Developing stable and efficient catalysts for the electroreduction of nitrogen remains a huge challenge and single atom catalysts(SACs)are expected to achieve relatively high ammonia selectivity at low applied potenti...Developing stable and efficient catalysts for the electroreduction of nitrogen remains a huge challenge and single atom catalysts(SACs)are expected to achieve relatively high ammonia selectivity at low applied potential.Based on density functional theory calculations,the potential application of 27 single transition metal(TM=Sc-Zn,Y-Ag,Hf-Au)atoms supported by N(O)-dualdoped graphene(TM-O_(2)N_(2)/G)for the electroreduction of nitrogen is intensively investigated.At low nitrogen coverage,W(Mo,Nb,Ta)-O_(2)N_(2)/G are predicted to yield low ammonia selectivity(<13%)at limiting-potential of-0.58,-0.53,-0.56,and-0.76 V starting from adsorbed nitrogen with side-on mode,respectively.With the increasing N_(2)coverage,the TM-O_(2)N_(2)/G is reconstructed as TM-(N_(2))2N_(2)/graphene.The electroreduction of nitrogen proceeds from end-on adsorbed nitrogen molecule with high ammonia selectivity,and the limiting-potentials are theoretically predicted as-0.20,-0.40,-0.29,and-0.21 V on W(Mo,Nb,Ta)-(N_(2))2N_(2)/G,respectively.It is suggested that utilizing the reorganization of local coordination environments of SACs by high coverage of reactant molecules under reaction condition can not only enhance the activity at lower limiting-potential but also improve the ammonia selectivity.展开更多
基金This work is partially supported by the National Key Research and Development Program of China(No.2018YFA0208600)the National Natural Science Foundation of China(Nos.U19A2015 and 11974103)+2 种基金CAS Project for Young Scientists in Basic Research(No.YSBR-051)Zhongyuan Scholar of Henan Province(No.224000510007)Wenhua Zhang is supported by USTC Tang Scholarship,and the calculations are performed on the High Performance Computing Center of Henan Normal University and the supercomputing center of the University of Science and Technology of China(No.USTC-SCC).
文摘Developing stable and efficient catalysts for the electroreduction of nitrogen remains a huge challenge and single atom catalysts(SACs)are expected to achieve relatively high ammonia selectivity at low applied potential.Based on density functional theory calculations,the potential application of 27 single transition metal(TM=Sc-Zn,Y-Ag,Hf-Au)atoms supported by N(O)-dualdoped graphene(TM-O_(2)N_(2)/G)for the electroreduction of nitrogen is intensively investigated.At low nitrogen coverage,W(Mo,Nb,Ta)-O_(2)N_(2)/G are predicted to yield low ammonia selectivity(<13%)at limiting-potential of-0.58,-0.53,-0.56,and-0.76 V starting from adsorbed nitrogen with side-on mode,respectively.With the increasing N_(2)coverage,the TM-O_(2)N_(2)/G is reconstructed as TM-(N_(2))2N_(2)/graphene.The electroreduction of nitrogen proceeds from end-on adsorbed nitrogen molecule with high ammonia selectivity,and the limiting-potentials are theoretically predicted as-0.20,-0.40,-0.29,and-0.21 V on W(Mo,Nb,Ta)-(N_(2))2N_(2)/G,respectively.It is suggested that utilizing the reorganization of local coordination environments of SACs by high coverage of reactant molecules under reaction condition can not only enhance the activity at lower limiting-potential but also improve the ammonia selectivity.
