Local Spin-State Tuning of Iron Single-Atom Electrocatalyst by S-Coordinated Doping for Kinetics-Boosted Ammonia Synthesis

Li Y, Ji Y, Zhao Y, Chen J, Zheng S, Sang X, Yang B, Li Z, Lei L, Wen Z, Feng X, Hou Y (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Advanced Materials Wiley

Book Volume: 34

Article Number: 2202240

Journal Issue: 28

DOI: 10.1002/adma.202202240

Abstract

The electrochemical nitrogen reduction reaction (e-NRR) is envisaged as alternative technique to the Haber–Bosch process for NH3 synthesis. However, how to develop highly active e-NRR catalysts faces daunting challenges. Herein, a viable strategy to manipulate local spin state of isolated iron sites through S-coordinated doping (FeSA-NSC) is reported. Incorporation of S in the coordination of FeSA-NSC can induce the transition of spin-polarization configuration with the formation of a medium-spin-state of Fe (t2g6 eg1), which is beneficial for facilitating eg electrons to penetrate the antibonding π-orbital of nitrogen. As a consequence, a record-high current density up to 10 mA cm−2 can be achieved, together with a high NH3 selectivity of ≈10% in a flow cell reactor. Both experimental and theoretical analyses indicate that the monovalent Fe(I) atomic center in the FeSA-NSC after the S doping accelerates the N2 activation and protonation in the rate-determining step of *N2 to *NNH.

Involved external institutions

Zhejiang University CN China (CN) Wuhan University of Technology CN China (CN) Chinese Academy of Sciences (CAS) / 中国科学院 CN China (CN) Technische Universität Dresden DE Germany (DE)

How to cite

APA:

Li, Y., Ji, Y., Zhao, Y., Chen, J., Zheng, S., Sang, X.,... Hou, Y. (2022). Local Spin-State Tuning of Iron Single-Atom Electrocatalyst by S-Coordinated Doping for Kinetics-Boosted Ammonia Synthesis. Advanced Materials, 34(28). https://doi.org/10.1002/adma.202202240

MLA:

Li, Yan, et al. "Local Spin-State Tuning of Iron Single-Atom Electrocatalyst by S-Coordinated Doping for Kinetics-Boosted Ammonia Synthesis." Advanced Materials 34.28 (2022).

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