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

Photocatalytic CO reduction, 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 on the modulation of the coordination structure of MN -type active sites (M = Co or Ni; = 4 or 5) anchored on a periodic mesoporous organosilica (PMO) support to improve photocatalytic CO reduction. The PMO was functionalized with pendant 3,6-di(2'-pyridyl)pyridazine (dppz) groups to allow immobilization of molecular Co and Ni complexes with polypyridine ligands. A comparative analysis of CO 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)]Cl sensitizer revealed strong influence of the coordination environment on the catalytic performance. CoN-PMO demonstrated a superior CO photoreduction activity than the other materials and displayed a cobalt-based turnover number (TON) of 92 for CO evolution at ∼75% selectivity after 3 h irradiation in the presence of 4CzIPN. The hybrid CoN-PMO catalyst exhibited better activity than its homogeneous [CoN] counterpart, indicating that the heterogenization promotes the formation of isolated active sites with improved longevity and faster catalytic rate.