<p>Electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) represents a sustainable approach to alleviate the global concern associated with excessive CO<sub>2</sub> emission. Recently, metal-based sulfides are emerged as a special class of electrocatalysts for efficient formate production, which however suffer from massive S loss during CO<sub>2</sub>RR due to the compositional reduction. Herein, we synthesize a series of tin sulfides with high crystallinity (i.e., SnS, Sn<sub>2</sub>S<sub>3</sub>, and SnS<sub>2</sub>) as model catalysts, and reveal that the strength distribution of Sn-S bonds in atomic configurations is essential for efficient formate production. Typically, the strong and uniformly distributed Sn-S bonds in SnS<sub>2</sub> are beneficial for inhibiting S leaching and forming favorable Sn/SnS<sub>2</sub> heterointerfaces for CO<sub>2</sub>RR, while the weaker Sn-S bonds in SnS promote the reduction into metallic Sn. Specially, the Sn<sub>2</sub>S<sub>3</sub> with mixed bonding strengths undergoes consecutive dissociation, starting from cleaving the weakest Sn-S bonds and then inducing accelerative reduction. Resultantly, the SnS<sub>2</sub> achieves the highest Faraday efficiency of 93.8%±0.59% at −1.0 V<sub>RHE</sub> and a high partial current density of 195.3 mA cm<sup>−2</sup> at −1.2 V<sub>RHE</sub>. This study could provide insight into the role of metal-sulfur bonds in catalysts for efficient CO<sub>2</sub>-to-formate conversion.</p>

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Strong and uniform Sn-S bond strength in tin sulfides-based electrocatalysts enables efficient CO2-to-formate conversion

  • Guoyu Hou,
  • Honghua Cui,
  • Yicheng Li,
  • Ya Liu,
  • Zhenyi Yang,
  • Ming Zhao,
  • Zhong-Zhen Luo,
  • Zhigang Zou,
  • Yu Zhang

摘要

Electrochemical CO2 reduction reaction (CO2RR) represents a sustainable approach to alleviate the global concern associated with excessive CO2 emission. Recently, metal-based sulfides are emerged as a special class of electrocatalysts for efficient formate production, which however suffer from massive S loss during CO2RR due to the compositional reduction. Herein, we synthesize a series of tin sulfides with high crystallinity (i.e., SnS, Sn2S3, and SnS2) as model catalysts, and reveal that the strength distribution of Sn-S bonds in atomic configurations is essential for efficient formate production. Typically, the strong and uniformly distributed Sn-S bonds in SnS2 are beneficial for inhibiting S leaching and forming favorable Sn/SnS2 heterointerfaces for CO2RR, while the weaker Sn-S bonds in SnS promote the reduction into metallic Sn. Specially, the Sn2S3 with mixed bonding strengths undergoes consecutive dissociation, starting from cleaving the weakest Sn-S bonds and then inducing accelerative reduction. Resultantly, the SnS2 achieves the highest Faraday efficiency of 93.8%±0.59% at −1.0 VRHE and a high partial current density of 195.3 mA cm−2 at −1.2 VRHE. This study could provide insight into the role of metal-sulfur bonds in catalysts for efficient CO2-to-formate conversion.