Rationally designed ternary CdSe/WS2/g-C3N4 hybrid photocatalysts with significantly enhanced hydrogen evolution activity and mechanism insight

Excellent light harvest, efficient charge separation and sufficiently exposed surface active sites are crucial for a given photocatalyst to obtain excellent photocatalytic performances. The construction of two-dimensional/two-dimensional (2D/2D) or zero-dimensional/2D (0D/2D) binary heterojunctions is one of the effective ways to address these crucial issues. Herein, a ternary CdSe/WS₂/g-C₃N₄ composite photocatalyst through decorating WS₂/g-C₃N₄ 2D/2D nanosheets (NSs) with CdSe quantum dots (QDs) was developed to further increase the light harvest and accelerate the separation and migration of photogenerated electron-hole pairs and thus enhance the solar to hydrogen conversion efficiency. As expected, a remarkably enhanced photocatalytic hydrogen evolution rate of 1.29 mmol g⁻¹ h⁻¹ was obtained for such a specially designed CdSe/WS₂/g-C₃N₄ composite photocatalyst, which was about 3.0, 1.7 and 1.3 times greater than those of the pristine g-C₃N₄ NSs (0.43 mmol g⁻¹ h⁻¹), WS₂/g-C₃N₄ 2D/2D NSs (0.74 mmol g⁻¹ h⁻¹) and CdSe/g-C₃N₄ 0D/2D composites (0.96 mmol g⁻¹ h⁻¹), respectively. The superior photocatalytic performance of the prepared ternary CdSe/WS₂/g-C₃N₄ composite could be mainly attributed to the effective charge separation and migration as well as the suppressed photogenerated charge recombination induced by the constructed type-II/type-II heterojunction at the interfaces between g-C₃N₄ NSs, CdSe QDs and WS₂ NSs. Thus, the developed 0D/2D/2D ternary type-II/type-II heterojunction in this work opens up a new insight in designing novel heterogeneous photocatalysts for highly efficient photocatalytic hydrogen evolution.     

Fabrication of hollow g-C3N4@α-Fe2O3/Co-Pi heterojunction spheres with enhanced visible-light photocatalytic water splitting activity

For the first time, g-C₃N₄@α-Fe₂O₃/Co-Pi heterojunctional hollow spheres were successfully fabricated via thermal condensation method followed by solvothermal and photo-deposition treatment, which showed excellent photocatalytical property. Except for the Z-scheme charge transfer between α-Fe₂O₃ and g-C₃N₄, the Co-Pi could further reduce the combination of photogenerated electrons and holes as a hole storage agent, resulting in remarkably enhanced visible-light photocatalytic water splitting activity with the H₂ production rate of 450 μmol h⁻¹g⁻¹, which is 15.7 times higher than that of g-C₃N₄. Moreover, the photocatalytic activity of the prepared ternary hollow photocatalysts showed almost no significant weakness after five cycles, which indicated their good performance stability. The as-prepared g-C₃N₄@α-Fe₂O₃/Co-Pi also possessed good activity for overall water splitting with the hydrogen production rate reaching 9.8 μmol h⁻¹g⁻¹. This synthesized g-C₃N₄@α-Fe₂O₃/Co-Pi composite is expected to be a promising candidate for water splitting.     

Hybridization of g-C3N4 quantum dots with 1D branched TiO2 fiber for efficient visible light-driven photocatalytic hydrogen generation

