贵金属复合纳米粒子的研究进展

贵金属复合纳米粒子具有不同于单组分纳米粒子的独特的光、电和催化等物理与化学性能,是构筑新型功能复合材料的重要单元,在传感器、光学材料、催化剂及生物领域都有着重要应用,已成为当前纳米材料科学研究领域中的前沿和热点。本文主要评述了具有核壳、异质结构以及合金结构的贵金属复合纳米粒子的制备、物理与化学性能及应用等方面的研究进展。     

LDHs/碳复合纳米材料的催化性能研究进展

层状双金属氢氧化物(LDHs)是一类典型的结构可调的阴离子层状功能材料,直接或经焙烧、还原处理后可作为高活性、高稳定性、廉价的催化剂或催化剂载体应用到催化领域.碳纳米材料自身良好的力学、电学、化学性质使其可作为理想的功能组元构筑LDHs/碳复合纳米材料,进而增强催化性能.本文综述了由LDHs与碳材料构筑的复合纳米催化材料的设计、可控制备及其在电催化、光催化、催化加氢及氧化等多相催化领域的应用进展,并从材料的可控制备及应用方面讨论了LDHs/碳复合纳米材料在多相催化领域面临的挑战与发展前景.     

贵金属杂化纳米材料的合成及性能研究进展

近年来,杂化纳米材料的出现极大地拓展了纳米材料的应用范围,其特殊的结构、性能、尺寸和形貌使其不仅保持了各组分材料的特性及功能,更涌现了不同于各组分材料所不具备的新颖的、多样化的特殊性能和应用潜能,因此其制备方法和性能应用已经成为了研究热点.运用纳米技术将贵金属纳米粒子与其他性能优异的物质结合形成的贵金属杂化纳米材料被广泛运用到电化学、光催化、免疫传感、生物催化和医药化学等领域.本文综述了贵金属杂化纳米材料的制备方法、结构组成、性能特点、应用前景以及最新的发展趋势,重点介绍了贵金属杂化纳米材料的合成及应用.     

贵金属基纳米酶的研究进展

贵金属纳米材料在纳米尺度具有独特的光学、 电学性质及优异的催化性能, 是一类重要的功能纳米材料. 基于贵金属材料的纳米酶研究是贵金属纳米材料在生物医学领域的一个前沿研究方向. 贵金属基纳米酶具有特殊的光学性质、 较好的化学稳定性、 可调控的类酶活性及良好的生物相容性, 是目前纳米生物医学领域的热点研究材料. 本文总结了贵金属基纳米酶的活性种类、 活性机理、 活性调控以及在生物医学等领域的潜在应用.     

中空贵金属纳米材料氧还原催化的研究进展（英文）

中空纳米结构具有比表面积大、传质可控和活性位点明确等优势,其结构设计与电催化应用在能源转化与储存领域引起了广泛关注.特别是中空贵金属纳米材料用于氧还原催化时,中空内腔引入到贵金属纳米结构,不仅暴露更多的活性位点,还能减少贵金属的用量,这将为贵金属催化剂的大规模应用提供一个理想的研发平台.本文综合评述了近年来中空贵金属的合成策略及其氧还原催化应用.首先,回顾了中空贵金属在氧还原催化剂研制中的优势与意义;然后,介绍了近期关于中空贵金属的制备策略(硬模板法、软模板法、自模板和无模板法等)及其优势;最后,分析了中空贵金属在氧还原领域所面临的挑战,并对其设计进行了展望.     

贵金属多孔纳米结构的模板法制备及生物检测应用

贵金属多孔纳米材料是一类非常重要的新型多功能纳米材料,其具有独特的空心内部、多孔的外壁以及可调的形貌等,表现出优异的光、电、催化等特性。调制贵金属多孔纳米材料的尺寸、形状、排列和空间取向等对促进其在拉曼光谱、生物传感等方面的应用至关重要。模板法是利用与目标产物的纳米尺度特征相匹配的预制结构来指导纳米材料的合成,可以制备出其他方法难以制备的新型多孔纳米结构材料。基于模板的多样性,能够便捷的调节多孔贵金属的孔径、尺寸和组分,充分的开发贵金属纳米结构的特性。本文着重介绍了贵金属多孔纳米材料的类型和调控这些纳米结构的各种模板方法,分析了各种制备方法的优势和不足,并简要综述了贵金属多孔纳米结构在生物检测方面的一些应用进展。     

功能化金纳米材料在肿瘤诊疗中的研究与应用

作为一种重要的贵金属, 金具有表面等离子共振的光学特性, 在材料、 催化和医学诊疗等领域有着广泛且重要的应用. 本文综合评述了表面功能化的金纳米材料在肿瘤诊断及治疗领域的相关研究, 并对金纳米材料在肿瘤诊疗领域的未来发展进行了展望.     

