Thermal Transformation of Molecular Ni2+-N4 Sites for Enhanced CO2 Electroreduction Activity

Title
Thermal Transformation of Molecular Ni2+-N4 Sites for Enhanced CO2 Electroreduction Activity
Authors
황윤정사영진정혜진Dongyup ShinHu Young JeongStefan Ringe김형준주상훈
Issue Date
2020-10
Publisher
ACS catalysis
Citation
VOL 10-10931
Abstract
Atomically dispersed nickel sites complexed on nitrogen-doped carbon (Ni– N/C) have demonstrated considerable activity for the selective electrochemical carbon dioxide reduction reaction (CO2RR) to CO. However, the high-temperature treatment typically involved during the activation of Ni– N/C catalysts makes the origin of the high activity elusive. In this work, Ni(II) phthalocyanine molecules grafted on carbon nanotube (NiPc/CNT) and heat-treated NiPc/CNT (H-NiPc/CNT) are exploited as model catalysts to investigate the impact of thermal activation on the structure of active sites and CO2RR activity. H-NiPc/CNT exhibits a ∼4.7-fold higher turnover frequency for CO2RR to CO in comparison to NiPc/CNT. Extended X-ray absorption fine structure analysis and density functional theory (DFT) calculations reveal that the heat treatment transforms the molecular Ni2+– N4 sites of NiPc into Ni+– N3V (V: vacancy) and Ni+– N3 sites incorporated in the graphene lattice that concomitantly involves breakage of Ni– N bonding, shrinkage in the Ni– N– C local structure, and decrease in the oxidation state of the Ni center from +2 to +1. DFT calculations combined with microkinetic modeling suggest that the Ni– N3V site appears to be responsible for the high CO2RR activity because of its lower barrier for the formation of *COOH intermediate and optimum *CO binding energy. In situ/operando X-ray absorption spectroscopy analyses further corroborate the importance of reduced Ni+ species in boosting the CO2RR activity.
URI
http://pubs.kist.re.kr/handle/201004/71887
ISSN
2155-5435
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