Quasi-Covalently Coupled Ni-Cu Atomic Pair for Synergistic Electroreduction of CO2.
Quasi-Covalently Coupled Ni-Cu Atomic Pair for Synergistic Electroreduction of CO2.
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DOI：
10.1021/jacs.2c00937
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发表时间：
2022-05
影响因子：
15
通讯作者：
Jianbing Zhu;Meiling Xiao;Dezhang Ren;Rui Gao;Xiaozhi Liu;Zhen Zhang;Dan Luo;Wei Xing;Dong Su;A. Yu;Zhongwei Chen
中科院分区：
文献类型：
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作者：
Jianbing Zhu;Meiling Xiao;Dezhang Ren;Rui Gao;Xiaozhi Liu;Zhen Zhang;Dan Luo;Wei Xing;Dong Su;A. Yu;Zhongwei Chen
为二氧化碳还原反应（CO2RR）开发高活性、选择性和稳定性的电催化剂是建立可工业化实施的二氧化碳转化体系，从而实现人工闭环的关键。这只能通过基于分子尺度上的操作活性位点知识的合理材料设计来实现。在理论筛选的启发下，我们首次操纵了一种新的Ni-Cu原子对构型，以提高CO2RR性能。系统表征和理论建模表明，二次Cu金属的加入使Ni三维轨道能量正向移动到费米能级，从而加速了速率决定步骤*COOH的形成。此外，Cu对竞争性析氢反应的固有不活性对Ni-Cu部分上的水解离造成了相当大的反应屏障。由于这些特性，所开发的Ni/Cu-N-C催化剂表现出优异的催化活性和选择性，在-0.6 V （vs RHE）下具有创纪录的20,695 h-1的周转率和97.7%的CO生成法拉第效率。此外，operando x射线吸收精细结构光谱监测的动态结构演变揭示了Ni中心与CO2分子之间的相互作用以及Ni- cu原子对对CO2RR活性的协同作用。
Developing highly active, selective, and stable electrocatalysts for the carbon dioxide reduction reaction (CO2RR) is crucial to establish a CO2 conversion system for industrial implementation and, therefore, to realize an artificially closed carbon loop. This can only be achieved through the rational material design based upon the knowledge of the operational active site at the molecular scale. Enlightened by theoretical screening, herein, we for the first time manipulate a novel Ni-Cu atomic pair configuration toward improved CO2RR performance. Systematic characterizations and theoretical modeling reveal that the secondary Cu metal incorporation positively shifts the Ni 3d orbital energy to the Fermi level and thus accelerates the rate-determining step, *COOH formation. In addition, the intrinsic inactivity of Cu toward the competing hydrogen evolution reaction causes a considerable reaction barrier for water dissociation on the Ni-Cu moiety. Due to these attributes, the as-developed Ni/Cu-N-C catalyst exhibits excellent catalytic activity and selectivity, with a record-high turnover frequency of 20,695 h-1 at -0.6 V (vs RHE) and a maximum Faradaic efficiency of 97.7% for CO production. Furthermore, the dynamic structure evolution monitored by operando X-ray absorption fine-structure spectroscopy unveils the interaction between the Ni center and CO2 molecules and the synergistic effect of the Ni-Cu atomic pair on CO2RR activity.