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<p>Tandem systems that integrate CO-generating catalysts with copper have shown promise for enhanced carbon dioxide reduction reaction (CO<sub>2</sub>RR) performance. Sulfur-containing single-atom catalysts are particularly effective for CO production; however, the role and positioning of sulfur in facilitating both CO<sub>2</sub>-to-CO conversion and tandem CO<sub>2</sub>RRs remain elusive. Here we show model thiophene-decorated nickel porphyrins as model single-atom catalysts that exhibit tandem activities in the CO<sub>2</sub>RR. Spectroscopic and theoretical analyses reveal that thiophene substituents induce ligand holes, regulating the <i>d</i> orbitals and <i>d</i>-band centre of the nickel centre to reduce the reaction barrier and promote CO formation. Coupling these single-atom catalysts with a copper catalyst achieves a Faradaic efficiency of 74.3% and a partial current density of 445.8 mA cm<sup>−2</sup> for C<sub>2</sub> products in a neutral solution, a 46% improvement over bare copper. Operando studies confirm the formation of CO intermediates from the single-atom catalysts, highlighting their role in facilitating tandem catalysis.</p><p></p>

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Model thiophene-decorated nickel porphyrins for tandem CO2 reduction

  • 期刊论文

  • 发表日期：

    2025年10月9日

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  • Yi-Hsuan Lu,
  • Yu-Jhih Shen,
  • Hsin-Jung Tsai,
  • Yen-Hua Lee,
  • Yong-Yi Huang,
  • Zih-Yi Lin,
  • Wen-Yang Huang,
  • Tsung-Ju Lee,
  • Guan-Lin Chen,
  • Nozomu Hiraoka,
  • Hirofumi Ishii,
  • Hsueh-Ju Liu,
  • Shao-Hui Hsu,
  • Chun-Chih Chang,
  • Aoni Xu,
  • Sung-Fu Hung

摘要

Tandem systems that integrate CO-generating catalysts with copper have shown promise for enhanced carbon dioxide reduction reaction (CO2RR) performance. Sulfur-containing single-atom catalysts are particularly effective for CO production; however, the role and positioning of sulfur in facilitating both CO2-to-CO conversion and tandem CO2RRs remain elusive. Here we show model thiophene-decorated nickel porphyrins as model single-atom catalysts that exhibit tandem activities in the CO2RR. Spectroscopic and theoretical analyses reveal that thiophene substituents induce ligand holes, regulating the d orbitals and d-band centre of the nickel centre to reduce the reaction barrier and promote CO formation. Coupling these single-atom catalysts with a copper catalyst achieves a Faradaic efficiency of 74.3% and a partial current density of 445.8 mA cm−2 for C2 products in a neutral solution, a 46% improvement over bare copper. Operando studies confirm the formation of CO intermediates from the single-atom catalysts, highlighting their role in facilitating tandem catalysis.