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用于将乙醇氧化为二氧化碳的三元电催化剂:使铱能够断裂 C-C 键。

Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

机构信息

Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973, United States.

出版信息

J Am Chem Soc. 2013 Jan 9;135(1):132-41. doi: 10.1021/ja306384x. Epub 2012 Dec 14.

Abstract

Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

摘要

C-C 键的断裂是乙醇电氧化(EOR)为 CO(2)的主要障碍。我们最近证明,三元 PtRhSnO(2)电催化剂可以在室温下实现该反应,其中 Rh 具有独特的断裂 C-C 键的能力。在本文中,我们报告了 Ir 可以作为三元催化剂的一个组成部分诱导 C-C 键断裂的发现。我们对几种碳载纳米颗粒(NP)电催化剂进行了表征和比较,这些催化剂由 SnO(2) NP 核和多金属纳米岛(MM'=PtIr、PtRh、IrRh、PtIrRh)组成,采用种子生长方法制备。采用一系列表征技术来确定合成的 MM'/SnO(2) NPs 的组成和结构,同时电化学和原位红外反射吸收光谱研究阐明了活性和反应中间体和产物性质的趋势。与传统的 Pt/C 和 Pt/SnO(2)/C 催化剂相比,这些 MM'/SnO(2)/C 电催化剂中的几种 EOR 反应性和 CO(2)形成选择性都显著提高。我们证明,具有高 Ir 含量的 PtIr/SnO(2)/C 催化剂具有出色的催化性能,具有最负的 EOR 起始电位和对乙醇完全氧化为 CO(2)的合理良好选择性。

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