Highly efficient electrocatalytic CO2 reduction by a CrIII quaterpyridine complex.
Proc Natl Acad Sci U S A
; 121(14): e2319288121, 2024 Apr 02.
Article
in En
| MEDLINE
| ID: mdl-38527206
ABSTRACT
Design tactics and mechanistic studies both remain as fundamental challenges during the exploitations of earth-abundant molecular electrocatalysts for CO2 reduction, especially for the rarely studied Cr-based ones. Herein, a quaterpyridyl CrIII catalyst is found to be highly active for CO2 electroreduction to CO with 99.8% Faradaic efficiency in DMF/phenol medium. A nearly one order of magnitude higher turnover frequency (86.6 s-1) over the documented Cr-based catalysts (<10 s-1) can be achieved at an applied overpotential of only 190 mV which is generally 300 mV lower than these precedents. Such a high performance at this low driving force originates from the metal-ligand cooperativity that stabilizes the low-valent intermediates and serves as an efficient electron reservoir. Moreover, a synergy of electrochemistry, spectroelectrochemistry, electron paramagnetic resonance, and quantum chemical calculations allows to characterize the key CrII, CrI, Cr0, and CO-bound Cr0 intermediates as well as to verify the catalytic mechanism.
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01-internacional
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MEDLINE
Language:
En
Journal:
Proc Natl Acad Sci U S A
Year:
2024
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Article
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