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.     

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.     

One-pot hydrothermal synthesis of CdS/NiS photocatalysts for high H2 evolution from water under visible light

The development of efficient and stable noble-metal-free photocatalysts is crucial for hydrogen evolution from water splitting as clean energy. This study reports uniform CdS/NiS spherical nanoparticles through a simple one-pot hydrothermal method with the aid of KOH. The prepared CdS/NiS composites show superior photocatalytic activities toward the water splitting under visible light. A suitable amount of KOH in the synthesis benefits to form CdS/NiS photocatalysts with the improved activity. The CdS/NiS composite including 10 mol% metal percentage of Ni exhibits the highest photocatalytic activity. The high hydrogen evolution rate of 24.37 mmol h^?1 g^?1 is achieved over the CdS/NiS composite photocatalyst. The CdS/NiS photocatalyst has good photocatalytic stability in the recycling uses. The present CdS/NiS as a noble-metal-free photocatalyst provides the superior visible-light driven catalytic activity for hydrogen evolution.     

Experiments combined with theoretical research on the effect of hydrogen evolution by the nanosheet of NiS–CdS–CN catalyst

A ternary composite photocatalyst of nickel sulfide supported on the heterojunction of ultrathin cadmium sulfide-carbon based on g-C₃N₄ nanosheets was prepared by aqueous-phase in low-temperature innovatively, and its chemical compositions were confirmed by XRD, FT-IR and XPS. The morphology of two-dimensional nanosheet heterojunction was verified by SEM, TEM, HRTEM and BET, and the addition of nickel is beneficial to improve the specific surface area of the catalyst. The larger surface area was more beneficial to accelerate the carrier migration and reactant diffusion. Meanwhile, the electron structures were analyzed by UV–vis, work function, bader charge and ELF charge calculated by GGA-PBE, which proved that the electrons at heterojunction interface of CdS–C₃N₄ were transferred from g-C₃N₄ to CdS, and the strong interaction existed in two layers between CdS and g-C₃N₄ by reformed the bonds of Cd–N, and the doping Ni can regulate the interface electron transport mechanism of CdS–C₃N₄ heterojunction. The hydrogen evolution performance showed that the ternary composite photocatalyst was better than both of the single system of cadmium sulfide or carbon nitride and the binary system containing NiS–CdS or CdS–C₃N₄. Through the characterization and theoretical calculation of the results, we found that the synergistic effect of NiS–CdS–C₃N₄ system could solve the problems of high recombination rate of photo-electrons and holes, and insufficient active sites existing in single materials of g-C₃N₄ or CdS during the photocatalytic reaction.     

Interfacial optimization of CeO2 nanoparticles loaded two-dimensional graphite carbon nitride toward synergistic enhancement of visible-light-driven photoelectric and photocatalytic hydrogen evolution

A novel series of CeO₂ nanoparticles (CeNP) loaded two-dimensional (2D) graphite carbon nitride nanosheet (CeNP/g-C₃N₄) composites which possess heterojunction are prepared with different proportions of CeNP by a reliable and straightforward method. The samples were employed to degrade the rhodamine B (RhB) and produce hydrogen. The microstructure, morphology, composition and surface chemical states of the samples are analyzed, and the ability of the photoelectric response is characterized. The characterization ensures uniform loading of CeNP over the g-C₃N₄ surface and a co-existence of Ce³⁺/Ce⁴⁺ in the CeNP/g-C₃N₄ composite. The FT-IR spectra have revealed the changes in the local dipole moment of amino groups, vibration mode of the constituent functional group and electronegativity, indicating the electric interaction between CeNP and g-C₃N₄. The photocatalytic hydrogen evolution efficiency of the CeNP/g-C₃N₄ increased initially and then decreased with the increasing of loaded CeNP. The CeNP/g–C₃N₄–C with 20 mg of CeNP was found to be the optimum proportion, which exhibited outstanding separation efficiency of the photo-generated carriers. The electron spin-resonance (ESR) spectra exhibit that the production of superoxide free radicals (?O₂^?) was much higher than that of hydroxyl free radicals (?OH) indicating that ?O₂^? species play a predominant role in the photocatalytic action. The mechanism for enhanced photocatalytic activity of the CeNP/g-C₃N₄ is attributed to the interfacial optimization, which improved the photo-generated carrier separation.     

