Rationally designing a Step-scheme (S-scheme) hetero-structured photocatalyst with high redox capability and separation efficiency of photoinduced carriers is considered as an attractive approach to address the shortcomings of single component and traditional hetero-structured photocatalyst. Herein, enlightened by the predictions of density functional theory (DFT), a unique S-scheme heterojunction photocatalyst was successfully fabricated by incorporating zero-dimensional (0D) Cd0.5Zn0.5S (CZS) on two-dimensional (2D) lamellar Cu2MoS4 (CMS) plates via a facile coprecipitation method, which substantially enhances the photocatalytic activity for hydrogen (H2) generation. CZS nanoparticles deposited on the surface of CMS nanoplates play a crucial role in creating highly intimate heterojunction interfaces and abundant exposed reaction sites, laying the foundation for improved photocatalytic performance. Furthermore, the significant difference in Fermi levels and band structures between CZS and CMS result in the formation of the internal electric field (IEF) and energy band bending at the interface of the heterojunction. This S-scheme charge transfer path enables 0D/2D CZS/CMS heterojunction possesses an exceptional capacity to maintain the robust redox potential and boosts the separation efficiency of light-induced carriers, as verified by DFT calculations and energy band structure analyses. As expected, the optimal heterojunction exhibits a satisfactory H2 generation rate of 13.1 mmol & sdot;g-1 & sdot;h_ 1, which is nearly 7.7-fold higher than that of individual CZS. This study is expected to inspire the design of morphology-controlled heterostructured photocatalyst with S-scheme charge transfer route for photocatalytic H2 generation.

Rational design of photocatalysts with photothermal effect to maximize light utilization is pivotal in achieving superior photocatalytic efficiency. In this work, by coating Cd0.9Zn0.1S (CZS) nanorods on hollow FeNi2S4 (FNS) microspheres with photothermal effect, a novel FeNi2S4@Cd0.9Zn0.1S (FNS@CZS) Step-scheme (S-scheme) heterojunction photocatalyst was constructed for efficient photothermal-assisted hydrogen (H2) evolution via simultaneously employing light and thermal energy. The hollow structure of FNS microsphere not only provides abundant reactive sites but also serves as a supportive substrate for CZS nanorods, effectively inhibiting their agglomeration. And the unique hollow structure of FNS allows for multiple reflections and refractions of visible light, enhancing the local temperature of the photocatalyst. This effectively minimizes thermal losses within the composite system, thereby enhancing the efficiency of light energy utilization. Furthermore, the formation of the S-scheme heterojunction facilitates the efficient separation of photogenerated charge carriers and enhances the activity of redox reactions, thereby boosting the overall photocatalytic activity. Experimental results reveal that the H2 production rate of the FNS@CZS heterojunction reaches 12.9 mmol & sdot;g- 1 & sdot;h- 1, which is 25.1 times higher than that of pristine CZS. By controlling the experimental temperature, the impact of the photothermal effect on the photocatalytic H2 production rate has been clarified. According to relevant evidence from infrared thermography and DFT calculations, comprehensive analyses and discussions were conducted on the photothermal effect and S-scheme charge transfer mechanisms. This study offers guidance on designing photothermalenhanced photocatalysts to achieve satisfactory H2 production activity.

Piezoelectric materials have advantages of fine-tuning photocatalytic performance through harvesting mechanical energy and open a new avenue in facilitating green catalytic reaction. Herein, polyvinylidene fluoride (PVDF), a flexible piezoelectric material, was introduced to synthesize a novel Cd0.9Zn0.1S-ZnO@C/PVDF (CZS-ZO@C/PVDF) piezo-photocatalytic film by spin coating and immersion phase conversion method. Benefiting from the piezoelectricity of PVDF and the internal electric field (IEF) of CZS-ZO@C Step-scheme (S-Scheme) heterojunction, CZS-ZO@C/PVDF was able to induce a hydrogen generation rate of 34.9 mmol g−1 h−1 activated by ultrasound and visible light (U-L), which is ∼17.5 times of Cd0.9Zn0.1S/PVDF (CZS/PVDF) and ∼7.4 times of the photocatalysis rate activated by visible light only (L). Piezoelectric measurements and COMSOL simulation illustrated the excellent piezoelectricity of CZS-ZO@C/PVDF film, which exhibits a piezoelectric coefficient (d33) of 9.9 pm V−1 and a piezoelectric potential of 874 mV (under 0.5 MPa). The reaction mechanism for the exceptional piezo-photocatalytic performance was finally disclosed through density functional theory (DFT) calculation and electrochemical tests. This study enriches the application scope of piezoelectric materials in sustainable energy catalysis and provides a new direction to develop efficient piezoelectric photocatalysts.

