Journal
APPLIED CATALYSIS B-ENVIRONMENTAL
Volume 290, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.apcatb.2021.120067
Keywords
Co-based molecular catalysts; Spin state; CO2 electroreduction; CO2 activation
Funding
- National Science Fund for Distinguished Young Scholars [21925204]
- NSFC [U1932146, U19A2015]
- National Key Research and Development Program of China [2019YFA0405600]
- Key Research Program of Frontier Sciences of the CAS [QYZDB-SSW-SLH017]
- Fundamental Research Funds for the Central Universities
- USTC Research Funds of the Double First-Class Initiative [YD2340002002]
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The high-spin state of Co2+ facilitated CO2 activation over Co-salophen-X, with Co-salophen-Br exhibiting the highest Faradaic efficiency for CO at 98.5%. Density functional theory calculations revealed that the high-spin state of Co sites decreased the reaction energy barrier for CO formation.
A typical mode of CO2 activation is that d electrons at the d orbital of transition metals transfer to the unoccupied pi* orbital of CO2. Thus the exploration of the relationship between d-electron behaviors and CO2 activation is of great importance. Herein, we demonstrate that high-spin state of 3d electrons in Co2+ facilitated the activation of CO2 over Co-salophen-X (X represents to Cl, Br, or I). Among these catalysts, Co-salophen-Br exhibited the highest Faradaic efficiency for CO. Notably, the Faradaic efficiency for CO over Co-salophen-Br reached 98.5 % at -0.70 V versus reversible hydrogen electrode, which was 1.5 and 1.2 times as high as those over Co-salophen-Cl (64.8 %) and Co-salophen-I (81.8 %), respectively. Density functional theory calculations revealed that high-spin state of Co sites decreased the reaction energy barrier for the formation of CO. Based on the analysis of electronic state, the ratio of high-spin state was 65.6 % for Co-salophen-Br, which was the highest among the three Co-based molecules. The Co sites with high-spin state promoted the electron transfer from high-energy 3d orbital (3d(z2) and 3d(x2-y2)) of Co to the unoccupied pi* orbital of CO2, improving catalytic performance.
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