In Situ‐Illuminated X‐Ray Photoelectron Spectroscopy Investigation of S‐Scheme Ta2O5/ZnIn2S4 Core–Shell Hybrid Nanofibers for Highly Efficient Solar‐Driven CO2 Overall Splitting

Exploring and designing highly efficient solar‐driven CO 2 overall splitting photocatalysts toward carbon neutrality is still challenging. Herein, a novel core–shell Ta 2 O 5 /ZnIn 2 S 4 heterojunction photocatalyst is fabricated where ZnIn 2 S 4 nanosheets are deposited on mesoporous Ta 2 O 5 nanofibers via electrospinning and hydrothermal methods. In situ‐illuminated X‐ray photoelectron spectra analysis and density functional theory calculation imply that the photoelectrons in ZnIn 2 S 4 can transfer to Ta 2 O 5 though a 2D/1D interface, accelerating the separation of photogenerated electron–hole pairs driven by the built‐in electric field under illumination, coupling the S‐scheme charge transfer mechanism. As a result, the total yield of CO 2 overall splitting (including CO and CH 4 ) over ZISTO0.1 is about 4.1 and 5.74 times that of pristine Ta 2 O 5 nanofibers and ZnIn 2 S 4 nanosheets, respectively. This work may pave a promising strategy of designing heterojunction photocatalysts with S‐scheme pathways toward solar fuel generation.