| 内容提要: |
As a metallic cocatalyst, the photothermal effect of NiCo2S4 in the process of photocatalytic hydrogen evolution has not been deeply discussed elsewhere. It has been well known that how to intrinsically speed the photogenerated electrons transfer and active absorbed Water (*H2O) to release more hydrogen proton (*H) are extremely meaningful to photocatalytic hydrogen evolution improvement. Herein, a convenient and mild two-step solvothermal strategy was developed to meticulously design the interface contact structure between a noble-metal-free cocatalyst NiCo2S4 and semiconductor ZnIn2S4 nanoflower, which facilitated the charge rearrangement at the interface to boost the separation of photogenerated carriers. Importantly, photothermal effect induced by NiCo2S4 was demonstrated to ameliorate slow kinetics of water splitting with the apparent activation energy reduction form 50.5 kJ·mol-1 to 38.8 kJ·mol-1, which was responsible for improving photocatalytic hydrogen evolution rate of 6834.6 μmol·g-1·h-1 accompanied by apparent quantum efficiency of 13.0% at 400 nm. The electron transfer was accelerated due to localized electric field enhancement determined by Finite difference time domain (FDTD) simulations. The decline of Gibbs free energy barrier of adsorbed water from 2.94 eV on ZIS to 1.62 eV on NCS/ZIS resulted in H-OH bond activating was demonstrated using density functional theory (DFT). This work will provide an effective pathway to design semiconductor-metal-based photothermal assisted photocatalytic system and expand the application of metallic NiCo2S4 in solar-to-fuel conversion. |