水滑石基催化剂催化合成碳纳米材料的研究进展

碳纳米材料是一类推动能源存储、 多相催化、 高性能复合和生物医药等领域发展的重要材料, 可控合成碳纳米材料对相关领域的发展具有重要意义. 水滑石(LDHs)材料具有层板金属种类及含量可调等特点, 经焙烧、 还原后可制备出金属种类、 密度和粒径分布各异的高分散、 高稳定金属纳米催化剂, 可实现高效催化生长各种类型的碳纳米材料. 此外, 通过调控反应条件和反应器等, 可以影响LDHs基金属纳米催化剂催化生长的碳纳米材料的结构和性能. 本文总结了LDHs基金属纳米催化剂的可控制备、 碳纳米材料结构调控以及利用LDHs基催化剂制备的碳纳米材料的应用等方面的研究工作, 并阐明了催化剂的可控制备是控制合成碳纳米材料的核心手段, 这为利用LDHs基催化剂进一步合成更高性能碳纳米材料的研究指明了方向. 此外, 本文还结合近些年在光、 电及光热催化方面的研究进展, 展望了基于新型LDHs纳米结构生长碳纳米材料的研究前景.     

无机镍纳米复合材料

纳米复合材料因具有独特的物理、化学性能而成为纳米领域研究的热点。镍纳米材料作为一种重要的过渡金属纳米材料,在磁学、电化学、催化等领域具有广泛的应用。将它与其他金属、氧化物等材料复合,一方面使其固有性质得到明显改善,另一方面利用其他组成和镍基材料的协同作用,可得到具有新特性的异质材料,因此研究镍基纳米复合材料的合成具有重要的科学意义。由于纳米材料的结构不同,其复合位置和复合方式均存在不同,本文按照复合材料的结构特征,分别从核壳型、负载型、多节段纳米线3种类型对镍纳米复合材料的研究进展进行评述,在介绍这些材料的合成方法、结构特点的基础上,综述各种方法、各类结构的优缺点及应用前景,为类似复合材料的合成提供借鉴。     

甲壳素基新材料研究进展

甲壳素/壳聚糖良好的生物相容性、生物可降解性及独特的生理活性使其成为非常有应用价值的天然高分子材料,当前已成为新材料领域的研究热点.甲壳素/壳聚糖具有良好的可加工性能,可固定贵金属、半导体纳米材料等活性催化物质,同时其本身也具有催化作用,是一类绿色环境友好的高分子催化材料.良好的生物相容性和生物可降解性使甲壳素/壳聚糖...     

在导电高分子薄膜表面沉积密度可控的银纳米粒子

<正>由于导电高分子的导电性和化学性质可以在导体和半导体区间内快速调节[1],因此其复合材料受到了越来越多的关注[2].金属纳米粒子在光电子器件、检测及传感等诸多领域表现出独特的性能[3],在生物技术领域中的重要性尤为突出[4].因此,如果将导电高分子和金属纳米粒子结合在一起,将有利于拓展导电高分子的应用范围.本文研究了银纳米粒子在聚苯胺薄膜表面的沉积行为,分别用原子力显微镜(AFM)和扫描电子显     

聚吡咯/聚苯胺复合型导电聚合物防腐蚀性能

采用循环伏安法,在含吡咯和苯胺的0.3 mol/L草酸水溶液中制备了聚吡咯/聚苯胺(PPy/Pani)的复合型导电聚合膜。采用红外光谱、极化曲线、自腐蚀电位-时间曲线、扫描电子显微镜和电化学阻抗谱研究了共聚膜的防腐蚀性能。结果表明,在1 mol/L H2SO4中,PPy、Pani与不锈钢基体发生氧化还原反应,促进不锈钢表面发生钝化;当苯胺与吡咯浓度比为1∶3时,制备得到的复合型导电聚合膜所保护的不锈钢自腐蚀电流最小,自腐蚀电位最高,保护时间最长。PPy、Pani及其共聚膜在3.5%NaCl溶液中电化学阻抗谱表明,所制备的PPy、Pani及其共聚物膜与不锈钢基体发生氧化还原反应,使其表面钝化;当Cl-到达不锈钢表面时,破坏钝化膜导致不锈钢腐蚀。     

