Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction

The electronic character of porphyrin active sites for electrocatalytic reduction of CO2 to CO in a two-dimensional covalent organic framework (COF) was tuned by modification of the reticular structure. Efficient charge transport along the COF backbone promotes electronic connectivity between remote functional groups and the active sites and enables the modulation of the catalytic properties of the system. A series of oriented thin films of these COFs was found to reduce CO2 to CO at low overpotential (550 mV) with high selectivity (faradaic efficiency of 87%) and at high current densities (65 mA/mg), a performance well beyond related molecular catalysts in regard to selectivity and efficiency. The catalysts…

• NS
  National Science Foundation

  Award: DE-AC02-05CH11231
• UD
  U.S. Department of Energy

  Awards: -AC02-05CH11231, 101528-002, 05CH11231, AC02-05CH11231, DE-AC02, DESC0001015, DE-AC02-05CH11231, DE-AC02-
• KF
  Kavli Foundation
• CI
  Canadian Institute for Advanced Research
• BA
  British Academy
• RS
  Royal Society
• AO
  Academy of Medical Sciences
• EN
  Eidgenössisches Nuklearsicherheitsinspektorat
• OO
  Office of Science

  Awards: AC02-05CH11231, -AC02-05CH11231, DE-AC02, DESC0001015
• BE
  Basic Energy Sciences

  Awards: DE-AC02, AC02-05CH11231, DESC0001015, 101528-002, DE-AC02-05CH11231, -AC02-05CH11231
• AR
  Army Research Office

  Awards: WG11NF-15-1-0047, DE-AC02-05CH11231
• LB
  Lawrence Berkeley National Laboratory

  Awards: DE-AC02-05CH11231, 05CH11231, 101528-002, AC02-05CH11231