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Active Sites of Cobalt Phthalocyanine in Electrocatalytic CO2 Reduction to Methanol (in EN)

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [1];  [1];  [2];  [1];  [1];  [2];  [1];  [2];  [1]
  1. Yale Univ., New Haven, CT (United States)
  2. Oregon State Univ., Corvallis, OR (United States)
+ Show Author Affiliations
Many metal coordination compounds catalyze CO2 electroreduction to CO, but cobalt phthalocyanine hybridized with conductive carbon such as carbon nanotubes is currently the only one that can generate methanol. The underlying structure–reactivity correlation and reaction mechanism desperately demand elucidation. Here, in this study, we report the first in situ X-ray absorption spectroscopy characterization, combined with ex situ spectroscopic and electrocatalytic measurements, to study CoPc-catalyzed CO2 reduction to methanol. Molecular dispersion of CoPc on CNT surfaces, as evidenced by the observed electronic interaction between the two, is crucial to fast electron transfer to the active sites and multi-electron CO2 reduction. CO, the key intermediate in the CO2-to-methanol pathway, is found to be labile on the active site, which necessitates a high local concentration in the microenvironment to compete with CO2 for active sites and promote methanol production. A comparison of the electrocatalytic performance of structurally related porphyrins indicates that the bridging aza-N atoms of the Pc macrocycle are critical components of the CoPc active site that produces methanol. In situ X-ray absorption spectroscopy identifies the active site as Co(I) and supports an increasingly non-centrosymmetric Co coordination environment at negative applied potential, likely due to the formation of a Co−CO adduct during the catalysis.
Research Organization:
Yale Univ., New Haven, CT (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
FG02-07ER15909
Other Award/Contract Number:
CBET-2129963
CHE-1651717
CBET-2151049
OSTI ID:
2575820
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 2 Vol. 63; ISSN 1521-3773; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
EN

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