The hybrid 1D branched TiO₂ loaded with g-C₃N₄ QDs was successfully fabricated that plays a significant role in photocatalysis. The 1D branched TiO₂ prepared by electrospinning followed by alkali-hydrothermal process, and g-C₃N₄ QDs were grafted over it by a chemical vapor deposition method. The composite display enhancement in photocatalytic hydrogen evolution is about 10.57 mmol. g⁻¹.h⁻¹ in comparison to the g-C₃N₄ sample that only produces 0.32 mmol. g⁻¹.h⁻¹ while the HBTiO₂ sample evolved a negligible amount of hydrogen under visible light. The composite sample shows quantum efficiency for HER at 420 nm light is 18.6% that is much higher than the other two samples. The specific surface area of the composite sample is 92.39 m²g^-1 that is about 13 times more than bulk g-C₃N_4. The bandgap of HBTiO₂/g-C₃N₄ QDs, g-C₃N₄, and HBTiO₂ samples calculated as 2.71 eV, 2.67eV, and 3.24eV, respectively. The TRPL spectra imply that the duration of the lifetime of composite becomes longer which effectually overwhelm the electron-hole recombination. The 1D branched TiO₂ fiber reduces the charge recombination by fast transfer of electron while g-C₃N₄ QDs facilitate the visible light absorption by improving the optical properties. The formation of the type II heterostructure system remarkably promotes the separation and transfer of electron holes and facilitates the photo-reduction reaction.     

The charge transfer pathway of g-C3N4 decorated Au/Bi(VO4) composites for highly efficient photocatalytic hydrogen evolution

In this report, a novel g-C₃N₄/Au/BiVO₄ photocatalyst has been prepared successfully by assembling gold nanoparticles on the interface of super-thin porous g-C₃N₄ and BiVO₄, which exhibits outstanding photocatalytic performance toward hydrogen evolution and durable stability in the absence of cocatalyst. FESEM micrograph analysis suggested that the intimate contact between Au, BiVO₄, and g-C₃N₄ in the as-developed photocatalyst allows a smooth migration and separation of photogenerated charge carriers. In addition, the XRD, EDX and XPS analysis further confirmed the successful formation of the as-prepared g-C₃N₄/Au/BiVO₄ photocatalyst. The photocatalytic hydrogen production activity of the developed photocatalyst was evaluated under visible-light irradiation (λ > 420 nm) using methanol as a sacrificial reagent. By optimizing the 5-CN/Au/BiVO₄ composite shows the highest H₂ evolution rate (2986 μmolg⁻¹h⁻¹), which is 15 times higher than that of g-C₃N₄ (199 μmolg⁻¹h⁻¹) and 10 time better than bare BiVO₄ (297 μmolg⁻¹h⁻¹). The enhancement in photocatalytic activity is attributed to efficient separation of the photoexcited charges due to the anisotropic junction in the g-C₃N₄/Au/BiVO₄ system. The enhancement in photocatalytic activity is attributed to efficient separation of the photoexcited charges due to the anisotropic junction in the g-C₃N₄/Au/BiVO₄ system.     

CaH2-assisted structural engineering of porous defective graphitic carbon nitride (g-C3N4) for enhanced photocatalytic hydrogen evolution

The practical applications of graphitic carbon nitride (g-C₃N₄) for photocatalytic hydrogen evolution is strictly hindered by the low surface area, poor light harvesting capability and detrimental recombination of photoexcited charge carriers. Herein, using melamine as precursor and metal hydride (i.e., CaH₂) as active agent, we facilely incorporate various types of defects (i.e., nitrogen (N) vacancies (V_N), cyano groups (CN) and surface absorbed oxygen species(O_abs)) into g-C₃N₄ within a single step. The as-prepared material (denoted as MM-H) exhibits narrowed bandgap, promoted photoexcited electron-hole separation rate and facilitated charge transfer kinetics with enlarged BET surface area and massive porosity. As a result, a prominently enhanced photocatalytic H₂ productivity efficiency (1305.9 μmol h⁻¹g⁻¹) is shown on MM-H. This performance is better than that of g-C₃N₄ with CaH₂ post-treatment (617.3 μmol h⁻¹g⁻¹) and raw bulk-C₃N₄ (178.2 μmol h⁻¹g⁻¹). This work opens up a new dimension for designing high performance g–C₃N₄–based catalysts targeting various photocatalytic processes.     

