Ammonia Synthesis Using Single-Atom Catalysts Based on Two-Dimensional Organometallic Metal Phthalocyanine Monolayers under Ambient Conditions

Chun Xiang Huang, Guoliang Li, Li Ming Yang, Eric Ganz

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

We have identified three novel metal phthalocyanine (MPc, M = Mo, Re, and Tc) single-atom catalyst candidates with excellent predicted performance for the production of ammonia from electrocatalytic nitrogen reduction reaction (NRR) through a combination of high-throughput screening and first-principles calculations on a series of 3d, 4d, and 5d transition metals anchored onto extended Pc monolayer catalysts. Analysis of the energy band structures and projected density of states of N2-MPc revealed significant orbital hybridization and charge transfer between the adsorbed N2 and catalyst MPc, which accounts for the high catalytic activity. Among 30 MPc catalysts, MoPc and TcPc monolayers were found to be the most promising new NRR catalysts, as they exhibit excellent stability, low onset potential, and high selectivity. A comprehensive reaction pathway search found that the maximum free energy changes for the MoPc and TcPc monolayers are 0.33 and 0.54 eV, respectively. As a distinctive nature of this work, the hybrid reaction pathway was considered extensively and searched systematically. The onset potential of the hybrid pathway is found to be smaller than or comparable to that of the commonly known pure pathway. Thus, the hybrid path is highly competitive with low onset potential and high activity. The hybrid pathway is expected to have an important impact on future research on the mechanism of NRR, and it will open up a new way to explore the mechanism of the NRR reaction. We hope that our work will provide impetus to the creation of new catalysts for reduction of N2 to NH3. This work provides new insights into the rational design of NRR catalysts and explores novel reaction pathways under ambient or mild conditions.

Original languageEnglish (US)
Pages (from-to)608-621
Number of pages14
JournalACS Applied Materials and Interfaces
Volume13
Issue number1
DOIs
StatePublished - Jan 13 2021

Bibliographical note

Funding Information:
C.-X.H. and L.-M.Y. gratefully acknowledge the support from the National Natural Science Foundation of China (21673087, 21873032, 21903032, and 22073033), startup fund (2006013118 and 3004013105) from Huazhong University of Science and Technology, and the Fundamental Research Funds for the Central Universities (2019kfyRCPY116). C.-X.H. and G.L. are grateful for computational resources from the computing cluster at 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.

Funding Information:
C.-X.H. and L.-M.Y. gratefully acknowledge the support from the National Natural Science Foundation of China (21673087, 21873032 21903032, and 22073033), startup fund (2006013118 and 3004013105) from Huazhong University of Science and Technology, and the Fundamental Research Funds for the Central Universities (2019kfyRCPY116). C.-X.H. and G.L. are grateful for computational resources from the computing cluster at 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.

Publisher Copyright:
© 2020 American Chemical Society.

Keywords

  • electrocatalytic nitrogen reduction reaction
  • first-principles calculations
  • high-throughput screening
  • single-atom catalyst
  • two-dimensional materials

PubMed: MeSH publication types

  • Journal Article

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