2D/2D covalent organic framework/CdS Z-scheme heterojunction for enhanced photocatalytic H_(2) evolution:Insights into interfacial charge transfer mechanism

Covalent organic frameworks(COFs)with high crystallinity and flexible designability have been consid-ered as promising candidates for photocatalytic hydrogen evolution.However,the existence of unpropi-tious exciton effects in COFs leads to poor charge separation,and thus results in low photocatalytic effi-ciency.Herein,to improve the photoelectron migration efficiency,we designed a 2D/2D organic/inorganic direct Z-scheme COF-based heterojunction(TpTAP/CdS),by the in-situ growing of CdS nanosheets on the COF copolymerized via 2,4,6-tris(4-aminophenyl)-1,3,5-triazine(TAP)and 1,3,5-triformylphloroglucinol(Tp).The femtosecond transient absorption(fs-TA)decay kinetics of TpTAP-COF and TpTAP/CdS further reveal the processes of shallow electron trapping and the recombination of the free photogenerated electron-hole pairs.In particular,the transient absorption traces for TpTAP-COF and TpTAP/CdS normal-ized to the photoinduced absorption peak can effectively verify the Z-scheme charge transfer between TpTAP-COF and CdS,which could enhance the charge mobility and separation,thus reducing the pho-tocorrosion of CdS.Additionally,ultraviolet photoelectron spectroscopy(UPS),in-situ X-ray photoelec-tron spectroscopy(XPS),transient photovoltage measurements,and electron spin resonance(ESR)spec-troscopy further confirm the establishment of the internal electric field(IEF).This work demonstrates the important role of COFs in the construction of 2D/2D organic/inorganic direct Z-scheme heterojunctions and offers a new avenue to explain the criticality of dynamics of the photogenerated carriers for the construction of Z-scheme heterojunctions.