Well-designed NiS/CdS nanoparticles heterojunction for efficient visible-light photocatalytic H2 evolution

Heterojunction photocatalysts based on semiconducting nanoparticles show excellent performance in many photocatalytic reactions. In this study, 0D/0D heterojunction photocatalysts containing CdS and NiS nanoparticles (NPs) were successfully synthesized by a chemical precipitation method. The NiS NPs were grown in situ on CdS NPs, ensuring intimate contact between the semiconductors and improving the separation efficiency of hole-electron pairs. The obtained NiS/CdS composite delivered a photocatalytic H₂ evolution rate (7.49 mmol h^?1 g^?1), which was 39.42 times as high as that of pure CdS (0.19 mmol h^?1 g^?1). This study demonstrates the advantages of 0D/0D heterojunction photocatalysts for visible light-driven photocatalytic hydrogen production.     

Mesoporous g-C3N4 decorated by Ni2P nanoparticles and CdS nanorods together for enhancing photocatalytic hydrogen evolution

Ni₂P nanoparticles and CdS nanorods were grew together on a mesoporous g-C₃N₄ through a facile in-situ solvothermal approach. Under visible light (λ > 400 nm), the as-prepared ternary PCN–CdS-5% Ni₂P composite displays a high H₂ evolution rate with 2905.86 μmol g^?1 h^?1, which is about 14, 18 and 279 times that of PCN–CdS, PCN–Ni₂P and PCN, respectively. The enhanced photocatalytic activity is mainly attributed to the improved separation efficiency of the photocarriers by the type II PCN–CdS heterojunction and the effective extraction of photogenerated electrons by Ni₂P. Meanwhile, Ni₂P acts as co-catalyst to provide the photocatalytic active site for hydrogen reduction. In addition, PCN–CdS-5% Ni₂P composite exerts good stability in 12-h cycles.     

Increased photocatalytic hydrogen evolution and stability over nano-sheet g-C3N4 hybridized CdS core@shell structure

A novel visible-light-active CdS@g-C₃N₄ photocatalyst was synthesized via a chemisorption method. This core@shell structure catalyst exhibited enhanced photocatalytic H₂ production activity under visible-light (λ ≥ 420 nm) irradiation. The nano-sheet g-C₃N₄ was successfully coated on CdS nanoparticles with intimate contact. When the content of g-C₃N₄ in the hybridized composite is 3 wt. %, the hydrogen-production rate of the CdS@g-C₃N₄ is 2.5 and 2.2 times faster than pure CdS and bulk g-C₃N₄, respectively. Superior stability was also observed in the cyclic runs. The improvement in stability and activity result from the ability of the π-conjugated g-C₃N₄ material in transporting photo-induced holes. The core@shell structure promoted separation of the photo-generated electron-hole pair and accelerated the emigration speed of the hole from the valence band of CdS. This effect also results in a greatly improved amount of hydrogen production. The possible mechanism for the photocatalytic activity and stability of CdS@g-C₃N₄ are tentatively proposed.     

In-situ growth of CdS quantum dots on g-C3N4 nanosheets for highly efficient photocatalytic hydrogen generation under visible light irradiation

Well dispersed CdS quantum dots were successfully grown in-situ on g-C₃N₄ nanosheets through a solvothermal method involving dimethyl sulfoxide. The resultant CdS–C₃N₄ nanocomposites exhibit remarkably higher efficiency for photocatalytic hydrogen evolution under visible light irradiation as compared to pure g-C₃N₄. The optimal composite with 12 wt% CdS showed a hydrogen evolution rate of 4.494 mmol h⁻¹ g⁻¹, which is more than 115 times higher than that of pure g-C₃N₄. The enhanced photocatalytic activity induced by the in-situ grown CdS quantum dots is attributed to the interfacial transfer of photogenerated electrons and holes between g-C₃N₄ and CdS, which leads to effective charge separation on both parts.     

