Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance

Lijuan Zhang; Hanfeng Zhou; Xiaoju Yang; Shengbo Zhang; Haimin Zhang; Xuan Yang; Xintai Su; Jiangwei Zhang; Zhang Lin

doi:10.1002/anie.202217473

Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Atomically Dispersed Sn Protuberance

Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202217473. doi: 10.1002/anie.202217473. Epub 2023 Feb 20.

Authors

Lijuan Zhang^{1

2}, Hanfeng Zhou¹, Xiaoju Yang³, Shengbo Zhang⁴, Haimin Zhang⁴, Xuan Yang³, Xintai Su¹, Jiangwei Zhang⁵, Zhang Lin¹

Affiliations

¹ School of Environment and Energy, Guangdong Provincial Key Laboratory of Solid Wastes Pollution Control and Recycling, South China University of Technology, Guangzhou, Guangdong, 510006, P. R. China.
² SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Theoretical Chemistry of Environment, South China Normal University, Guangzhou, 510006, China.
³ School of Chemistry and Chemical Engineering, Hubei Engineering Research Center for Biomaterials and Medical Protective Materials, Huazhong University of Science and Technology (HUST), 1037 Luoyu Rd, Wuhan, 430074, China.
⁴ Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences (China).
⁵ Science Center of Energy Material and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, China.

PMID: 36738169
DOI: 10.1002/anie.202217473

Abstract

Atomically dispersed metal catalysts show potential advantages in N₂ reduction reaction (NRR) due to their excellent activity and efficient metal utilization. Unfortunately, the reported catalysts usually exhibit unsatisfactory NRR activity due to their poor N₂ adsorption and activation. Herein, we report a novel Sn atomically dispersed protuberance (ADP) by coordination with substrate C and O to induce positive charge accumulation on Sn site for improving its N₂ adsorption, activation and NRR performance. The extended X-ray absorption fine structure (EXAFS) spectra confirmed the local coordination structure of the Sn ADPs. NRR activity was significantly promoted via Sn ADPs, exhibiting a remarkable NH₃ yield (R_NH3 ) of 28.3 μg h^-1 mg_cat ^-1 (7447 μg h^-1 mg_Sn ^-1 ) at -0.3 V. Furthermore, the enhanced N₂ H_x intermediates was verified by in situ experiments, yielding consistent results with DFT calculation. This work opens a new avenue to regulate the activity and selectivity of N₂ fixation.

Keywords: Atomically Dispersed Sn; Hydrogen Evolution Suppression; Main-Group Elements (MGEs); N2 Reduction Reaction; p-Electron Backdonation.

Abstract

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