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In-Silico Screening the Nitrogen Reduction Reaction on Single-Atom Electrocatalysts Anchored on MoS2

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Abstract

We show that a Single-Atom Electrocatalyst (SAC) for the Nitrogen Reduction Reaction (NRR) can provide an environmentally green alternative to the Haber–Bosch high-temperature high-pressure process, replacing the water gas shift production of H2 with H extracted from water. Anchoring the single atom on a two-dimensional substrate provides control to tune NRR catalytic performance toward a SAC possessing high utilization, high activity, and high selectivity. Experimental results suggest that this can significantly improve the activity and selectivity of NRR, but the specific reaction mechanism remains uncertain. This makes it difficult to select new catalytic materials for further optimization. Here we use Density Functional Theory to study the NRR catalytic mechanism on a catalytic model using a MoS2 substrate to support a single atom site. We correct for solvation effects on the electrochemical reactions. We started with Fe@MoS2, for which there are promising experimental reports, and conducted a systematic study of the NRR reaction mechanisms. These results show that N2 adsorption, hydrogenation of N2, desorption of NH3, and Hydrogen Evolution are all critical steps affecting the reaction rates. Based on these steps, we scanned 23 transition metal elements to find improved catalysts. We identified Ir@MoS2 (Mo top site) as the best candidate, predicted to have good catalytic activity and selectivity with 64.11% Faraday Efficiency. These results on the mechanism for NRR and the in silico search for alternative catalysts provide new promising targets for synthesizing novel and efficient SAC@MoS2 NRR catalysts.

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Acknowledgements

TC thanks to the National Natural Science Foundation of China (21903058), the Natural Science Foundation of Jiangsu Higher Education Institutions (SBK20190810), the Jiangsu Province High-Level Talents (JNHB-106), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) for financial support. HY thanks China Postdoctoral Science Foundation (2019M660128) for financial support. This work was partly supported by the Collaborative Innovation Center of Suzhou Nano Science & Technology. WAG thanks NSF (CBET-2005250) for support.

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Authors and Affiliations

  1. Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou, 215123, China

    Liang Xu, Miao Xie, Hao Yang, Peiping Yu, Bingyun Ma & Tao Cheng

  2. Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, 91125, USA

    William A. Goddard III

Authors
  1. Liang Xu
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  2. Miao Xie
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  3. Hao Yang
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  4. Peiping Yu
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  5. Bingyun Ma
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  6. Tao Cheng
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  7. William A. Goddard III
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Correspondence to Tao Cheng or William A. Goddard III.

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Xu, L., Xie, M., Yang, H. et al. In-Silico Screening the Nitrogen Reduction Reaction on Single-Atom Electrocatalysts Anchored on MoS2. Top Catal 65, 234–241 (2022). https://doi.org/10.1007/s11244-021-01546-6

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  • DOI: https://doi.org/10.1007/s11244-021-01546-6

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