Conjugated π Electrons of MOFs Drive Charge Separation at Heterostructures Interface for Enhanced Photoelectrochemical Water Oxidation.

Photoanode material with high efficiency and stability is extensively desirable in photoelectrochemical (PEC) water splitting for green/renewable energy source. Herein, novel heterostructures is constructed via coating rutile TiO nanorods with metal organic framework (MOF) materials UiO-66 or UiO-67 (UiO-66@TiO and UiO-67@TiO ), respectively. The π electrons in the MOF linkers could increase the local electronegativity near the heterojunction interface due to the conjugation effect, thereby enhancing the internal electric field (IEF) at the heterojunction interface. The IEF could drive charge transfer following Z-scheme mechanism in the prepared heterostructures, inducing photogenerated charge separation efficiency increasing as 156% and 253% for the UiO-66@TiO and UiO-67@TiO , respectively. Correspondingly, the UiO-66@TiO and UiO-67@TiO enhanced the photocurrent density as approximate two- and threefolds compared with that of pristine TiO for PEC water oxidation in universal pH electrolytes. This work demonstrates an effective method of regulating the IEF of heterojunction toward further improved charge separation.