. The present study shows that MON can act as an active support for the Pd nanocatalyst.     

不同络合剂对Pd/MWCNTs催化剂的甲酸电催化氧化性能影响

以添加Na2CO3和NH3.H2O为络合剂的微波多元醇法制备碳纳米管载Pd催化剂(Pd/MWCNTs),并考察了络合剂对催化剂甲酸电催化氧化性能的影响。结果表明,NH3.H2O络合剂制备的Pd/MWCNTs催化剂,其Pd晶粒平均粒径最小(5.2 nm),对甲酸氧化的催化活性和稳定性最好。NH3.H2O与PdCl2能形成络合物,可能会促进微波合成中碳纳米管上形成均匀分散且较小粒径的Pd粒子,因此提高了催化剂的甲酸氧化催化性能。     

六种贵金属取代杂多化合物的制备、表征和初步催化研究

用取代法制备了十二钼锗（硅）酸的Ｐｄ,Ｉｒ,Ｒｕ取代化合物,由ＩＲ,ＵＶ及ＥＰＲ方法测定表明,产物仍保持了其母体化合物的Ｋｅｇｇｉｎ结构,同时Ｐｄ,Ｉｒ,Ｒｕ等贵金属阳离子确定取代了Ｋｅｇｇｉｎ结构中的一个Ｍｏ原子,电化学研究表明Ｒｕ,Ｉｒ取代了母体化合物中的１个Ｍｏ后,多酸母体上的氧化－还原可逆性增强,而Ｐｄ取代化合物由于在电极上的吸附作用使其电化学行为不能被清晰观察到,对上述化合物初步的催化研     

褐藻海带生物质残渣对水中Pd（Ⅱ）的吸附研究

用乙醇处理褐藻海带得到其生物质残渣（Residue of Laminaria japonica,简称ROLJ）,探讨了ROLJ对水溶液中Pd(Ⅱ)的吸附性能.实验考察了溶液pH、接触时间、温度和初始Pd(Ⅱ)浓度等因素对吸附效果的影响,并探讨了ROLJ对Pd(Ⅱ)的吸附动力学及等温吸附特性.结果表明:在pH为3～4范围内,吸附效果最好;吸附平衡时间为80min;吸附动力学符合伪二级动力学模型;Langmuir等温吸附方程能较好地描述Pd(Ⅱ)在ROLJ上的吸附特性,303 K 时ROLJ对Pd(Ⅱ)静态饱和吸附容量为294.12mg/g.热力学分析结果表明,实验条件下ROLJ对Pd(Ⅱ)的吸附反应是自发、吸热和熵值增加的过程.用0.1M HCl+5%硫脲溶液可洗脱回收Pd(Ⅱ),ROLJ是一种有应用前景的钯吸附回收材料.     

Copper nanoclusters: Synthesis,characterization and properties

Metal nanoclusters with a core size smaller than 2 nm have attracted much attention because of their unique physical and chemical properties.Among the studied metal nanoclusters,gold and silver have been studied extensively by size-controlled synthesis, structural characterization and properties investigations.Recently,considerable research effort has been devoted to the investiga- tion of copper nanoclusters.In this review,we highlight recent progress in the study of copper nanoclusters in terms of synthesis methods,characterization techniques and their novel optical and catalytic properties.     

室温高聚物电解质氢催化传感器

分别采用混合压膜法和浸渍还原原位化学沉积法,以Pd为催化剂,高聚物质子导体Nafion膜为电解质,研制复合膜电极构成两种不同的室温固态电解质催化氢传感器。探索出以Pd盐自制Pd黑和浸渍还原制备膜电极的工艺条件,考察了一些因素对传感性能的影响,并进行了讨论。     

金原子簇催化应用的研究进展

在最近的10年里,原子精确的金原子簇(AunLm,L为有机配体)已经被证明是一种新型的纳米金催化剂.不同尺寸的AunLm催化剂表现出独特的电子和晶体结构,为关联催化性能和催化剂结构的内在关系及研究纳米金催化的化学反应机制提供了新的研究平台.在这篇综述中,主要介绍金原子簇催化剂在催化反应中的应用,如选择性氧化和加氢,及C—C偶联反应等,同时,也讨论金原子簇催化剂的尺寸效应、配体效应(例如,芳香族vs脂肪族)、杂金属掺杂(如铜、银、钯、铂)等.最后,在原子尺度上研究了金原子簇催化的反应机制以及结构-活性的构建关系.     

反相微乳液法制备Ni-B非晶态合金团簇

采用W/O型微乳液法,用KBH4还原Ni(Ac)2制备Ni-B非晶态合金团簇.扫描电镜(SEM)和透射电子显微镜(TEM)测试表明,团簇形貌呈球形,尺寸为10~15 nm,分布较均匀,基本达到单分散.热分析(DSC)测试表明,Ni-B样品的热稳定性明显高于水溶液体系用KBH4还原Ni(Ac)2制得的Ni-B非晶态合金纳米颗粒.热处理实验及XRD测试结果表明,Ni-B非晶态合金团簇的晶化过程包括两个步骤,即Ni-B非晶态合金晶化成晶态Ni-B合金和Ni-B晶态合金分解成纳米晶Ni和单质B.     