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.     

Facile strategy to fabricate Ni2P/g-C3N4 heterojunction with excellent photocatalytic hydrogen evolution activity

Transition metal phosphides are considered as the most prospective replacements for noble metal cocatalysts used for H₂ evolution during photocatalytic water splitting. In this work, Ni₂P/g-C₃N₄ composite photocatalyst was synthesized using a simple in-situ hydrothermal method by one step. Benefiting from the excellent light trapping, efficient transfer of charge carriers and strong stability of Ni₂P nanoparticles, as well as the stable interface contact between Ni₂P and g-C₃N₄, the Ni₂P/g-C₃N₄ exhibit greatly enhanced H₂ evolution performance during photocatalytic water splitting. The optimized H₂ evolution rate can reach 3344 μmol h^?1 g^?1 over 17.5 wt% Ni₂P/g-C₃N₄, which is 68.2 times greater than that of pure g-C₃N₄ and even much greater than that of 15 wt% Pt/g-C₃N₄. The apparent quantum efficiency (QE) is about 9.1% under 420 nm monochromatic. The enhancement mechanism was demonstrated in detail by transient photocurrent responses, photoluminescence spectra and electrochemical impedance spectroscopy. This work develops a facile strategy to fabricate transition metal phosphide/semiconductor heterojunction systems with potential application for photocatalytic H₂ evolution.     

In-situ growth of mesoporous Nb2O5 microspheres on g-C3N4 nanosheets for enhanced photocatalytic H2 evolution under visible light irradiation

Large-surface-area mesoporous Nb₂O₅ microspheres were successfully grown in-situ on the surface of g-C₃N₄ nanosheets via a facile solvothermal process with the aid of Pluronic P123 as a structure-directing agent. The resultant g-C₃N₄/Nb₂O₅ nanocomposites exhibited enhanced photocatalytic activity for H₂ evolution from water splitting under visible light irradiation as compared to pure g-C₃N₄. The optimal composite with 38.1 wt% Nb₂O₅ showed a hydrogen evolution rate of 1710.04 μmol h^?1 g^?1, which is 4.7 times higher than that of pure g-C₃N₄. The enhanced photocatalytic activity could be attributed to the sufficient contact interface in the heterostructure and large specific surface area, which leads to effective charge separation between g-C₃N₄ and Nb₂O₅.     

Manganese dioxides with different exposed crystal plane supported on g-C3N4 for photocatalytic H2 evolution from water splitting

A series of MnO₂/g-C₃N₄ composites with different exposed crystal plane were successfully prepared by different synthesized method. UV–Vis, PL, ESR and electrochemical results suggest that the visible-light absorbance, photoexcited electron-separation efficiency and oxygen defects are greatly dependent on the exposed crystal-faceted MnO₂ supported on g-C₃N₄. The experimental results display that the exposed crystal plane of MnO₂ have great influences on the photocatalytic hydrogen evolution performance, and the m-MnOCN composite with exposed (111) crystal plane exhibits superior photocatalytic performance for the release of H₂ under visible light irradiation, followed by the order of b-MnOCN [002]> p-MnOCN [110]. Moreover, Mechanism studies have shown that the possible mechanism of photocatalytic hydrogen evolution reaction is Z-scheme mechanism.     