An emerging approach that employs both light and vibration energy on binary photo-/piezoelectric semiconductor materials for efficient hydrogen (H2) evolution has garnered considerable attention. ZnIn2S4 (ZIS) is recognized as a promising visible-light-activated photocatalyst. However, its effectiveness is constraint by the slow separation dynamics of photoexcited carriers. Density functional theory (DFT) predictions have shown that the integration of piezoelectric BiFeO3 (BFO) is conducive to the reduction of the H2 adsorption free energy (ΔGH*) for the photocatalytic H2 evolution reaction, thereby enhancing the reaction kinetics. Informed by theoretical predictions, piezoelectric BFO polyhedron particles were successfully synthesized and incorporated with ZIS nanoflowers to create a ZIS/BFO heterojunction using an ultrasonic-assisted calcination method. When subjected to simultaneous ultrasonic treatment and visible-light irradiation, the optimal ZIS/BFO piezoelectric enhanced (piezo-enhanced) heterojunction exhibited a piezoelectric photocatalytic (piezo-photocatalytic) H2 evolution rate approximately 6.6 times higher than that of pristine ZIS and about 3.0 times greater than the rate achieved under light-only conditions. Moreover, based on theoretical predictions and experimental results, a plausible mechanism and charge transfer route for the enhancement of piezo-photocatalytic performance were studied by the subsequent piezoelectric force microscopy (PFM) measurements and DFT calculations. The findings of this study strongly confirm that both the internal electric field of the step-scheme (S-Scheme) heterojunction and the alternating piezoelectric field generated by the vibration of BFO can enhance the transportation and separation of electron-hole pairs. This study presents a concept for the multipath utilization of light and vibrational energy to harness renewable energy from the environment.

The reasonable design and fabrication of heterojunction could regulate the photocatalytic performance to some extent, yet it is still a great challenge to construct the S-scheme heterostructure with the stable as well as tight interface on the surface of semiconductor photocatalysts. Herein, the ZnIn2S4/Cu2MoS4 (ZIS/CMS) S-scheme heterostructure was fabricated by in-situ assembling ZIS nanosheets on the CMS plates, obtaining a mossy tile-like morphology. Owing to the compact interface resulting from in-situ growth, this unique architecture efficiently facilitated the separation and transfer of light-induced charges, guaranteed the larger interface area, and enriched the active sites for photocatalytic redox reactions. After adjusting the mass ratio of CMS in ZIS/CMS, S-scheme heterostructure exhibited the remarkable performance with an optimal H2 producing rate up to 1298 μmol·h-1 g-1, about 13.8 times than that of pristine ZIS. The mechanism and driving force of charge transfer and separation in S-scheme heterostructure photocatalysts were explained and discussed. This investigation will provide new insight into design and construction of S-scheme heterojunction photocatalysts for H2 evolution.

The polarized electric field inside piezoelectric materials has been proven to be a promising technique to boost photogenerated charge separation. Herein, a novel flexible SnFe2O4/ZnIn2S4/polyvinylidene fluoride ((CH2CF2)n, PVDF) (P–SZ) film piezophotocatalyst was successfully synthesized by combining PVDF, an organic piezoelectric material, with a SnFe2O4/ZnIn2S4 (SFO/ZIS) type II heterojunction photocatalyst. The hydrogen evolution rate of SFO/ZIS heterojunction with a SFO content of 5% is about 846.79 μmol·h−1·g−1, which is 3.6 times that of pristine ZIS. Furthermore, after being combined with PVDF, the optimum hydrogen evolution rate of P–SZ is about 1652.7 μmol·h−1·g−1 in the presence of ultrasound, which exceeds that of 5% SFO/ZIS by an approximate factor of 2.0. Based on experimental results, the mechanism of the improved photocatalytic performance of P–SZ was proposed on the basis of the piezoelectric field in PVDF and the formed heterojunction between SFO and ZIS, which effectively boosted the separation of photoinduced charges. This work provides an efficient strategy for multi-path collection and utilization of natural solar and vibrational energy to enhance photoactivity.