In-situ synthesis of PdAg/g-C3N4 composite photocatalyst for highly efficient photocatalytic H2 generation under visible light irradiation

Novel PdAg bimetallic alloy nanoparticle modified graphitic carbon nitride (g-C₃N₄) nanosheet was designed and prepared by an in situ chemical reduction procedure. By optimizing the loading content of the PdAg alloy NPs, the PdAg/g-C₃N₄ composite photocatalyst showed a champion photocatalytic hydrogen generation rate of 3.43 mmol h⁻¹ g⁻¹, and the apparent quantum yield (AQY) was determined to be 8.43% at 420 nm. Moreover, the photoluminescence and photoelectrochemical experimental results suggest that a higher separation efficiency of photo-induced charge carriers (e^- and h⁺) was obtained after loading PdAg alloy NPs on g-C₃N₄. The experimental outcomes indicate that there is a synergistic effect formed between PdAg and g-C₃N₄, which could significantly promote the charge transfer photo-induced charge carriers in the hybrid sample. A reasonable catalytic mechanism for the enhanced photocatalytic performance of the composite photocatalyst was proposed and verified by TRPL measurement, which could be taken as a guidance for the development of novel high performance catalytic system.     

Bimetallic PtNi alloy modified 2D g-C3N4 nanosheets as an efficient cocatalyst for enhancing photocatalytic hydrogen evolution

Platinum-based alloy materials as effective cocatalysts in improving the performance of photocatalytic H₂ production have raised great interest. Herein, a facile strategy of chemical reduction is established to synthesize bimetallic PtNi nanoparticles on 2D g-C₃N₄ nanosheets with excellent photocatalytic activity. The addition of PtNi nanoparticles can provide new H⁺ reduction sites and increase more active sites of the material. The synergistic effect between PtNi alloy nanoparticles and 2D g-C₃N₄ nanosheets can regulate electronic structure, narrow the band, accelerate charge transfer efficiency and inhabit the recombination of photo-induced electron (e⁻) and hole pairs (h⁺), contributing to the improvement of hydrogen evolution activity. The optimal hydrogen evolution rate of Pt_0.6Ni_0.4/CN shows higher hydrogen evolution rate (9528 μmol·g⁻¹·h⁻¹), which is 13.1 times than that of pure g-C₃N₄ nanosheets. Besides, a possible mechanism of photocatalytic hydrogen generation has been brought up according to a series of physical and chemical characterization. This work also provides a potential idea of developing cocatalysts integrating metal alloys with 2D g-C₃N₄ nanosheets for promoting photocatalytic hydrogen evolution.     

Montmorillonite-hybridized g-C3N4 composite modified by NiCoP cocatalyst for efficient visible-light-driven photocatalytic hydrogen evolution by dye-sensitization

The photocatalytic hydrogen evolution performance of g-C₃N₄ was enhanced via the hybridization with montmorillonite (MMT) and using NiCoP as cocatalyst. The highest hydrogen-evolution rate from water splitting under visible-light irradiation observed over MMT/g-C₃N₄/15%NiCoP was 12.50 mmol g⁻¹ h⁻¹ under 1.0 mmol L⁻¹ of Eosin Y-sensitization at pH of 11, which was ∼26.0 and 1.6 times higher than that of MMT/g-C₃N₄ (0.48 mmol g⁻¹ h⁻¹) and g-C₃N₄/15%NiCoP (7.69 mmol g⁻¹ h⁻¹). The apparent quantum yield at 420 nm reached 40.3%. The remarkably improved photocatalytic activity can be ascribed to the increased dispersion of g-C₃N₄ layers, staggered conduction band potentials between g-C₃N₄ and NiCoP, as well as the electrostatic repulsion originated from negatively charged MMT. This work demonstrates that MMT can be an outstanding support for the deposition of catalytically active components for photocatalytic hydrogen production.     