A review on amperometric immunoassays for tumor markers based on the use of hybrid materials consisting of conducting polymers and noble metal nanomaterials

Conducting polymers possess good conductivity, can be easily modified, have a particular redox activity. Noble metal nanomaterials, in turn, possess high conductivity, catalytic properties and large surface-to-volume ratios. Synergistic materials consisting of both conducting polymer and metal nanomaterial therefore are most useful materials for use in electrochemical immunosensors with improved sensitivity and specificity. This review (with 75 references) gives an overview on advances in conducting polymer based noble metal nanomaterial hybrids for amperometric immunoassay of the 13 most common tumor markers. The review is divided into the following sections: (1) Polyaniline based noble metal nanomaterial hybrids; (2) Polyaniline derivative-based noble metal nanomaterial hybrids; (3) Polypyrrole-based noble metal nanomaterial hybrids. A final section covers future perspectives regarding challenges on the design of electrochemical immunoassays.

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Graphical abstract Advances on conducting polymer and noble metal nanomaterial hybrids for amperometric immunoassay of tumor marker are reviewed. Future perspectives regarding challenges on the construction of electrochemical immunosensing interface for tumor marker are discussed.

     

聚苯胺/金属纳米粒子复合物的制备及性能

基于国内外最新研究文献及本课题组研究工作,从发展历史、制备方法、多功能性方面系统综述了近年来发展起来的聚苯胺/金属纳米粒子复合物。在聚苯胺基体中引入金属纳米粒子的方法可归纳为3大类：原位复合法、直接共混法和层层自组装法。所形成的有机聚苯胺和无机金属杂化复合物不仅能保留各自原有的特异性能,而且二组分之间还存在着相互协同作用,能够极大地提升基体聚苯胺材料的性能,电导率最高可提高100倍,电氧化催化电流最高可提高10倍。分散在聚苯胺膜中的极少量铂微粒就能使不锈钢板的腐蚀电位稳定在钝化区域。聚苯胺/金属纳米粒子复合物所表现出的突出的固有电导性、优异的反应催化性和极强的金属防腐性,使其跻身于为数不多的新型高性能复合材料之列,显示出了诱人的应用前景。     

Magnetic hybrid modified electrodes, based on magnetite nanoparticle containing polyaniline and poly(3,4-ethylenedioxythiophene)

In this paper, we report on the direct electrodeposition of magnetic hybrids based on magnetite nanoparticle containing poly(3,4-ethylenedioxythiophene) (PEDOT) and polyaniline (PANI) in the presence of magnetite and the special conducting electrolyte, potassium tetraoxalate. The optimal electropolymerization processes (monitored by scanning electron microscopy) were performed potentiostatically, and the incorporation of the iron oxide into the polymeric film was demonstrated by Diffuse Reflectance UV-Visible Spectroscopy (DR-UV?Cvis) and transmission electron microscopic measurements. Electrochemical quartz crystal nanobalance proved that both the neat PEDOT and the PEDOT/magnetite hybrid show anion exchange behaviour. Cyclic voltammetric features of the polymers and their hybrids exhibited an enhanced redox capacity of the composites. The difference in the effect of the scanning rate on this capacity increase in the two cases could be interpreted by the assumption that the presence of magnetite manifests dominantly in the enhanced intrinsic electroactivity of PANI, while in the case of the PEDOT composite, the extra charge is more connected to the charge surplus originating from the redox activity of the nanoparticles.     

In-situ loading ultrafine AuPd particles on ceria: highly active catalyst for solvent-free selective oxidation of benzyl alcohol

Ce(III) oxide was synthesized under the protection of nitrogen gas, which had strong ability to reduce noble metal ions (e.g., Au, Pd ions) into metallic forms under oxygen-free conditions. On the basis of the surface redox reaction between the Ce(III) oxide support and noble metal ions, an effective and novel approach was presented to prepare noble metal/CeO(2) nanocatalysts, and a series of AuPd/CeO(2) nanocomposites with different Au:Pd molar ratios and metal loadings were obtained in the absence of any extra reducing and protective agents. The resultant composites were characterized by different techniques including X-ray diffraction, transmission electron microspectroscopy, X-ray photoelectron microspectroscopy, and ICP-AES analysis. It was demonstrated that in the AuPd/CeO(2) composites the content of Ce(III) reached about 30%, and the AuPd bimetallic particles with average size of 2.6 or 3.3 nm and narrow size distribution were uniformly distributed on the CeO(2) nanorods. The AuPd/CeO(2) composites were found to be excellent heterogeneous nanocatalysts for the selective oxidation of benzyl alcohol under solvent-free conditions. It was shown that all the AuPd/CeO(2) catalysts exhibited good selectivity toward benzaldehyde; especially, the catalyst with Au:Pd = 1:5 and metal loading of 1.2 wt % displayed extremely high activity with a TOF = 30.1 s(-1) at 160 °C.     

