Embedding Covalency into Metal Catalysts for Efficient Electrochemical Conversion of CO2
Embedding Covalency into Metal Catalysts for Efficient Electrochemical Conversion of CO2
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DOI：
10.1021/ja503782w
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发表时间：
2014-08-13
影响因子：
15
通讯作者：
Kim, Hyungjun
中科院分区：
文献类型：
--
作者：
Lim, Hyung-Kyu;Shin, Hyeyoung;Kim, Hyungjun
二氧化碳转换是发展当前和未来可持续碳经济的一项重要技术。许多研究都集中在二氧化碳的电化学转化成各种有用的化学物质上。然而，目前还没有一种解决方案具有足够高的效率和稳定性，以证明其实际适用性。在这项工作中，我们利用基于第一性原理的高通量筛选，提出了银基催化剂，可以有效地将CO2电化学还原为CO，同时将过电位降低0.4-0.5 V。我们发现了共价辅助电化学反应（CAER）机制，其中p嵌段掺杂剂通过将部分共价施加到金属催化剂上，从而对反应的能量调节产生了主要影响，从而大大提高了金属催化剂的催化活性，远远超过了d嵌段掺杂剂引起的调节。特别是硫或砷的掺杂可以有效地减少过电位，具有良好的结构稳定性和电化学稳定性。我们期望这项工作能够提供有用的见解，以指导可行策略的发展，以克服当前电化学CO2转化技术的局限性。
CO2 conversion is an essential technology to develop a sustainable carbon economy for the present and the future. Many studies have focused extensively on the electrochemical conversion of CO2 into various useful chemicals. However, there is not yet a solution of sufficiently high enough efficiency and stability to demonstrate practical applicability. In this work, we use first-principles-based high-throughput screening to propose silver-based catalysts for efficient electrochemical reduction of CO2 to CO while decreasing the overpotential by 0.4-0.5 V. We discovered the covalency-aided electrochemical reaction (CAER) mechanism in which p-block dopants have a major effect on the modulating reaction energetics by imposing partial covalency into the metal catalysts, thereby enhancing their catalytic activity well beyond modulations arising from d-block dopants. In particular, sulfur or arsenic doping can effectively minimize the overpotential with good structural and electrochemical stability. We expect this work to provide useful insights to guide the development of a feasible strategy to overcome the limitations of current technology for electrochemical CO2 conversion.