TY - JOUR
T1 - Stable, active CO2 reduction to formate via redox-modulated stabilization of active sites
AU - Li, Le
AU - Ozden, Adnan
AU - Guo, Shuyi
AU - Garcı́a de Arquer, F. Pelayo
AU - Wang, Chuanhao
AU - Zhang, Mingzhe
AU - Zhang, Jin
AU - Jiang, Haoyang
AU - Wang, Wei
AU - Dong, Hao
AU - Sinton, David
AU - Sargent, Edward H.
AU - Zhong, Miao
N1 - Funding Information:
This work was supported financially by the National Key R&D Program of China (No. 2020YFA0406102), the National Natural Science Foundation of China (grant number 91963121), the Natural Science Foundation of Jiangsu Province (Grant No. BK20190056), and the Frontiers Science Center for Critical Earth Material Cycling of Nanjing University. Parts of the calculations were performed using computational resources on an IBM Blade cluster system from the High-Performance Computing Center (HPCC) of Nanjing University. We thank Yimeng Min, Christine Gabardo, and Ziyun Wang for discussions during the study.
Publisher Copyright:
© 2021, The Author(s).
PY - 2021/12/1
Y1 - 2021/12/1
N2 - Electrochemical reduction of CO2 (CO2R) to formic acid upgrades waste CO2; however, up to now, chemical and structural changes to the electrocatalyst have often led to the deterioration of performance over time. Here, we find that alloying p-block elements with differing electronegativities modulates the redox potential of active sites and stabilizes them throughout extended CO2R operation. Active Sn-Bi/SnO2 surfaces formed in situ on homogeneously alloyed Bi0.1Sn crystals stabilize the CO2R-to-formate pathway over 2400 h (100 days) of continuous operation at a current density of 100 mA cm−2. This performance is accompanied by a Faradaic efficiency of 95% and an overpotential of ~ −0.65 V. Operating experimental studies as well as computational investigations show that the stabilized active sites offer near-optimal binding energy to the key formate intermediate *OCHO. Using a cation-exchange membrane electrode assembly device, we demonstrate the stable production of concentrated HCOO– solution (3.4 molar, 15 wt%) over 100 h.
AB - Electrochemical reduction of CO2 (CO2R) to formic acid upgrades waste CO2; however, up to now, chemical and structural changes to the electrocatalyst have often led to the deterioration of performance over time. Here, we find that alloying p-block elements with differing electronegativities modulates the redox potential of active sites and stabilizes them throughout extended CO2R operation. Active Sn-Bi/SnO2 surfaces formed in situ on homogeneously alloyed Bi0.1Sn crystals stabilize the CO2R-to-formate pathway over 2400 h (100 days) of continuous operation at a current density of 100 mA cm−2. This performance is accompanied by a Faradaic efficiency of 95% and an overpotential of ~ −0.65 V. Operating experimental studies as well as computational investigations show that the stabilized active sites offer near-optimal binding energy to the key formate intermediate *OCHO. Using a cation-exchange membrane electrode assembly device, we demonstrate the stable production of concentrated HCOO– solution (3.4 molar, 15 wt%) over 100 h.
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U2 - 10.1038/s41467-021-25573-9
DO - 10.1038/s41467-021-25573-9
M3 - Article
C2 - 34471135
AN - SCOPUS:85114192013
VL - 12
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 5223
ER -