Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene
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Yufang Liu1(
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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)-dual-doped graphene (TM-O2N2/G) for the electroreduction of nitrogen is intensively investigated. At low nitrogen coverage, W(Mo, Nb, Ta)-O2N2/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 N2 coverage, the TM-O2N2/G is reconstructed as TM-(N2)2N2/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)-(N2)2N2/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.
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Enhanced nitrogen electroreduction performance by the reorganization of local coordination environment of supported single atom on N(O)-dual-doped graphene
), Yufang Liu1(
)
Abstract
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)-dual-doped graphene (TM-O2N2/G) for the electroreduction of nitrogen is intensively investigated. At low nitrogen coverage, W(Mo, Nb, Ta)-O2N2/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 N2 coverage, the TM-O2N2/G is reconstructed as TM-(N2)2N2/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)-(N2)2N2/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.
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Acknowledgements
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), CAS Project for Young Scientists in Basic Research (No. YSBR-051), and 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).
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