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氧化还原响应性聚合物模板作为银纳米粒子的先进多功能催化剂载体。

Redox-Responsive Polymer Template as an Advanced Multifunctional Catalyst Support for Silver Nanoparticles.

机构信息

Department of Chemistry , University of Saskatchewan , 110 Science Place , Saskatoon , Saskatchewan S7N 5C9 , Canada.

Department of Chemical Engineering , Indian Institute of Technology Gandhinagar , Palaj , Gandhinagar , Gujarat 382355 , India.

出版信息

Langmuir. 2018 Sep 11;34(36):10560-10568. doi: 10.1021/acs.langmuir.8b02336. Epub 2018 Aug 30.

Abstract

Hybridization of metal nanoparticles (NPs) with redox-switchable polymer supports not only mitigates their aggregation, but also introduces interfacial electron pathways desirable for catalysis and numerous other applications. The large surface area and surface accessible atoms for noble metal nanoparticles (e.g., Ag, Au, Pt) offer promising opportunities to address challenges in catalysis and environmental remediation. Herein, AgNPs were supported onto redox-switchable polyaniline that acts as an advanced multifunctional conducting template for enhanced catalytic activity. At the initial stage of reduction of Ag, leucoemeraldine is oxidized in situ to pernigraniline (PG), which acts as interfacial pathway between NPs for electron transport. With the contribution of BH, PG acts as an electron-acceptor site, which creates interfacial electron-hole pairs, serving as additional active catalytic reduction sites. The use of a redox-responsive composite system as a template enhances catalyst performance through adjustable charge injection across interfacial sites, along with catalyst reusability for the reduction of 4-nitrophenol (4-NPh). Strikingly, from X-ray photoelectron spectroscopy results it was observed that in situ reduction of Ag onto the conductive polymer alters the electronic character of the catalyst. The unique multielectronic effects of such Ag-supported NPs enrich the scope of such catalytic systems via a tunable interface, diversified catalytic activity, fast kinetics, minimization of AgNPs aggregation, and maintenance of high stability under multiple reaction cycles.

摘要

金属纳米粒子 (NPs) 与氧化还原开关聚合物载体的杂交不仅减轻了它们的聚集,而且还引入了界面电子途径,这对于催化和许多其他应用是理想的。贵金属纳米粒子(例如 Ag、Au、Pt)的大表面积和表面可及原子为解决催化和环境修复中的挑战提供了有前途的机会。在此,AgNPs 被负载到作为先进多功能导电模板的氧化还原开关聚苯胺上,以提高催化活性。在 Ag 还原的初始阶段,白亚甲基蓝被原位氧化为永固紫(PG),PG 作为 NPs 之间的界面电子传输途径。在 BH 的贡献下,PG 充当电子受体位点,形成界面电子-空穴对,充当额外的活性催化还原位点。使用氧化还原响应性复合系统作为模板,通过在界面位点可调电荷注入增强了催化剂的性能,并且还提高了用于还原 4-硝基苯酚(4-NPh)的催化剂的可重复使用性。引人注目的是,从 X 射线光电子能谱结果中观察到,Ag 在导电聚合物上的原位还原改变了催化剂的电子特性。这种负载有 Ag 的 NPs 的独特多电子效应通过可调界面、多样化的催化活性、快速动力学、最小化 AgNPs 聚集以及在多个反应循环中保持高稳定性,丰富了此类催化系统的范围。

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