Manipulating the Coordination Structure of Molecular Cobalt Sites in Periodic Mesoporous Organosilica for CO2 Photoreduction

The catalytic activity towards CO2 photoreduction, including reaction rate, product selectivity, and longevity, is highly sensitive to the coordination structure of the catalytic active sites, and the precise design of the active site remains a challenge in heterogeneous catalysts. Herein, we report modulation of the coordination structure of MNx-type active sites (M = Co or Ni; x = 4 or 5) anchored on a periodic mesoporous organosilica (PMO) support to improve photocatalytic CO2 reduction. The PMO was functionalised with pendant 3,6-di(2′-pyridyl)pyridazine (dppz) groups to allow immobilisation of molecular Co and Ni complexes with polypyridine ligands. A comparative analysis of CO2 photoreduction in the presence of an organic photosensitizer (4CzIPN, 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) and a conventional [Ru(bpy)3]Cl2 sensitiser revealed strong influence of the coordination environment on the catalytic performance. CoN5-PMO demonstrated a superior CO2 photoreduction activity than the other materials and displayed a cobalt-based turnover number (TONCO) of 92 for CO evolution at ~75% selectivity after 3 h irradiation in the presence of 4CzIPN. The hybrid CoN5-PMO catalyst exhibited better activity than its homogeneous [CoN5] counterpart, indicating that the heterogenisation promotes the formation of isolated active sites with improved longevity and faster catalytic rate.