Construction of ternary hybrid layered reduced graphene oxide supported g-C3N4-TiO2 nanocomposite and its photocatalytic hydrogen production activity

Reduced graphene oxide (rGO) supported g-C₃N₄-TiO₂ ternary hybrid layered photocatalyst was prepared via ultrasound assisted simple wet impregnation method with different mass ratios of g-C₃N₄ to TiO₂. The synthesized composite was investigated by various characterization techniques, such as XRD, FTIR, Raman Spectra, FE-SEM, HR-TEM, UV vis DRS Spectra, XPS Spectra and PL Spectra. The optical band gap of g-C₃N₄-TiO₂/rGO nanocomposite was found to be red shifted to 2.56 eV from 2.70 eV for bare g-C₃N₄. It was found that g-C₃N₄ and TiO₂ in a mass ratio of 70:30 in the g-C₃N₄-TiO₂/rGO nanocomposite, exhibits the highest hydrogen production activity of 23,143 μmol g^?1h^?1 through photocatalytic water splitting. The observed hydrogen production rate from glycerol-water mixture using g-C₃N₄-TiO₂/rGO was found to be 78 and 2.5 times higher than g-C₃N₄ (296 μmol g^?1 h^?1) and TiO₂ (11,954 μmol g^?1 h^?1), respectively. A direct contact between TiO₂ and rGO in the g-C₃N₄-TiO₂/rGO nanocomposite produces an additional 10,500 μmol g^?1h^?1 of hydrogen in 4 h of photocatalytic reaction than the direct contact between g-C₃N₄ and rGO. The enhanced photocatalytic hydrogen production activity of the resultant nanocomposite can be ascribed to the increased visible light absorption and an effective separation of photogenerated electron-hole pairs at the interface of g-C₃N₄-TiO₂/rGO nanocomposite. The effective separation and transportation of photogenerated charge carriers in the presence of rGO sheet was further confirmed by a significant quenching of photoluminescence intensity of the g-C₃N₄-TiO₂/rGO nanocomposite. The photocatalytic hydrogen production rate reported in this work is significantly higher than the previously reported work on g-C₃N₄ and TiO₂ based photocatalysts.     

2D MOFs enriched g-C3N4 nanosheets for highly efficient charge separation and photocatalytic hydrogen evolution from water

Here we report a 2D-2D heterostructure of g-C₃N₄/UMOFNs photocatalysts via mechanical grinding two kinds of two-dimensional nanosheets of g-C₃N₄ nanosheets and UMOFNs, which exhibits enhanced H₂ evolution from water with simulated solar irradiation. g-C₃N₄ nanosheets are in close contact with UMOFNs, and there is a certain interaction between them, showing the effect of superimposition on the two-dimensional layer. The 2D-2D heterostructure offers a maximal photocatalytic hydrogen production activity of 1909.02 μmol g⁻¹ h⁻¹ with 3 wt% of UMOFNs, which is 3-fold higher than that of g-C₃N₄ nanosheets (628.76 μmol g⁻¹ h⁻¹) and 15-flod higher than that of bulk g-C₃N₄ (124.30 μmol g⁻¹ h⁻¹). The significant increasement of photocatalysis is due to 2D-2D heterostructure possessing a short charge transfer distance and large contact area between g-C₃N₄ and UMOFNs. The highly dispersed NiO, CoO and π-π bonds in UMOFNs of 2D-2D structure also promote charge transfer and enhance the photocatalytic activity.     

In- situ solid-phase fabrication of Ag/AgX (X=Cl,Br, I)/g-C3N4 composites for enhanced visible-light hydrogen evolution

In this work, a series of Ag/AgX (X = Cl, Br, I)/g-C₃N₄ (Ag/AgX/CN) composites were successfully fabricated by an in-situ solid phase method. The morphology and structure, photoluminescence and photoelectrochemical properties of composites were investigated in detail. The as-prepared Ag/AgX/CN composites were used as H₂ evolution photocatalysts under visible-light irradiation with a sacrificial agent. The experimental results revealed that Ag/AgI/CN-4 composite possesses highest-H₂ evolution rate (up to 59.22 μmol g⁻¹ h⁻¹) which are approximately 31 times higher than that of pure g-C₃N₄ (1.94 μmol g⁻¹ h⁻¹). In addition, Ag/AgCl/CN-4 and Ag/AgBr/CN-4 composites also present high photocatalytic activities yielding, 26.39 and 18.05 μmol_H2 g⁻¹ h⁻¹_, respectively. The enhanced photocatalytic activities of Ag/AgI/CN-4 composite might be attributed to the synergistic effect between Ag/AgI nanoparticles and g-C₃N₄ and the localized surface plasmon resonance effect of metallic Ag. Moreover, Ag/AgI/CN-4 composite showed excellent recyclability and stability after five cycling photocatalytic tests (about 25 h). Furthermore, the possible photocatalytic mechanism of Ag/AgI/CN composites is proposed.     

