Titanium-Porphyrin Metal-Organic Frameworks as Visible-Light-Driven Catalysts for Highly Efficient Sonophotocatalytic Reduction of Cr(VI).

In this work, we synthesized and characterized four titanium-porphyrin metal-organic frameworks (MOFs) [DGIST-1(M), M = Co(II), Fe(III), Zn(II), and H2] and used them as visible-light-driven catalysts for sonophotocatalytic Cr(VI) reduction. DGIST-1(M) exhibited open-framework, broad light absorption stemmed from ligand and sensitive photocurrent responses owing to the integration of one-dimensional Ti-oxo chains and 4-connected conjugated TCPP ligand (TCPP = tetrakis(4-carboxyphenyl)-porphyrin). DGIST-1(M) presented efficient reduction of Cr(VI) to Cr(III) in aqueous solution when used as sonophotocatalytic catalysts. The average reduction rates upon Cr(VI) were 0.920, 0.476, 0.377, and 0.194 mg·L-1·min-1 for DGIST-1(H2), DGIST-1(Zn), DGIST-1(Co), and DGIST-1(Fe), which are 1.15-2.45 times higher than those in photocatalysis. Sonophotocatalytic experiments and electron paramagnetic resonance measurement proved that Ti-oxo chain units and porphyrin ligand in the structures of DGIST-1(M) existed as catalytic active centers for sonophotocatalytic reduction of Cr(VI). Photoluminescence and UV absorption spectra revealed that the unity of photocatalysis and sonochemistry strengthened the migration of photogenerated electrons from DGIST-1(M) to Cr(VI), which improved the activities of catalysts. This study suggested that the association of titanium-porphyrin MOFs and sonophotocatalytic technology is an impactful program for enhancing MOF-based photocatalytic systems.