Enhanced N_(2)electroreduction activity of single-atom catalysts:Modulating the linear scaling relationship by coordination engineering and dual-site strategies  

作　　者：Renyi Li Caimu Wang Jiao Zhang Wei Guo 

机构地区：[1]Centre for Quantum Physics,Key Laboratory of Advanced Optoelectronic Quantum Architecture and Measurement(MOE),School of Physics,Beijing Institute of Technology,Beijing 100081,China [2]Frontiers Science Center for High Energy Material(MOE),Beijing Institute of Technology,Beijing 100081,China

出　　处：《Nano Research》2025年第3期696-709,共14页纳米研究(英文版)

基　　金：financially supported by the National Natural Science Foundation of China(No.51971037).

摘　　要：The volcano plot is widely used to elucidate the activity trends among different catalysts,thereby effectively screening and guiding catalyst design.However,the inherent linear scaling relationship(LSR)constrains the breakthrough in the activity of catalysts,and the understanding of the activity limit in volcano plot is still ambiguous.In this work,by employing first-principles calculations and microkinetic modeling,we proposed coordination engineering(CE)and dual-site(DS)strategies to surpass the Sabatier’s limitation of WS_(2)-supported TM(TM@WS_(2))single-atom catalysts(SACs)for electrocatalytic nitrogen reduction reaction(eNRR).We found that the LSR betweenΔG(^(*)N_(2)→^(*)N_(2)H)andΔG(^(*)NH_(2)→^(*)NH_(3))was optimized to be closer to the ideal space of eNRR activity after modulating TM@WS_(2)SACs by these two design strategies.By combining the reaction selectivity trend plot,we picked out N-Os@WS_(2),C-Ir@WS_(2),Fe_(2)@WS_(2),and Ru_(2)@WS_(2)as optimal eNRR catalysts with low limiting potential(UL),and N-Os@WS_(2)SAC(UL:-0.28 V)outperforms the best eNRR catalyst among TM@WS_(2)SACs.By constructing explicit solvent models,we conducted a detailed study on the reaction kinetics of proton transfer over these four catalysts.We propose that the activity enhancement in TM@WS_(2)SACs for eNRR can be attributed to the ligand effect and geometric effect brought about by CE and DS strategies,improving the donation-backdonation process of electron transfer between N_(2)and the active sites.The designed catalyst has certain resistance to demetallization and agglomeration under simulated solvent environment.This work provides a feasible design strategy for the activity enhancement of SACs and brings a new perspective to deeply understanding the volcano plot in heterogeneous catalysis.

关 键 词：linear scaling relationship volcano plot single-atom catalysts density functional theory(DFT) electrochemical nitrogen reduction 

分 类 号：O64[理学—物理化学]