Single-atom catalysts based on two-dimensional metalloporphyrin monolayers for ammonia synthesis under ambient conditions
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Li-Ming Yang1(
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We systematically investigated the catalytic performance of 3d, 4d, and 5d transition metals anchored onto two-dimensional extended porphyrin (PP) substrates as nitrogen reduction reaction (NRR) electrocatalysts, employing density functional theory (DFT) calculations and four-step high-throughput screening. Four novel metalloporphyrin (MPP, M = Zr, Nb, Hf, and Re) single-atom catalyst candidates have been identified due to their excellent catalytic performance (low onset potential, high stability, and selectivity). Through comprehensive reaction path search, the maximum Gibbs free energy changes for NRR on the ZrPP (enzymatic-consecutive hybrid path), NbPP (consecutive path), HfPP (enzymatic-consecutive hybrid path), and RePP (distal path) catalysts are 0.38, 0.41, 0.53, and 0.53 eV, respectively. Band structures, projected density of states, and charge/spin distributions show that the high catalytic activity is due to significant orbital hybridizations and charge transfer between N2 and MPP catalysts. We hope our work will promote experimental synthesis of these NRR electrocatalysts and provide new opportunities to the electrochemical conversion of N2 to NH3 under ambient conditions.
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Single-atom catalysts based on two-dimensional metalloporphyrin monolayers for ammonia synthesis under ambient conditions
), Li-Ming Yang1(
)
Abstract
We systematically investigated the catalytic performance of 3d, 4d, and 5d transition metals anchored onto two-dimensional extended porphyrin (PP) substrates as nitrogen reduction reaction (NRR) electrocatalysts, employing density functional theory (DFT) calculations and four-step high-throughput screening. Four novel metalloporphyrin (MPP, M = Zr, Nb, Hf, and Re) single-atom catalyst candidates have been identified due to their excellent catalytic performance (low onset potential, high stability, and selectivity). Through comprehensive reaction path search, the maximum Gibbs free energy changes for NRR on the ZrPP (enzymatic-consecutive hybrid path), NbPP (consecutive path), HfPP (enzymatic-consecutive hybrid path), and RePP (distal path) catalysts are 0.38, 0.41, 0.53, and 0.53 eV, respectively. Band structures, projected density of states, and charge/spin distributions show that the high catalytic activity is due to significant orbital hybridizations and charge transfer between N2 and MPP catalysts. We hope our work will promote experimental synthesis of these NRR electrocatalysts and provide new opportunities to the electrochemical conversion of N2 to NH3 under ambient conditions.
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Acknowledgements
C.-X. H., S.-Y. L., C. L., and L.-M. Y. gratefully acknowledge support from the National Natural Science Foundation of China (Nos. 22073033, 21873032, 21673087, and 21903032), the startup fund (Nos. 2006013118 and 3004013105) from Huazhong University of Science and Technology, the Fundamental Research Funds for the Central Universities (No. 2019kfyRCPY116), and the Innovation and Talent Recruitment Base of New Energy Chemistry and Device (B21003). C.-X. H., S.-Y. L., and G.-L. L. gratefully acknowledge support from Guangdong Basic and Applied Basic Research Foundation (No. 2021A1515010382). This work was carried out at the computing clusters of the Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education & School of Chemistry, South China Normal University. The work was carried out at the LvLiang Cloud Computing Center of China, and the calculations were performed on TianHe-2. The computing work in this paper is supported by the Public Service Platform of High Performance Computing by Network and Computing Center of HUST.
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