Cooperation between single atom catalyst and support to promote nitrogen electroreduction to ammonia:A theoretical insight  

作　　者：Wanying Guo Siyao Wang Hongxia Wang Qinghai Cai Jingxiang Zhao 

机构地区：[1]College of Chemistry and Chemical Engineering,Harbin Normal University,Harbin 150025,Heilongjiang,China

出　　处：《Journal of Energy Chemistry》2024年第9期336-344,共9页能源化学（英文版）

基　　金：financially supported in China by the Natural Science Funds for Distinguished Young Scholar of Heilongjiang Province (No. JC2018004)

摘　　要：The co-catalysis between single atom catalyst(SAC)and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions,encompassing multiple intermediates and pathways.Herein,we utilized defective BC_(3)monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction(NRR)for ammonia(NH_(3))production.The results showed that these SACs can be firmly stabilized on these defective BC_(3)supports with high stability against aggregation.Furthermore,co-activation of the inert N_(2)reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation.Our high-throughput screening revealed that the Mo/DV_(CC)and W/DV_(CC)exhibit superior NRR catalytic performance,characterized by a low limiting potential of−0.33 and−0.43 V,respectively,which can be further increased under acid conditions based on the constant potential method.Moreover,varying NRR catalytic activities can be attributed to the differences in the valence state of active sites.Remarkably,further microkinetic modeling analysis displayed that the turnover frequency of N_(2)–to–NH_(3)conversion on Mo/DV_(CC)is as large as 1.20×10^(−3)s^(−1)site^(−1) at 700 K and 100 bar,thus guaranteeing its ultra-fast reaction rate.Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.

关 键 词：CO-CATALYSIS Single atom catalyst Nitrogen reduction DFT computations 

分 类 号：TQ113.2[化学工程—无机化工] O643.36[理学—物理化学]