Achieving High-Efficient Photoelectrocatalytic Degradation of 4-Chlorophenol via Functional Reformation of Titanium-Oxo Clusters
Jingjing Liu, Jing-Jing Liu, Shengnan Sun, Jiang Liu, Jiang Liu, Yi Kuang, Jingwen Shi, Long‐Zhang Dong, Ning Li, Jiani Lu, Jiao‐Min Lin, Shun‐Li Li, Ya‐Qian Lan
Abstract
Rational design of crystalline catalysts with superior light absorption and charge transfer for efficient photoelectrocatalytic (PEC) reaction coupled with energy recovery remains a great challenge. In this work, we elaborately construct three stable titanium-oxo clusters (TOCs, Ti 10 Ac 6, Ti 10 Fc 8, and Ti 12 Fc 2 Ac 4 ) modified with a monofunctionalized ligand (9-anthracenecarboxylic acid (Ac) or ferrocenecarboxylic acid (Fc)) and bifunctionalized ligands (Ac and Fc). They have tunable light-harvesting and charge transfer capacities and thus can serve as outstanding crystalline catalysts to achieve efficient PEC overall reaction, that is, the integration of anodic organic pollutant 4-chlorophenol (4-CP) degradation and cathodic wastewater-to-H 2 conversion. These TOCs can all exhibit very high PEC activity and degradation efficiency of 4-CP. Especially, Ti 12 Fc 2 Ac 4 decorated with bifunctionalized ligands exhibits better PEC degradation efficiency (over 99%) and H 2 generation than Ti 10 Ac 6 and Ti 10 Fc 8 modified with a monofunctionalized ligand. The study of the 4-CP degradation pathway and mechanism revealed that such better PEC performance of Ti 12 Fc 2 Ac 4 is probably due to its stronger interactions with the 4-CP molecule and better • OH radical production. This work not only presents the effective combination of organic pollutant degradation and simultaneously H 2 evolution reaction using crystalline coordination clusters as both anodic and cathodic catalyst but also develops a new PEC application for crystalline coordination compounds.