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The rational design of durable and nonprecious nanocomposite photocatalysts with efficient charge separation and abundant active sites is still a grand challenge for photocatalytic hydrogen production from water reduction. Herein, a novel ternary nanocomposite, MoO 2 decorated Mn 0.5 Cd 0.5 S/Cu 2 O p-n heterojunction has been constructed via a facile two-step route employing the energy band engineering theory. Impressively, the optimized ternary Mn 0.5 Cd 0.5 S/Cu 2 O/MoO 2 nanocomposite displays a robust photocatalytic H 2 -evolution rate of 733.24 μmol h−1 under simulated solar light irradiation, more 4.2 times higher than pure Mn 0.5 Cd 0.5 S. The results demonstrated that the p-n heterojunction formed between n-type Mn 0.5 Cd 0.5 S and p-type Cu 2 O could markedly promote the interfacial charge transfer/separation through the internal electric field, whereas the MoO 2 cocatalyst with low overpotential could effectively collect photoinduced electrons and dramatically facilitate the H 2 -evolution kinetics. Moreover, both Cu 2 O and MoO 2 could improve the light-harvesting ability of pristine Mn 0.5 Cd 0.5 S, further contributing to the boosted hydrogen generation activity. [Display omitted] • MoO 2 decorated Mn 0.5 Cd 0.5 S/Cu 2 O p-n heterojunction synthesized for H 2 -production. • Multichannel charge-carrier transfer between Mn 0.5 Cd 0.5 S, Cu 2 O and MoO 2 discussed. • High H 2 -production rate achieved over composite, 4.2 folds higher than Mn 0.5 Cd 0.5 S. [ABSTRACT FROM AUTHOR]

[Display omitted] • Direct Z-scheme Mn 0.5 Cd 0.5 S/CoTiO 3 heterojunction was designed. • Mechanism for the enhanced photoactivity over Mn 0.5 Cd 0.5 S/CoTiO 3 heterojunction discussed. • High ammonia production rate achieved over heterojunction, 5.1-fold higher than Mn 0.5 Cd 0.5 S. The exploration and design of highly efficient and robust photocatalysts composed of earth-abundant materials for ambient photocatalytic N 2 fixation to ammonia remains a significant challenge. Here, we have fabricated a stable and highly efficient direct Z-scheme Mn 0.5 Cd 0.5 S/CoTiO 3 heterostructure for N 2 fixation by depositing Mn 0.5 Cd 0.5 S nanoparticles on CoTiO 3 surface. Under ambient conditions, the optimized Mn 0.5 Cd 0.5 S/CoTiO 3 heterojunction achieved a significant NH 3 production rate of 121.9 μmol g-1h−1 without cocatalyst modification, representing a 5.1- and 5.9-fold increase over pristine Mn 0.5 Cd 0.5 S and CoTiO 3 , respectively, and also exceeding most previously reported photocatalytic systems. The significant improvement in ammonia production primarily results from the Z-scheme charge transfer path between the Mn 0.5 Cd 0.5 S and CoTiO 3 components, which enables effective separation of photoinduced carriers while maintaining their robust redox capacity, thus dramatically boosting ammonia generation performance. This research may provide new insights for advancing other alternative Z-scheme photocatalytic systems with remarkable stability and exceptional efficiency in N 2 fixation. [ABSTRACT FROM AUTHOR]

The rational design of hierarchical heterojunction photocatalysts with efficient spatial charge separation remains an intense challenge in hydrogen generation from photocatalytic water splitting. Herein, a noble-metal-free MoS 2 /g-C 3 N 4 /ZnIn 2 S 4 ternary heterostructure with a hierarchical flower-like architecture was developed by in situ growth of 3D flower-like ZnIn 2 S 4 nanospheres on 2D MoS 2 and 2D g-C 3 N 4 nanosheets. Benefiting from the favorable 2D-2D-3D hierarchical heterojunction structure, the resultant MoS 2 /g-C 3 N 4 /ZnIn 2 S 4 nanocomposite loaded with 3 wt% g-C 3 N 4 and 1.5 wt% MoS 2 displayed the optimal hydrogen evolution activity (6291 μmol g−1 h−1), which was a 6.96-fold and 2.54-fold enhancement compared to bare ZnIn 2 S 4 and binary g-C 3 N 4 /ZnIn 2 S 4 , respectively. Structural characterizations reveal that the significantly boosted photoactivity is closely associated with the multichannel charge transfer among ZnIn 2 S 4 , MoS 2 , and g-C 3 N 4 components with suitable band-edge alignments in the composites, where the photogenerated electrons migrate from g-C 3 N 4 to ZnIn 2 S 4 and MoS 2 through the intimate heterojunction interfaces, thus enabling efficient electron-hole separation and high photoactivity for hydrogen evolution. In addition, the introduction of MoS 2 nanosheets highly benefits the improved light-harvesting capacity and the reduced H 2 -evolution overpotential, further promoting the photocatalytic H 2 -evolution performance. Moreover, the MoS 2 /g-C 3 N 4 /ZnIn 2 S 4 ternary heterostructure possesses prominent stability during the photoreaction process owing to the migration of photoinduced holes from ZnIn 2 S 4 to g-C 3 N 4 , which is deemed to be central to practical applications in solar hydrogen production. [ABSTRACT FROM AUTHOR]

