Heterogenous CO Reduction Photocatalysis of Transparent Coordination Polymer Glass Membranes Containing Metalloporphyrins.

Transparent and grain boundary-free substrates are essential to immobilize molecular photocatalysts for efficient photoirradiation reactions without unexpected light scattering and absorption by the substrates. Herein, membranes of coordination polymer glass immobilizing metalloporphyrins were examined as a heterogeneous photocatalyst for carbon dioxide (CO) reduction under visible-light irradiation. [Zn(HPO)(HPO)](ImH) (Im = imidazolate) liquid containing iron(III) 5,10,15,20-tetraphenyl-21H,23H-porphine chloride (Fe(TPP)Cl, 0.1-0.5 w/w%) was cast on a borosilicate glass substrate, followed by cooling to room temperature, resulting in transparent and grain boundary-free membranes with the thicknesses of 3, 5, and 9 μm. The photocatalytic activity of the membranes was in proportion to the membrane thickness, indicating that Fe(TPP)Cl in the subsurface of membranes effectively absorbed light and contributed to the reactions. The membrane photocatalysts were intact during the photocatalytic reaction and showed no recrystallization or leaching of Fe(TPP)Cl.