Transmetalation reaction between hydrophobic silver nanoparticles and aqueous chloroaurate ions at the air-water interface

The transmetalation reaction between a sacrificial nanoparticle and more noble metal ions in solution has emerged as a novel method for creating unique hollow and bimetallic nanostructures. In this report, we investigate the possibility of carrying out the transmetalation reaction between hydrophobic silver nanoparticles assembled and constrained at the air-water interface and subphase gold ions. We observe that facile reduction of the subphase gold ions by the sacrificial silver nanoparticles occurs resulting in the formation of elongated gold nanostructures that appear to cross-link the sacrificial silver particles. This transmetalation reaction may be modulated by the insertion of an electrostatic barrier in the form of an ionizable lipid monolayer between the silver nanoparticles and the aqueous gold ions that impacts the gold nanoparticle assembly. Transmetalation reactions between nanoparticles constrained into a close-packed structure and appropriate metal ions could lead to a new strategy for metallic cross-linking of nanoparticles and generation of coatings with promising optoelectonic behavior.     

Magnetic hybrid modified electrodes,based on magnetite nanoparticle containing polyaniline and poly(3,4-ethylenedioxythiophene)

In this paper, we report on the direct electrodeposition of magnetic hybrids based on magnetite nanoparticle containing poly(3,4-ethylenedioxythiophene) (PEDOT) and polyaniline (PANI) in the presence of magnetite and the special conducting electrolyte, potassium tetraoxalate. The optimal electropolymerization processes (monitored by scanning electron microscopy) were performed potentiostatically, and the incorporation of the iron oxide into the polymeric film was demonstrated by Diffuse Reflectance UV-Visible Spectroscopy (DR-UV–vis) and transmission electron microscopic measurements. Electrochemical quartz crystal nanobalance proved that both the neat PEDOT and the PEDOT/magnetite hybrid show anion exchange behaviour. Cyclic voltammetric features of the polymers and their hybrids exhibited an enhanced redox capacity of the composites. The difference in the effect of the scanning rate on this capacity increase in the two cases could be interpreted by the assumption that the presence of magnetite manifests dominantly in the enhanced intrinsic electroactivity of PANI, while in the case of the PEDOT composite, the extra charge is more connected to the charge surplus originating from the redox activity of the nanoparticles.

     

碳包覆Pd/TiO2光催化产氢协同胺类选择性氧化合成亚胺(英文)

负载型金属纳米催化剂由于其优异的光催化性能,被广泛应用于光催化产氢协同胺类氧化偶联合成高附加值亚胺体系。但在反应过程中,金属表面对H原子和亚胺表现出较强的吸附能力,导致了亚胺易于发生自氢化反应而生成仲胺,显著降低了亚胺的选择性。在本文中,我们证实了在Pd/Ti O₂表面构建超薄碳层(Pd/Ti O₂@C)是一种解决上述问题的有效策略。在Pd/Ti O₂表面构筑的超薄碳层可以有效调控H原子和亚胺在其表面的吸附行为,避免了光催化氧化偶联过程中亚胺的自氢化。因此,Pd/Ti O₂@C光催化剂在光催化产氢协同胺类选择性氧化合成亚胺体系中展现出优异的亚胺选择性。本研究提供了一种便捷有效的策略推动负载型金属纳米催化剂在光催化产氢协同合成高附加值产物体系中的应用。     

Electrochemical Polymerization of Aniline in Polyamide and Polyvinyl Alcohol Matrices

The electrochemical polymerization of aniline was studied in polymer matrices (polyamid-12 and polyvinyl alcohol) on an electrode in the potential cycling mode from –0.2 to +0.8 V vs. SCE. The indices of this process such as the potentials and currents of the polyaniline redox peaks, polymerization rate, and properties of the conducting composite formed depend on the nature of the matrix polymer and are a function of the extent of interaction of this matrix polymer with aniline and polyaniline.