Spin Polarization Enhanced Ethanol Selectivity in Electrocatalytic CO 2 Reduction on the Paramagnetic CuO Surface

Tao, Fujun [Northern Illinois University, DeKalb, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:000000031156842X); Wang, Jianxin [Northern Illinois University, DeKalb, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0009000204105240); Xu, Jiayi [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000317636251); Chen, Guangji [Angstrom Advanced Inc., Stoughton, MA (United States)]; Xiao, Xudong [Northern Illinois University, DeKalb, IL (United States)]; Li, Mengyuan [Northern Illinois University, DeKalb, IL (United States)] (ORCID:0009000725491781); Zhang, Haozhe [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000163635271); Zhou, Xinwei [Argonne National Laboratory (ANL), Argonne, IL (United States)]; Liu, Yuzi [Argonne National Laboratory (ANL), Argonne, IL (United States)]; Wostoupal, Owen S. [Northern Illinois University, DeKalb, IL (United States)] (ORCID:0000000247551569); Yang, Zhenzhen [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000210733799); Shi, Bing [Argonne National Laboratory (ANL), Argonne, IL (United States)]; Fry, H. Christopher [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000183435189); Pearson, John E. [Argonne National Laboratory (ANL), Argonne, IL (United States)]; Li, Haiming [Angstrom Advanced Inc., Stoughton, MA (United States)]; Zheng, Chong [Northern Illinois University, DeKalb, IL (United States)] (ORCID:000000023681305X); Liu, Cong [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000221455034); Liu, Di-Jia [Argonne National Laboratory (ANL), Argonne, IL (United States); University of Chicago, IL (United States)] (ORCID:000000031747028X); Xu, Tao [Northern Illinois University, DeKalb, IL (United States)] (ORCID:0000000233437263)

doi:10.1021/jacs.6c05085

DOE OSTI · 3367687

Spin Polarization Enhanced Ethanol Selectivity in Electrocatalytic CO 2 Reduction on the Paramagnetic CuO Surface

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Abstract

We report an electrochemical CO 2 reduction reaction catalyzed by a paramagnetic and conductive CuO/Cu interface with spins polarized by a moderate external magnetic field (MF) of similar to 800 gauss, achieving a similar to 30% increase in CO 2 -to-C 2+ Faradaic efficiency (FE) compared to that in the absence of the MF in a flow cell electrolyzer. At a current density of 400 mA/cm 2 , the CO 2 -to-C 2+ FE reached 86.7 ± 2.7% with 47.9 ± 1.4% cathodic energy efficiency (EE) in contrast to the CO 2 -to-C 2+ FE of 67.6% with 36.4% of EE in the absence of MF. Notably, ethanol production exhibits a much higher response to the MF (similar to 55.6% increase in FE) than ethylene (similar to 6.4% increase in FE) at 400 mA/cm 2 . In situ surface-enhanced Raman spectroscopy (SERS) captured magnetic-field-enhanced *CO coverage and ethanol-forming C 2 intermediates on CuO/Cu, providing direct spectroscopic evidence of spin-modulated pathway selection. Here, computational study suggests that the enhancement of ethanol selectivity is due to the reduced reaction kinetic barrier under MF, while the ethylene selectivity is less affected, mainly due to the insensitivity of the kinetic barriers under MF.

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10 SYNTHETIC FUELS 25 ENERGY STORAGE 36 MATERIALS SCIENCE Electrical properties Electrolyzer, electrocatalysis, CO2 conversion, magnetic field, paramagnetic catalysts, spin polarization Ethanol Inorganic carbon compounds Magnetic properties Oxides

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Tao, Fujun [Northern Illinois University, DeKalb, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:000000031156842X), Wang, Jianxin [Northern Illinois University, DeKalb, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0009000204105240), Xu, Jiayi [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000317636251), Chen, Guangji [Angstrom Advanced Inc., Stoughton, MA (United States)], Xiao, Xudong [Northern Illinois University, DeKalb, IL (United States)], Li, Mengyuan [Northern Illinois University, DeKalb, IL (United States)] (ORCID:0009000725491781), Zhang, Haozhe [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000163635271), Zhou, Xinwei [Argonne National Laboratory (ANL), Argonne, IL (United States)], Liu, Yuzi [Argonne National Laboratory (ANL), Argonne, IL (United States)], Wostoupal, Owen S. [Northern Illinois University, DeKalb, IL (United States)] (ORCID:0000000247551569), Yang, Zhenzhen [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000210733799), Shi, Bing [Argonne National Laboratory (ANL), Argonne, IL (United States)], Fry, H. Christopher [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000183435189), Pearson, John E. [Argonne National Laboratory (ANL), Argonne, IL (United States)], Li, Haiming [Angstrom Advanced Inc., Stoughton, MA (United States)], Zheng, Chong [Northern Illinois University, DeKalb, IL (United States)] (ORCID:000000023681305X), Liu, Cong [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000221455034), Liu, Di-Jia [Argonne National Laboratory (ANL), Argonne, IL (United States); University of Chicago, IL (United States)] (ORCID:000000031747028X), Xu, Tao [Northern Illinois University, DeKalb, IL (United States)] (ORCID:0000000233437263). 2026-05-07. Spin Polarization Enhanced Ethanol Selectivity in Electrocatalytic CO 2 Reduction on the Paramagnetic CuO Surface. https://doi.org/10.1021/jacs.6c05085

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