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Designing S-scheme heterojunctions is an effective method to improve the charge localization on the surface of photocatalysts. Their effective charge transport routes can be enhanced with the help of interfacial noble metal nanoparticles. Herein, an Ag/CuO@ZnIn 2 S 4 plasma S-scheme heterojunction with heterogeneous interfacial covalent bonds was successfully designed. The 15% Ag/CuO@ZnIn 2 S 4 has promising photocatalytic performance and stability with the highest CO and CH 4 yields of 6.9 and 54.4 µmol g−1 h−1 and CH 4 selectivity of 92.8%. It is evidenced that the photogenerated charge can be efficiently separated and transported due to the influence of both the S-scheme electron migration mode and the Cu-S covalent bond. The process is further accelerated by using precious metals as cocatalysts, which can then selectively convert CO 2 into CH 4. This research is expected to provide helpful information for engineering S-scheme heterojunction photocatalysts and investigating their charge transfer kinetics. [Display omitted] • Design of a S-scheme heterojunction to promote the separation of carriers. • Built the Cu-S bonds to accelerate the transfer of charges. • Utilizing the LSPR effect to generate hot electrons and enhance light absorption. • The Ag/CuO@ZnIn 2 S 4 photocatalysts can selectively reduce CO 2 to CH 4. [ABSTRACT FROM AUTHOR]

• LSPR effect enhanced Z-scheme ZnO/Au/g-C 3 N 4 micro needles film (3-ZAC) has been prepared for the photoreduction of CO 2 into CO under UV–vis light irradiation. • Au NPs at the interface of ZnO/g-C 3 N 4 not only act as the electron-transfer bridge, but also as LSPR excited source to speed up the separation of electron-hole pairs photogenerated in the semiconductors. • DFT calculation and FDTD simulation methods has been used to prove the transfer processes of photogenerated electron. The photoproduction of CO from the photocatalytic CO 2 reduction process has been evidenced from 13C isotope tracer tests. • This work demonstrates the importance of the build-in electric field formed at g-C 3 N 4 /ZnO interface and local electromagnetic field of Au NPs for the photoreduction process, providing an inspiring concept for future advancement in this area. Local Surface Plasma Resonance (LSPR) effect enhanced Z-scheme ZnO/Au/g-C 3 N 4 micro-needles film (3-ZAC) has been prepared for the photoreduction of CO 2 into CO under UV–vis light irradiation. Photoreduction experiments show that 3-ZAC has the excellent photocatalytic performance and reusability. The CO production can be achieved 689.7 μmol/m2 after 8 h reaction time, which is 4.5 higher than that of the pure ZnO film. 13C isotope test shows that CO is produced from CO 2 by photoreduction. DFT calculations confirm that build-in electric field formed at g-C 3 N 4 /ZnO interface effectively promoted the electron transfer efficiency in Z-scheme interface. FDTD simulations prove that Au NPs not only act as electron-transfer bridge, but also as LSPR excited source to speed up the separation of electron-hole pairs. In-situ FTIR technique was used to investigate the CO 2 photoreduction process. The above characteristics together maximize the electron transfer efficiency, which causes the material has enhanced photocatalytic performance. [ABSTRACT FROM AUTHOR]