The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction
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电荷积累和自旋极化在活性炭基电催化氮还原催化剂中的关键作用
DOI：
10.1002/ange.201915001
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发表时间：
2020
影响因子：
--
通讯作者：
Shi‐Zhang Qiao
中科院分区：
文献类型：
--
作者：
Yuanyuan Yang;Lifu Zhang;Zhenpeng Hu;Yao Zheng;Cheng Tang;Ping Chen;Ruguang Wang;Kangwen Qiu;Jing Mao;Tao Ling;Shi‐Zhang Qiao
具有成本效益的碳基催化剂有望用于催化电化学N2还原反应（NRR）。然而，碳基催化剂对NRR的活性起源仍然不清楚，并且仍然缺乏合理设计碳基NRR电催化剂的方法和规则。基于理论计算和实验观察相结合，硫族/氧族元素（O，S，Se，Te）掺杂的碳材料作为潜在的NRR催化剂进行了系统的评价。杂原子掺杂诱导的电荷积累促进了N2在碳原子上的吸附，并且自旋极化增强了第一质子化形成 *NNH的电位决定步骤。Te掺杂和Se掺杂的C催化剂表现出高的固有NRR活性，其上级于大多数金属基催化剂。建立碳基材料的电子结构与NRR性能之间的相关性为其NRR应用铺平了道路。
Cost‐effective carbon‐based catalysts are promising for catalyzing the electrochemical N2reduction reaction (NRR). However, the activity origin of carbon‐based catalysts towards NRR remains unclear, and regularities and rules for the rational design of carbon‐based NRR electrocatalysts are still lacking. Based on a combination of theoretical calculations and experimental observations, chalcogen/oxygen group element (O, S, Se, Te) doped carbon materials were systematically evaluated as potential NRR catalysts. Heteroatom‐doping‐induced charge accumulation facilitates N2adsorption on carbon atoms and spin polarization boosts the potential‐determining step of the first protonation to form *NNH. Te‐doped and Se‐doped C catalysts exhibited high intrinsic NRR activity that is superior to most metal‐based catalysts. Establishing the correlation between the electronic structure and NRR performance for carbon‐based materials paves the pathway for their NRR application.