Facile synthesis of CeO2/g-C3N4 nanocomposites with significantly improved visible-light photocatalytic activity for hydrogen evolution

Ceria dioxide supported on graphitic carbon nitride (CeO₂/g-C₃N₄) composites were facilely synthesized to be application for photocatalytic hydrogen (H₂) generation in this present work. The physical and chemical properties of CeO₂/g-C₃N₄ nanocomposites were determined via a series of characterizations. The CeO₂/g-C₃N₄ composites prepared by facile thermal annealing and rotation-evaporation method exhibit excellent photocatalytic H₂ evolution with visible-light illumination. The best hydrogen generation rate of CeO₂/g-C₃N₄ composite with 1.5 wt% Pt is 0.83 mmol h⁻¹ g⁻¹, which is almost same as that of composite with 3 wt% Pt prepared by simple physical mixing method. The significantly developed photocatalytic activity of CeO₂/g-C₃N₄ composite is majorly ascribed to the stronger interfacial effects with the more visible-light absorbance and faster electron transfer. This work reveals that construction of the CeO₂/g-C₃N₄ composite with high disperse and close knit by the facile thermal annealing and rotation-evaporation method could be an effective method to achieve excellent photocatalytic hydrogen evolution performance.     

High-efficiency of novel hierarchical 3D macroporous g-C3N4 material on solar-driven photocatalytic water-splitting for hydrogen evolution

The use of multi-pore nanostructured g-C₃N₄ photocatalysts is an efficient approach to separate photogenerated charge carriers and increase visible light photocatalytic performance. Recent progress has yielded nanostructured material through hard templating, which limits potential applications. Integrating the 2D building block into multidimensional porous structures remains a significant challenge in scalable production. Herein, a novel technique based on P407 bubble clusters templating and fixation by freezing is described for the first time to fabricate a 3D opened-up macroporous g-C₃N₄ nanostructures for photocatalytic H₂ evolution. Three-dimensional hierarchical nanostructures provide more contact active sites and synergistically promote the creation of heterogeneous catalytic interfaces. This feature is very useful for understanding the transfer path of photoinduced charges as well as the origins of the high charge separation efficiency in photocatalytic reactions, thus yielding a remarkable visible light-induced H₂ evolution rate of 4213.6 μmol h⁻¹ g⁻¹, which is nearly 5.6 times (716 μmol h⁻¹ g⁻¹) higher than that of lamellar bulk g-C₃N₄. This newly developed approach offers a promising alternative to synthesize broad-spectral response 3D hierarchal g-C₃N₄ nanostructures and can be extended to assemble other functional nanomaterials as building blocks into macroscopic configurations coupled with electronic modulation strategy simultaneously.     

Rational design of plasmonic Ag@CoFe2O4/g-C3N4 p-n heterojunction photocatalysts for efficient overall water splitting

