Aneela Habib, Yiran Sun, Guosheng Shao, Peng Zhang
Photocatalyst driven artificial photosynthesis provides sustainable route for converting solar energy into chemical fuels. Here, cyano‐modified g‐C 3 N 4 ultrathin nanolayers are uniformly coated ontoelectrospun monoclinic ZrO 2 nanofibers (ZNF) via a facile one‐step gas‐solid reaction, forming a one‐dimensional coreshell heterostructure. The resulting Type‐II junctions noticeably broaden visible‐light absorption, accelerate charge migration, and suppress electron–hole recombination. Electron withdrawing cyano groups introduced in situ effectively tune the band structure, create favorable energy alignment for directional electron transfer, and enrich surface active sites. In situ irradiation X‐ray photoelectron spectroscopy reveals a dualactivesite system between cyano group and ZNF, confirming efficient photoinduced charge separation. Consequently, from this synergistic interface, the optimized composite achieves outstanding photocatalytic performance, yielding CO and CH 4 at 4.13 and 2.65 µmol g −1 h −1 , respectively, along with a high H 2 evolution rate of 1268 µmol g −1 h −1 under visible light. This work demonstrates an energy‐efficient and scalable strategy for designing surface engineered ZrO 2 /g‐C 3 N 4 nanofiber photocatalysts for efficient solardriven hydrogen evolutionand CO 2 reduction.