Synthesis and Photocatalytic Properties of Titanium‐Porphyrinic Aerogels

Abstract We present novel titanium‐porphyrinic gels (TPGs) and titanium‐porphyrinic aerogels (TPAs), in which porphyrinic ligand tetrakis(4‐carboxyphenyl)porphyrin is coordinated to Ti‐oxo clusters. These hierarchically porous TPAs, with micro‐, meso‐, and macropores and reactant‐concentration‐dependent Brunauer‐Emmett‐Teller surface areas of 407–738 m 2 g −1 , are prepared by CO 2 critical point drying of TPGs. Although the Ti 4+ → Ti 3+ photoreduction of TPAs is less efficient than that of crystalline microporous Ti‐porphyrinic framework DGIST‐1, prompt diffusion of O 2 and spin‐trapping agents into the TPA pores causes the rapid generation of reactive oxygen species (ROS), as observed by EPR spectroscopy. When used as an ROS scavenger, large 1,3‐diphenylisobenzofuran is degraded by the best‐performing TPA 10 times faster than by DGIST‐1, suggesting that the accessibility of molecules (reactants) to pores (reactive centers) strongly influences photocatalytic activity.