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Research Article

Single-atom catalysts based on two-dimensional metalloporphyrin monolayers for ammonia synthesis under ambient conditions

Chun-Xiang Huang1,2, Sheng-Yao Lv1,2, Cong Li1, Bin Peng2, Guoliang Li2( ), Li-Ming Yang1( )
Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education; Hubei Key Laboratory of Materials Chemistry and Service Failure; Hubei Engineering Research Center for Biomaterials and Medical Protective Materials; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education; Center for Computational Quantum Chemistry, School of Chemistry, South China Normal University, Guangzhou 510006, China
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Graphical Abstract

Four novel metal porphyrin MPP (M = Zr, Nb, Hf and Re) single-atom catalyst candidates with excellent performance for ammonia (NH3) synthesis from electrocatalytic nitrogen reduction reaction (NRR) have been identified through a combination of four-step high-throughput screening and first-principles calculations on a series of 3d, 4d, and 5d transition metals anchored onto porphyrin substrates.

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.

Keywords

electrocatalytic nitrogen reduction reactiontwo-dimensional (2D) extended metalloporphyrin (MPP) monolayersingle-atom catalysttwo-dimensional materialshigh-throughput screeningfirst-principles calculations

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Nano Research
Volume 15 Issue 5,
May 2022
Pages 4039-4047
DOI: 10.1007/s12274-021-4009-4
Cite this article:
Huang C-X, Lv S-Y, Li C, et al. Single-atom catalysts based on two-dimensional metalloporphyrin monolayers for ammonia synthesis under ambient conditions. Nano Research, 2022, 15(5): 4039-4047. https://doi.org/10.1007/s12274-021-4009-4
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Received: 13 May 2021
Revised: 27 October 2021
Accepted: 21 November 2021
Published: 08 February 2022
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2021
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