Room-temperature electrocatalytic nitrogen reduction reaction(NRR)is of paramount significance for the fertilizer industry and fundamental catalysis science.However,many NRR catalysts were based on the use of metals.H...Room-temperature electrocatalytic nitrogen reduction reaction(NRR)is of paramount significance for the fertilizer industry and fundamental catalysis science.However,many NRR catalysts were based on the use of metals.Herein,we focus on exploring boron-based,metal-free,efficient catalysts for NRR by den-sity functional theory calculations with van der Waals corrections(DFT+D3).Our results show that the NRR performance of the boron active site can be improved by tuning the N-coordination environment in a graphene sheet,and the B-N-C structures show excellent stability.By considering the correlation be-tween the Bader charges of the boron dopant over N-decorated graphene and their NRR activities,the ra-tional design principle of a boron-based catalyst for NRR is developed.The boron-site with one pyridinic nitrogen in a double-vacancy structure is found to be a highly active center,with low reaction energy(0.53 eV)and kinetic barrier(0.84 eV)through the distal mechanism.We also found that the charge loss of boron considerably hampers hydrogen adsorption,which in turn promotes the NRR efficiency by hin-dering the competing hydrogen evolution.This work offers new insights into developing low-cost,highly effective boron-based materials as promising electrocatalysts for green ammonia synthesis.展开更多
基金H.L.acknowledges the Center for Computational Materials Sci-ence,Institute for Materials Research,Tohoku University for the use of MASAMUNE-IMR(No.202212-SCKXX-0204)the In-stitute for Solid State Physics(ISSP)at the University of Tokyo for the use of their supercomputers+2 种基金the China BaoWu Low Carbon Metallurgical Innovation Foundation(No.BWLCF202113)the Fundamental Research Funds for the Cen-tral Universities(No.N2202012),JSPS KAKENHI(No.JP23K13703)the Iwatani Naoji Foundation.The authors thank the Beijing PARATERA Tech Co.,Ltd.for providing HPC resources.
文摘Room-temperature electrocatalytic nitrogen reduction reaction(NRR)is of paramount significance for the fertilizer industry and fundamental catalysis science.However,many NRR catalysts were based on the use of metals.Herein,we focus on exploring boron-based,metal-free,efficient catalysts for NRR by den-sity functional theory calculations with van der Waals corrections(DFT+D3).Our results show that the NRR performance of the boron active site can be improved by tuning the N-coordination environment in a graphene sheet,and the B-N-C structures show excellent stability.By considering the correlation be-tween the Bader charges of the boron dopant over N-decorated graphene and their NRR activities,the ra-tional design principle of a boron-based catalyst for NRR is developed.The boron-site with one pyridinic nitrogen in a double-vacancy structure is found to be a highly active center,with low reaction energy(0.53 eV)and kinetic barrier(0.84 eV)through the distal mechanism.We also found that the charge loss of boron considerably hampers hydrogen adsorption,which in turn promotes the NRR efficiency by hin-dering the competing hydrogen evolution.This work offers new insights into developing low-cost,highly effective boron-based materials as promising electrocatalysts for green ammonia synthesis.
