Rapid and Scalable Synthesis of Cuprous Halide-Derived Copper Nano-Architectures for Selective Electrochemical Reduction of Carbon Dioxide.
Rapid and Scalable Synthesis of Cuprous Halide-Derived Copper Nano-Architectures for Selective Electrochemical Reduction of Carbon Dioxide.
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DOI：
10.1021/acs.nanolett.9b01197
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发表时间：
2019-04
期刊：
影响因子：
10.8
通讯作者：
Huan Wang;Edward Matios;Chuanlong Wang;Jianmin Luo;Xuan Lu;Xiaofei Hu;Weiyang Li
中科院分区：
文献类型：
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作者：
Huan Wang;Edward Matios;Chuanlong Wang;Jianmin Luo;Xuan Lu;Xiaofei Hu;Weiyang Li
电化学还原二氧化碳（CO2）为增值化学品和燃料提供了一个有前途的途径，为环境和能源的可持续发展。铜（Cu）展示了一种独特的能力，可以催化二氧化碳的电化学转化为有价值的多碳产品。然而，开发一种快速、可扩展、经济高效的方法，在低过电位下合成高效、稳定、对多碳产物具有高选择性的Cu催化剂，仍然是一个难以实现的目标。在这项工作中，我们提出了一种简单的湿化学方法来产生定义明确的卤化亚铜（CuX, X = Cl， Br或I）微晶体，这些微晶体在边缘/顶点具有不同程度的截断，这可以归因于卤化物离子的氧化蚀刻机制。更重要的是，所得的卤化亚铜可以电化学转化为各种Cu纳米结构，从而表现出不同的CO2还原行为。本文首次报道了由自组装纳米颗粒组成的Cu纳米纤维，它有利于在低过电位下形成C2+3产物，对乙烷具有特殊的选择性。相比之下，由CuCl演化而来的Cu纳米立方对C1产物具有很高的选择性。cubr衍生的Cu纳米枝晶在过电位较低时易形成C1产物，而当过电位更负时，C2+3产物逐渐占主导地位，有利于乙烯的形成。这项工作明确揭示了卤化物衍生的Cu纳米结构对CO2产物选择性的临界形貌影响，也为研究CO2电还原的结构-性能关系提供了理想的平台。
Electrochemical reduction of carbon dioxide (CO2) into value-added chemicals and fuels provides a promising pathway for environmental and energy sustainability. Copper (Cu) demonstrates a unique ability to catalyze the electrochemical conversion of CO2 into valuable multicarbon products. However, developing a rapid, scalable and cost-effective method to synthesize efficient and stable Cu catalysts with high selectivity toward multicarbon products at a low overpotential is still hard to achieve and highly desirable. In this work, we present a facile wet chemistry approach to yield well-defined cuprous halide (CuX, X = Cl, Br or I) microcrystals with different degrees of truncations at edges/vertices, which can be ascribed to the oxidative etching mechanism of halide ions. More importantly, the as-obtained cuprous halides can be electrochemically transformed into varied Cu nanoarchitectures, thus exhibiting distinct CO2 reduction behaviors. The CuI-derived Cu nanofibers composed of self-assembled nanoparticles are reported for the first time, which favor the formation of C2+3 products at a low overpotential with a particular selectivity toward ethane. In comparison, the Cu nanocubes evolved from CuCl are highly selective toward C1 products. For CuBr-derived Cu nanodendrites, C1 products are subject to form at a low overpotential, while C2+3 products gradually become dominant with a favorable formation of ethylene when the potential turns more negative. This work explicitly reveals the critical morphology effect of halide-derived Cu nanostructures on the CO2 product selectivity, and also provides an ideal platform to investigate the structure-property relationship for CO2 electroreduction.