过渡金属(Mo,Fe,Co和Ni)基催化剂在电催化还原二氧化碳还原中应用

doi:10.1016/S1872-2067(18)63073-6

摘要/Abstract

摘要：

近年来，全球二氧化碳排放量逐年增加，对人们赖以生存的生态环境已造成严重威胁，因此将二氧化碳转化成高附加值的化学品和燃料受到前所未有的广泛关注.与目前已开发的转化技术（如热催化和光催化等）相比，电催化二氧化碳转化技术具有稳定的效率、可控的选择性、简单的反应单元和巨大的工业应用潜力，是一种更为理想的转化技术之一.从反应动力学来看，目前的催化剂仍难以克服反应过程中高的能量屏障以及迟缓的反应速度.另一方面，电催化二氧化碳转化包含多个质子和电子的耦合过程，反应过程包含多种路径，反应产物往往是混合物.在此背景下，如何发展高催化效率和高选择性电催化剂成为目前研究的焦点.在众多的电催化剂中，贵金属及其合金展现出较高的电催化二氧化碳还原活性，但储量小的缺点限制了其大规模的工业应用.铜基材料可以把二氧化碳转化为附加值更高的产品.然而，铜基材料仍难以克服选择性差、失活严重和效率低等缺点.作为一种更廉价的材料，碳基催化剂具有价廉、比表面积大、导电性好、化学性质稳定以及优异的机械性能等优点在电催化二氧化碳还原中得到了广泛的研究.然而，单纯的碳催化剂对于二氧化碳分子活化以及吸附反应中间体能力较低，导致了碳基材料催化电催化二氧化碳还原活性以及选择性较低.因此，开发出可实际应用的高效率和高选择性非贵金属电极材料是当前该技术研究中亟待解决的关键科学问题.
过渡金属基化合物在能源转化中展现出巨大的应用潜力.过渡金属价电子在d轨道，而d轨道邻近费米能级，d轨道电子填充的变化使得d轨道中心与费米能级相对位置发生变化，进而展现出多种催化活性.电催化二氧化碳还原是一个多电子和质子耦合过程，催化剂的本征活性由其表面电子结构决定.在此背景下，过渡金属基化合物价层电子轨道的多变性使其成为提高电催化二氧化碳还原效率和选择性的理想催化剂.对于电催化二氧化碳还原，不同中间体的标度关系是制约反应总效率的关键因素.Nørskov等研究发现，MoS₂，MoSe₂和Ni掺杂MoS₂催化剂上存在不同种类的活性位点.不同的活性位点可以分别吸附反应中间体并使中间体的吸附过程相对独立，从而有效打断中间体的标度关系.2014年，Salehi-Khojin等成功把MoS₂应用在高效电催化二氧化碳还原中.边缘Mo原子d带电子靠近费米能级的特性使其具有更高的电催化活性.其它研究工作者通过引入掺杂物质，进一步提高了MoS₂的电催化二氧化碳还原性能.Fe位点在理论上虽然具有很高的电催化二氧化碳转化活性，然而目前铁基催化剂的研究相对较少.Co基材料也可用于电催化二氧化碳转化.2016年，Xie等首次制备无机Co基材料用于电催化二氧化碳还原.部分氧化的钴可以促进速控步骤反应进程，进而降低整体反应的过电势.基于此，制备了超薄的Co₃O₄片层，发现价电子轨道中心更靠近费米能级时，电极材料展现出更高的催化活性.进一步研究发现氧空穴的存在也可以减小速控步骤的能量屏障.此外，Ni基材料也被证明具有高的催化二氧化碳转化活性.目前这些研究工作对如何构建高性能电极材料在理论上给出了指导方向，并且联系实验证明了方法的可行性.受到这些工作的启发，未来可将有巨大潜力的过渡金属基化合物化合物，例如过渡金属氮化物、过渡金属磷化物、过渡金属碳化物和过渡金属硼化物等，作为电催化剂研究其二氧化碳还原催化性能.另外，就目前的研究来看，将二氧化碳有效地还原到特定的产物仍存在巨大的挑战.如何优化过渡金属（Mo，Fe，Co和Ni）基催化剂价层d轨道结构，促进反应中间体吸附过程，将是解决催化活性和选择性这一科学问题的关键.

关键词: 过渡金属, 能源转换, 电催化, 二氧化碳

Abstract:

The electrochemical conversion of CO₂ into value-added chemicals and fuels has attracted widespread concern since it realizes the recycling of greenhouse gases. Production of new materials lies at the very core of this technology as it enables the improvement of developmental efficiency and selectivity by chemical optimization of morphology and electronic structure. Transition metal-based catalysts are particularly appealing as their d bands have valence electrons which are close to the Fermi level and hence overcome the intrinsic activation barriers and reaction kinetics. The study of Mo, Fe, Co, and Ni-based materials in particular is a very recent research subject that offers various possibilities in electrochemical CO₂ reduction applications. Herein, we summarize the recent research progress of Mo, Fe, Co, and Ni-based catalysts and their catalytic behavior in electrochemical CO₂ reduction. We particularly focus on the relationship between structures and properties, with examples of the key features accounting for the high efficiency and selectivity of the CO₂ reduction process. The most significant experimental and theoretical improvements are highlighted. Finally, we concisely discuss the scientific challenges and opportunities for transition metal-based catalysts.

Key words: Transition metal, Energy conversion, Electrocatalytic, CO₂

郝金辉, 施伟东. 过渡金属(Mo,Fe,Co和Ni)基催化剂在电催化还原二氧化碳还原中应用[J]. 催化学报, DOI: 10.1016/S1872-2067(18)63073-6.

Jinhui Hao, Weidong Shi. Transition metal (Mo, Fe, Co, and Ni)-based catalysts for electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(18)63073-6.

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