基于空壳钯和纳米金修饰的过氧化氢无酶传感器的研究

制备并表征了空壳钯纳米粒子,将空壳钯纳米粒子和金纳米粒子修饰在玻碳电极(GC)表面,构建了新型的过氧化氢无酶传感器.通过循环伏安等电化学方法研究了修饰电极的电化学特性,结果表明:Pd/AuNPs/GC对过氧化氢(H2O2)的电极反应具有催化作用,空壳钯和纳米金在催化过氧化氢还原过程中表现出了良好的协同作用.过氧化氢的浓度在2216μmol/L(R=0.9993)范围内,与修饰电极的电流之间呈现出良好的线性关系,检测限为0.2μmol/L(S/N=3).该传感器具有较好的稳定性、重现性、抗干扰性.     

Structural effects on the magnetic hyperthermia properties of iron oxide nanoparticles

Magnetic iron oxide nanoparticles(IONPs) are heavily explored as diagnostic and therapeutic agents due to their low cost, tunable properties, and biocompatibility. In particular, upon excitation with an alternating current(AC) magnetic field, the NPs generate localized heat that can be exploited for therapeutic hyperthermia treatment of diseased cells or pathogenic microbes. In this review, we focus on how structural changes and inter-particle interactions affect the heating efficiency of iron oxide-based magnetic NPs. Moreover, we present an overview of the different approaches to evaluate the heating performance of IONPs and introduce a new theranostic modality based on magnetic imaging guided–hyperthermia.     

Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold) nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD) properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R)-/(S)-2-phenylpropane-1-thiol, (R)-/(S)-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD) derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of many related nanomaterials.     

离子辐照形成空心银纳米颗粒

离子辐照是控制金属纳米颗粒分布和结构的有效方法。将能量为200 keV、剂量为5×10^16ions/cm2的Ag＋注入到非晶SiO2中,形成Ag纳米颗粒层,再用能量为200和500 ke V的Ar＋辐照Ag纳米颗粒。Ar＋辐照后,在部分较大的Ag纳米颗粒中出现空洞,空洞的平均尺寸随着Ar＋辐照剂量的增加而变大。辐照前,Ag纳米颗粒在非晶SiO2中沿纵向呈近似高斯分布;辐照后,投影射程附近的较大的Ag纳米颗粒平均尺寸变大,而投影射程下面的小颗粒逐渐消失。结合Trim程序模拟分析结果可知,Ar＋辐照时的核能量损失和电子能量损失是影响Ag纳米颗粒尺寸分布和结构的重要因素。     

金属纳米团簇在生物医学领域的研究进展

金属纳米团簇具有独特的超小尺寸和光、磁、催化等性能,以及优异的生物相容性等特征,在生物医学研究中备受关注.但其存在发光效率偏低、活体代谢速度较快等问题.为此介绍近几年通过合成优化和发光调控等方法提高金属纳米团簇的检测与成像灵敏度和肿瘤诊疗能力的研究进展.探究金属纳米团簇的肾代谢和生物酶催化性能;开发具有精确原子数、高效生物相容性和肿瘤靶向性的金属纳米团簇;突破其近红外发光量子产率限制,提高光声-磁共振造影等性能,将是未来该领域研究的重要方向.     

铬变酸-2R负载树脂分离富集微量金和钯

以铬变酸-2R（CT-2R）作为螯合剂, D₂₉₆强碱性阴离子交换树脂作为载体制备具有螯合基团的负载树脂, 并用红外光谱对其CT-2R负载树脂结构进行鉴定, 给出了负载树脂的吸附性能及分离富集Au(Ⅲ)和Pd(Ⅱ)的最佳条件. 结果表明, 在pH=1.0的HCl介质中, Au和Pd的氯络阴离子被吸附在树脂上与大量贱金属元素分离. 用0.1 mol/L HCl 40 g/L硫脲溶液以0.5 mL/min的流速进行洗脱, 树脂结构不被破坏, 可重复使用. 通过原子吸收光谱对标准样品的测定, 相对标准偏差（n=6）为5.72%和7.89%.     

水相中两种不同荧光CdS纳米粒子的合成

以巯基乙酸作稳定剂, 通过巯基与金属离子强吸附作用, 在水相中直接合成了两种不同粒径的CdS纳米粒子. 荧光光谱表明, 这两种CdS纳米粒子可以发射较强的对人眼较 敏感的蓝色和黄色荧光, 其表面的自由羧基可与各种生物分子, 如功能蛋白、 特异性抗 体等其中的氨基偶连, 为同时标记多种生物大分子奠定了基础.