Highly efficient and direct photocatalytic H₂ evolution from water via water splitting without using sacrificial reagents is a challenging approach to convert solar energy into renewable and storable chemical energy. Herein, by amalgamating the architecture recommendations and energy band engineering principles into the design formulation, a novel Ag@CoFe₂O₄/g-C₃N₄ plasmonic p-n heterojunction photocatalytic system is designed and constructed for the first time. The Ag@CoFe₂O₄/g-C₃N₄ photocatalyst so designed, under the illumination of the visible-light (λ > 420 nm), produced H₂ and O₂ in 2:1 stoichiometric amount at the rates of 335 μmol h^?1 and 186 μmol h^?1, respectively, with an apparent quantum yield reaching 3.35% at 420 nm, demonstrating that Ag@CoFe₂O₄ dimer colloids are responsible for oxidation and g-C₃N₄ for reduction. Moreover, in the presence of triethanolamine, the apparent quantum yield achieved by Ag@CoFe₂O₄/g-C₃N₄ is 16.47% with hydrogen produced at the rate 3.5 times higher than the CoFe₂O₄/g-C₃N₄ heterojunction photocatalyst with AQY of 5.49%. The combination of Ag plasmonic effect and internal electric field established at the interface of p-type CoFe₂O₄ and n-type g-C₃N₄ boosts the separation efficiency of photoexcitons from CoFe₂O₄ to g-C₃N₄, extending the visible-light absorption capacity of the systems. The generation of optimum amount of defects like oxygen vacancies at the p-n heterojunction interface due to the structural distortion of CoFe₂O₄ also plays a prominent photocatalytic enhancement by providing active sites for the adsorption of water molecules for the light driven catalytic reactions. Our work introduces a potential avenue to design efficient photocatalysts by constructing several other suitable p-n heterojunction semiconductor photocatalysts toward practical application in solar energy conversion.     

The synergistic effect of potassium ions and nitrogen defects on carbon nitride for enhanced photocatalytic hydrogen evolution

Ion doping is an effective method to improve the photocatalytic activity of graphitic carbon nitride (g-C₃N₄) by providing a photocarriers transfer channel. But limited by the bonds in heptazine rings, photoelectrons are still trapped in the structure. Therefore, both potassium ions and nitrogen defects were successfully introduced into g-C₃N₄ by high temperature calcination to accelerate the charges transfer between both interlayers and intralayer of g-C₃N₄. The results showed that the hydrogen production rate of g-C₃N₄ modified simultaneously by nitrogen defects and potassium ions reaches 1722.4 μmol·g⁻¹·h⁻¹, which is 8 times that of pristine g-C₃N₄. Based on various characterization techniques and DFT calculations, we attributed the enhanced photocatalytic hydrogen evolution to the improved light adsorption, more delocalized HOMO-LUMO, and stronger interlayer interactions. This work will provide a promising way to enhance photocatalytic hydrogen evolution of g-C₃N₄ and a possible mechanism was proposed.     

Melamine-phytic acid derived supramolecular synthesis of g-C3N4 for enhanced solar hydrogen evolution

It is an effective approach to regulate the structure of photocatalysts by introducing the heteroatoms into the lattice for extended light absorption and enhanced charge separation. In this work, the P atoms were introduced to substitute the corner C atoms of g-C₃N₄ by calcinating the melamine-phytic acid derived supramolecular with high-density phosphate groups, which is synthesized by hydrothermal method. The intermediate state produced by the introduction of P atoms leads to the enhanced light absorption of P–CN_(7.2g-IP6) with a negative shifted conduction band position, which benefits the photocatalytic hydrogen reaction kinetically. Moreover, the electron transferred from P atom to the surrounding N atoms results in the positively charged P center, which could act as Lewis acid site. Such formed Lewis acid site at positively charged P center together with the Lewis base sites, such as amine or imine groups in P–CN, makes it easier to separate photogenerated charges, thus enabling the P–CN_(7.2g-IP6) to exhibit an enhanced photocatalytic hydrogen rate of 2.743 mmol·g⁻¹·h⁻¹, which is about 6.77 times that of pristine g-C₃N₄ (0.405 mmol·g⁻¹·h⁻¹). This work provides an alternative approach to regulating the structure of photocatalysts.     

