Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production

Colloidal dye-sensitized photocatalysis is a promising route toward efficient solar fuel production by merging properties of catalysis, support, light absorption, and electron mediation in one. Metal-organic frameworks (MOFs) are host materials with modular building principles allowing scaffold property tailoring. Herein, we combine these two fields compare porous Zr-based MOFs UiO-66-NH2(Zr) UiO-66(Zr) to monoclinic ZrO2 as model colloid hosts co-immobilized molecular carbon dioxide reduction photocatalyst fac-ReBr(CO)3(4,4?-dcbpy) (dcbpy = dicarboxy-2,2?-bipyridine) photosensitizer Ru(bpy)2(5,5?-dcbpy)Cl2 (bpy 2,2?-bipyridine). These host-guest systems demonstrate selective CO2-to-CO acetonitrile presence an donor under visible irradiation, turnover numbers (TONs) increasing from ZrO2, UiO-66, UiO-66-NH2 turn. This attributed MOF facilitating hopping enhanced CO2 uptake due their innate porosity. Both phenomena pronounced for UiO-66-NH2(Zr), yielding TONs 450 which 2.5 times higher than MOF-free homogeneous conditions, highlighting synergistic effects between supramolecular photosystem components MOFs.