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Published on: October 17, 2011
Molecular-Bridged Core-Shell TiO2@CuFe Conductive Metal-Organic Framework Photoanode for Hydroxyl Radical-Mediated
Zihui Wang1, Xinwen Bai1, Jingzhe Tao1
1Department of Applied Chemistry, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, P. R. China.
None:
The solar-driven photoelectrochemical (PEC) oxidation of glycerol to value-added C3 products faces challenges due to the rapid charge recombination and unfavorable CC bond cleavage. This study presents a novel strategy through the rational design of a core-shell TiO2@CuFe-cMOF photoanode, where caffeic acid (CA) serves as a bifunctional molecular bridge to engineer a conformal, atomically coherent heterojunction interface. The unique architecture significantly enhances interfacial charge transport, suppresses carrier recombination, and promotes the selective generation of hydroxyl radicals (·OH) as the primary oxidant. Under AM 1.5 G illumination , the optimized photoanode achieves remarkable performance metrics: a photocurrent density of 1.67 mA cm-2 at 1.0 VRHE (~3.2-fold higher than pristine TiO2), together with glyceraldehyde (GLD) and 1,3-dihydroxyacetone (DHA) yields of 108 and 35.3 mmol m-2 h-1, representing ~3.0 times and ~2.3 times improvements over bare TiO2, respectively. The results reveal that the reaction proceeds dominantly via ·OH-mediated CH activation, with the CA-bridged core-shell structure effectively steering the reaction pathway toward valuable C3 products while suppressing over-oxidation to C1 byproducts. This study demonstrates the critical role of ligand-mediated interfacial engineering in designing efficient heterostructured photoanodes and establishes a sustainable paradigm for valorizing biomass-derived feedstocks through solar energy conversion.
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