Photothermal‐Enhanced S‐Scheme Heterojunction of Hollow Core–Shell FeNi2S4@ZnIn2S4 toward Photocatalytic Hydrogen Evolution

Abstract Herein, guided by the results of density functional theory prediction, the study rationally designs a hollow core–shell FeNi2S4@ZnIn2S4 (FNS@ZIS) Step‐scheme (S‐scheme) heterojunction for photocatalytic H2 evolution with photothermal‐assisted. The hollow FNS spheres offered substrate for coating the ZIS nanosheets, which can inhibit ZIS nanosheets from agglomerating into pellet, enrich the active site, increase specific surfaces, and raise the light absorption. Notably, due to its excellent photothermal properties, FNS core generated heat unceasingly inside under visible‐light irradiation and effectively prevent the heat loss of the reaction system, which increased the local temperature of photocatalysts and thus accelerated the charge migration. In addition, the S‐scheme heterojunction construction via in situ growth has a tight interface, which can facilitate the separation and transfer of carriers and achieve high redox potential. Owning to the distinctive construction, the hollow core–shell FNS@ZIS S‐scheme heterojunction show extraordinary stability and photocatalytic H2 evolution rate with 7.7 mmol h−1 g−1, which is ≈15.2‐fold than pristine ZIS. Based on the double evidence of theoretical predictions and experimental confirmations, the photothermal effect and electron transfer mechanism of this innovative material are investigated in depth by the following infrared thermography technology and deep DFT calculations.