A reasonable design of samples with efficient spatial separation for photoinduced electron−hole pairs toward the photocatalytic hydrogen evolution reaction (HER) has gained significant attention. Herein, a new C/MoS 2 @ZnIn 2 S 4 / Co 3 O 4 composite with a core−shell structure is designed toward photocatalytic hydrogen production on C/MoS 2 and Co 3 O 4 dual electron collectors. Co 3 O 4 nanoparticles as the co-catalyst would form a Schottky junction with ZnIn 2 S 4 nanosheets while the C/MoS 2 hollow core would form the step-scheme (S-scheme) heterojunction with ZnIn 2 S 4 sheets, which provides a dual photogenerated electron transfer pathway during the light irradiation process. In addition, the unique core− shell architecture offers large contact interfaces favoring the exposure of rich active sites, which facilitated the separation and the transfer of charges. Consequently, all these factors endowed the C/MoS 2 @ZnIn 2 S 4 /Co 3 O 4 composite with enhanced light absorption ability and an increased hydrogen evolution rate of 6.7 mmol•g −1 • h −1 under 420 nm light irradiation, which is about 23.4-and 4.5-fold that of ZnIn 2 S 4 and CMZ, respectively. This work offers a guideline for designing efficient composite photocatalysts toward the photocatalytic HER.

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