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具有可控CO电还原产物选择性的Pd-Cu双金属纳米催化剂的形态和组成设计

Morphological and Compositional Design of Pd-Cu Bimetallic Nanocatalysts with Controllable Product Selectivity toward CO Electroreduction.

作者信息

Zhu Wenjin, Zhang Lei, Yang Piaoping, Chang Xiaoxia, Dong Hao, Li Ang, Hu Congling, Huang Zhiqi, Zhao Zhi-Jian, Gong Jinlong

机构信息

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, 300072, P. R. China.

出版信息

Small. 2018 Feb;14(7). doi: 10.1002/smll.201703314. Epub 2017 Dec 27.

Abstract

Electrochemical conversion of carbon dioxide (electrochemical reduction of carbon dioxide) to value-added products is a promising way to solve CO emission problems. This paper describes a facile one-pot approach to synthesize palladium-copper (Pd-Cu) bimetallic catalysts with different structures. Highly efficient performance and tunable product distributions are achieved due to a coordinative function of both enriched low-coordinated sites and composition effects. The concave rhombic dodecahedral Cu Pd (CRD-Cu Pd) decreases the onset potential for methane (CH ) by 200 mV and shows a sevenfold CH current density at -1.2 V (vs reversible hydrogen electrode) compared to Cu foil. The flower-like Pd Cu (FL-Pd Cu) exhibits high faradaic efficiency toward CO in a wide potential range from -0.7 to -1.3 V, and reaches a fourfold CO current density at -1.3 V compared to commercial Pd black. Tafel plots and density functional theory calculations suggest that both the introduction of high-index facets and alloying contribute to the enhanced CH current of CRD-Cu Pd, while the alloy effect is responsible for high CO selectivity of FL-Pd Cu.

摘要

将二氧化碳电化学转化(二氧化碳电化学还原)为高附加值产品是解决二氧化碳排放问题的一种很有前景的方法。本文描述了一种简便的一锅法来合成具有不同结构的钯 - 铜(Pd - Cu)双金属催化剂。由于富集的低配位位点和组成效应的协同作用,实现了高效的性能和可调节的产物分布。与铜箔相比,凹面菱形十二面体CuPd(CRD - CuPd)使甲烷(CH₄)的起始电位降低了200 mV,并在-1.2 V(相对于可逆氢电极)下显示出七倍的CH₄电流密度。花状PdCu(FL - PdCu)在-0.7至-1.3 V的宽电位范围内对CO表现出高法拉第效率,与商业Pd黑相比,在-1.3 V时达到四倍的CO电流密度。塔菲尔曲线和密度泛函理论计算表明,高指数晶面的引入和合金化都有助于增强CRD - CuPd的CH₄电流,而合金效应是FL - PdCu具有高CO选择性的原因。

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