Exploring efficient and robust photocatalysts for solar hydrogen generation from water reduction is great significant in solving the energy shortage and environment contamination simultaneously. Herein, benefiting from the matchable energy band structures and band bending, the direct Z-scheme ZnIn 2 S 4 /NiWO 4 heterojunctions were successfully constructed by anchoring p-type NiWO 4 nanoparticles onto n-type ZnIn 2 S 4 nanosheets through a facile sonochemical route. By carefully regulating the interfacial structure, the optimized ZnIn 2 S 4 /NiWO 4 heterostructure without any cocatalyst displays excellent stability and remarkably improved photocatalytic hydrogen evolution activity (16.3 mmol∙g−1∙h−1), more 3.57-folds increment than bare ZnIn 2 S 4 photocatalyst. Mechanistic characterizations demonstrate that the dramatically boosted photocatalytic performance mainly results from the constructed Z-scheme heterostructure and intimately interfacial contact between ZnIn 2 S 4 and NiWO 4 , which results in the valid interfacial charge transfer channels, powerful redox potential and reduced hydrogen evolution energy barrier, as confirmed by the joint analysis of electron spin resonance (ESR) and photoelectrochemical measurements. More importantly, the photoinduced holes of ZnIn 2 S 4 are rapidly and effectively consumed in the unique Z-scheme charge transfer channels, which greatly favors the suppression of the photocorrosion caused by insufficient hole extraction during the photocatalytic reaction, thereby promoting the overall stability and reusability of the ZnIn 2 S 4 /NiWO 4 composite photocatalyst. This study paves the way for constructing other Z-scheme nano-heterostructure consisting of p-type and n-type semiconductors with efficient photoactivity and robust stability for energy and environmental applications. [Display omitted] • Z-scheme heterojunction consisting of p-type and n-type semiconductors was designed. • Mechanism for the enhanced photoactivity over ZnIn 2 S 4 /NiWO 4 heterojunction discussed. • High H 2 -production rate achieved over heterojunction, 3.57-fold higher than ZnIn 2 S 4. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ternary Mn 0.5 Cd 0.5 S/CB/CuS hierarchical multiheterojunction system was designed. • Synergetic effect between multifunctional CB and CuS dual cocatalysts discussed. • High H 2 -production rate achieved over composite, 4.79-fold higher than Mn 0.5 Cd 0.5 S. Developing exceptionally robust and cost-effective cocatalysts to suppress charge recombination and reduce the reaction energy barrier remains an enormous challenge for producing high-valued and storable hydrogen fuel from photocatalytic water splitting. Herein, novel Mn 0.5 Cd 0.5 S nanoparticles modified with multifunctional carbon black (CB) nanowires and CuS nanotubes as dual cocatalysts were fabricated via sonochemical loading, and subsequent in-situ deposition routes. In this ternary hierarchical architecture, both CB nanowires and CuS nanotubes can serve as normal electron cocatalysts to markedly promote the hydrogen generation performance by lowering the thermodynamic overpotential for hydrogen evolution. Moreover, due to the high electrical conductivity, the multifunctional CB material can also function as a bridge to effectively capture and transmit the photoexcited electrons from Mn 0.5 Cd 0.5 S to CuS with outstanding electrocatalytic hydrogen evolution activity, thus maximizing the carrier separation and H 2 -evolution reaction kinetics. Interestingly, the cooperative effects between CB and CuS dual cocatalysts are also helpful for improving the oxidation capacity of photoexcited holes by lowering the valence band position of Mn 0.5 Cd 0.5 S, which further accelerates the electron-hole separation. As a result, the constructed Mn 0.5 Cd 0.5 S/CB/CuS hierarchical multiheterojunction catalyst shows the superior hydrogen generation efficiency of 819.9 μmol h−1 and excellent stability under simulated solar light irradiation. [ABSTRACT FROM AUTHOR]