TY - JOUR
T1 - Sulfur-doping tunes p-d orbital coupling over asymmetric Zn-Sn dual-atom for boosting CO2 electroreduction to formate
AU - Peng, Bo
AU - She, Hao
AU - Wei, Zihao
AU - Sun, Zhiyi
AU - Deng, Ziwei
AU - Sun, Zhongti
AU - Chen, Wenxing
N1 - Publisher Copyright:
© The Author(s) 2025.
PY - 2025/12
Y1 - 2025/12
N2 - The interaction of p-d orbitals at bimetallic sites plays a crucial role in determining the catalytic reactivity, which facilitates the modulation of charges and enhances the efficiency of CO2 electroreduction process. Here, we show a ligand co-etching approach to create asymmetric Zn-Sn dual-atom sites (DASs) within metal-organic framework (MOF)-derived yolk-shell carbon frameworks (named Zn1Sn1/SNC). The DASs comprise one Sn center (p-block) partially doped with sulfur and one Zn center (d-block) with N coordination, facilitating the coupling of p-d orbitals between the Zn-Sn dimer. The N-Zn-Sn-S/N arrangement displays an asymmetric distribution of charges and atoms, leading to a stable adsorption configuration of HCOO* intermediates. In H-type cell, Zn1Sn1/SNC exhibits an impressive formate Faraday efficiency of 94.6% at -0.84 V. In flow cell, the asymmetric electronic architecture of Zn1Sn1/SNC facilitates high accessibility, leading to a high current density of -315.2 mA cm-2 at -0.90 V. Theoretical calculations show the asymmetric sites in Zn1Sn1/SNC with ideal adsorption affinity lower the CO2 reduction barrier, thus improve the overall efficiency of CO2 reduction.
AB - The interaction of p-d orbitals at bimetallic sites plays a crucial role in determining the catalytic reactivity, which facilitates the modulation of charges and enhances the efficiency of CO2 electroreduction process. Here, we show a ligand co-etching approach to create asymmetric Zn-Sn dual-atom sites (DASs) within metal-organic framework (MOF)-derived yolk-shell carbon frameworks (named Zn1Sn1/SNC). The DASs comprise one Sn center (p-block) partially doped with sulfur and one Zn center (d-block) with N coordination, facilitating the coupling of p-d orbitals between the Zn-Sn dimer. The N-Zn-Sn-S/N arrangement displays an asymmetric distribution of charges and atoms, leading to a stable adsorption configuration of HCOO* intermediates. In H-type cell, Zn1Sn1/SNC exhibits an impressive formate Faraday efficiency of 94.6% at -0.84 V. In flow cell, the asymmetric electronic architecture of Zn1Sn1/SNC facilitates high accessibility, leading to a high current density of -315.2 mA cm-2 at -0.90 V. Theoretical calculations show the asymmetric sites in Zn1Sn1/SNC with ideal adsorption affinity lower the CO2 reduction barrier, thus improve the overall efficiency of CO2 reduction.
UR - http://www.scopus.com/inward/record.url?scp=86000042820&partnerID=8YFLogxK
U2 - 10.1038/s41467-025-57573-4
DO - 10.1038/s41467-025-57573-4
M3 - Article
C2 - 40044667
AN - SCOPUS:86000042820
SN - 2041-1723
VL - 16
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 2217
ER -