Interfacial engineering to construct 2D-2D NiCo-LDH/g-C3N4 heterojunctions for enhanced photocatalytic hydrogen production performance

Photocatalytic water splitting provides a green method to solve the energy shortage issue. Combine two-dimensional carbon nitride nano sheets with other two-dimensional semiconductors can effectively increase the construct area and improve the utilization of photogenerated charges. Herein, 2D-2D NiCo-LDH/g-C₃N₄ composites were successfully prepared by a simple hydrothermal method. The lamellar NiCo-LDH was grown in situ on g-C₃N₄, in which way the hydrogen production rate was enhanced by about 21 times, reaching 755 μmol·g⁻¹·h⁻¹. According to the results of density functional theory （DFT） calculations, an S-type heterojunction is successfully constructed, which achieves the spatial separation of semiconductor photogenerated electron-hole with guaranteed strong redox capability. This work emphasizes that effective transport channels for transfer and separation of photogenerated charges can be created through efficient interfacial regulation strategy.     

Direct Z-scheme CoS/g-C3N4 heterojunction with NiS co-catalyst for efficient photocatalytic hydrogen generation

Facilitating the separation of photoexcited electron-hole pairs and enhancing the migration of photogenerated carriers are essential in photocatalytic reaction. CoS/g-C₃N₄/NiS ternary photocatalyst was prepared by hydrothermal and physical stirring methods. The optimized ternary composite achieved a hydrogen yield of 1.93 mmol g^?1 h^?1, 12.8 times that of bare g-C₃N₄, with an AQE of 16.4% at 420 nm. The enhanced photocatalytic activity of CoS/g-C₃N₄/NiS was mainly ascribed to the synergistic interaction between the Z-scheme heterojunction constructed by CoS and g-C₃N₄ and the NiS co-catalyst featuring a large amount of hydrogen precipitation sites, which realized the efficient separation and migration of photogenerated carriers. In addition, the CoS/g-C₃N₄/NiS heterojunction-co-catalyst system exhibited excellent photocatalytic stability and recyclability.     

Electron transfer via a carbon channel for efficient Z-scheme solar hydrogen production

Z-scheme photocatalysis provides a promising solution to photocatalytic solar water splitting, yet restricted by inferior interfacial charge transfer. Here, we demonstrate a Z-scheme composite photocatalyst made of Fe₂O₃, a carbon layer, and g-C₃N₄ that can achieve efficient hydrogen generation from solar water decomposition. The success relies on in-situ preparation of core-shell Fe₂O₃@C structure at the surface of g-C₃N₄. Carbon as an intermediate layer thus acts as a bridge that significantly accelerates the migration of photogenerated electrons from Fe₂O₃ conduction band to g-C₃N₄ valence band. As a result, the highest rate of H₂ generation reaches 5.26 mmol h⁻¹g⁻¹. This activity is approximately 33-time greater than that achieved over pristine g-C₃N₄ and about 4-time larger than that obtained over a Fe₂O₃/g-C₃N₄ heterojunction without internal carbon layer. This work explicates the potential insight of the composite and paves a promising way to engineer the charge transfer behavior.     

Facile synthesis of anatase/rutile TiO2/g-C3N4 multi-heterostructure for efficient photocatalytic overall water splitting

Rational design of high-efficiency heterostructure photocatalyst is an effective strategy to realize photocatalytic H₂ evolution from pure water, but remains still a considerable challenge. Herein, an anatase/rutile TiO₂/g-C₃N₄ (A/R/CN) multi-heterostructure photocatalyst was prepared by a facile thermoset hybrid method. The combination of two type-II semiconductor heterostructures (i.e., A/R and R/CN) significantly improve the separation and transfer efficiency of photogenerated carriers of anatase TiO₂, rutile TiO₂ and g-C₃N₄, and A/R/CN photocatalyst with high activity is obtained. The optimal A/R/CN photocatalyst exhibits significantly increased photocatalytic overall water splitting activity with a rate of H₂ evolution of 374.2 μmol g⁻¹h⁻¹, which is about 8 and 4 times that of pure g-C₃N₄ and P25. Moreover, it is demonstrated to be stable and retained a high activity (ca. 91.2%) after the fourth recycling experiment. This work comes up with an innovative perspective on the construction of multi-heterostructure interfaces to improve the overall photocatalytic water splitting performance.