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Highly efficient electrocatalytic CO 2 reduction by a Cr III quaterpyridine complex.

Jia-Wei WangZhi-Mei LuoGuangjun YangMarcos Gil-SepulcreStefanie GräfeOlaf RüdigerGangfeng Ouyang
Published in: Proceedings of the National Academy of Sciences of the United States of America (2024)
Design tactics and mechanistic studies both remain as fundamental challenges during the exploitations of earth-abundant molecular electrocatalysts for CO 2 reduction, especially for the rarely studied Cr-based ones. Herein, a quaterpyridyl Cr III catalyst is found to be highly active for CO 2 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 Cr II , Cr I , Cr 0 , and CO-bound Cr 0 intermediates as well as to verify the catalytic mechanism.
Keyphrases
  • highly efficient
  • molecular dynamics
  • single molecule
  • body composition
  • gold nanoparticles
  • molecular dynamics simulations
  • energy transfer
  • postmenopausal women
  • carbon dioxide