催化作用
吸附
镍
选择性
氧化还原
过渡金属
密度泛函理论
活动站点
Atom(片上系统)
化学
材料科学
无机化学
结晶学
计算化学
物理化学
有机化学
嵌入式系统
计算机科学
作者
Mengbo Ma,Fuhua Li,Qing Tang
出处
期刊:Nanoscale
[The Royal Society of Chemistry]
日期:2021-01-01
卷期号:13 (45): 19133-19143
被引量:28
摘要
Coordination engineering has recently emerged as a promising strategy to boost the activity of single atom catalysts (SACs) in electrocatalytic CO2 reduction reactions (CO2RR). Understanding the correlation between activity/selectivity and the coordination environment would enable the rational design of more advanced SACs for CO2 reduction. Herein, via density functional theory (DFT) computations, we systematically studied the effects of coordination environment regulation on the CO2RR activity of Ni SACs on C, N, or B co-doped graphene. The results reveal that the coordination environments can strongly affect the adsorption and reaction characteristics. In the C and/or N coordinated Ni-BXCYNZ (B-free, X = 0), only Ni acts as the active site. While in the B, C and/or N coordinated Ni-BXCYNZ (X ≠ 0), the B has transition-metal-like properties, where B and Ni function as dual-site active centers and concertedly tune the adsorption of CO2RR intermediates. The tunability in the adsorption modes and strengths also results in a weakened linear scaling relationship between *COOH and *CO and causes a significant activity difference. The CO2RR activity and the adsorption energy of *COOH/*CO are correlated to construct a volcano-type activity plot. Most of the B, C, and/or N-coordinated Ni-BXCYNZ (X ≠ 0) are located in the left region where *CO desorption is the most difficult step, while the C and/or N coordinated Ni-BXCYNZ (X = 0) are located in the right region where *COOH formation is the potential-determining step. Among all the possible Ni-BXCYNZ candidates, Ni-B0C3N1 and Ni-B1C1N2-N-oppo are predicted to be the most active and selective catalysts for the CO2RR. Our findings provide insightful guidance for developing highly effective CO2RR catalysts based on a codoped coordination environment.
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