1T-phase MoS2/holey ultrathin g-C3N4 nanosheets based 2D/2D heterostructure for enhanced photocatalytic hydrogen production

Although graphitic carbon nitride (g-C₃N₄) is widely used for photocatalytic hydrogen production, its practical application is restricted by the high recombination rate of photoinduced electron-hole pairs and limited active sites. In this work, holey ultrathin g-C₃N₄ nanosheets (HCN NSs) with rich active sites are prepared, followed by the growth of 1T-MoS₂ NSs on their surfaces to construct 2D/2D 1T-MoS₂/HCN heterostructure. Due to the high surface area and abundant hydrogen active sites of the hybrid, large and intimate 2D nanointerface between MoS₂ and HCN, hydrogen ion adsorption and charge separation/transport ability are greatly enhanced. As a result, 1T-MoS₂/HCN-4 with the optimal 1T-MoS₂ content of 8 wt% displays the highest H₂ production rate of 2724.2 μmol^?1 h^?1 g^?1 under simulated solar light illumination with apparent quantum efficiency of 8.1% (λ = 370 nm). Moreover, the 1T-MoS₂/HCN-4 hybrid manifests improved stability after a long-time test. This study opens the door to design highly-efficient g-C₃N₄ based 2D/2D heterostructures for photocatalytic H₂ production.     

Ag–AgBr/g-C3N4/ZIF-8 prepared with ionic liquid as template for highly efficient photocatalytic hydrogen evolution under visible light

In this study, a ternary photocatalyst named Ag–AgBr/g-C₃N₄/ZIF-8 (A/g/Z) was prepared by ionic liquid assisted in-situ growth method. The structure and composition of samples are studied by means of XRD, SEM, XPS, TEM, EIS, etc. The AgBr prepared by ionic liquid assisted method has good dispersion, and the protonated carbon nitride has better specific surface area and morphology structure. The structure of the composites is optimized by modifying g-C₃N₄ with MOFs and noble metals, and the existence of Ag⁺ can play a bridging role, so as to form multi-path electronic transmission route. The high efficiency of electron transfer greatly improved the efficiency of hydrogen evolution. It is worth noting that the surface plasmon resonance (SPR) effect produced by silver ions on the surface of g-C₃N₄ can improve the absorption of visible light. The A (1.1)/g/Z (6.5) exhibit high hydrogen evolution efficiency (2058 μmol g^?1 h^?1, which is 49 times than g-C₃N₄) at the absence of Pt co-catalyst. Furthermore, the transient photocurrent density of the composites is much higher than that of g-C₃N₄ and AgBr, the semicircle radius of EIS is also less than both. Through the five cycle experiment, the photocatalytic efficiency of the composite material remained above 91%.     

Facial synthesis of dandelion-like g-C3N4/Ag with high performance of photocatalytic hydrogen production

Nowadays, energy shortage is one of the major problems in the world. Photocatalytic hydrogen production is a new type of energy technology with good application prospect. As a new type of photocatalytic semiconductor material, g-C₃N₄ has attracted much attention as a photocatalyst. By ultrasonic treatment of a mixed solution of g-C₃N₄ and bovine serum albumin, followed by adding a certain amount of silver nitrate solution and then directly hydrothermal treatment, a special dandelion-like g-C₃N₄/Ag (D-g-C₃N₄/Ag) was prepared. The scanning electronic microscopy, transmission electronic microscopy, X-ray diffraction, Fourier transform infrared, fluorescence and physicochemical adsorption methods were used to characterize the morphology and structure of D-g-C₃N₄/Ag. In addition, the photocatalytic H₂ production of D-g-C₃N₄/Ag with different Ag loadings or in different sacrificial agents and different pH conditions were investigated. The results indicated that when triethanolamine was used as sacrificial agent, photocatalytic hydrogen efficiency was the best, and the rate of photocatalytic hydrogen production reached 862 μmol g⁻¹ h^{− 1} as the Ag loading was 4%.     

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.     

Fabrication of CdS/Zn2GeO4 heterojunction with enhanced visible-light photocatalytic H2 evolution activity

CdS/Zn₂GeO₄ (CG) composites were synthesized through the simple hydrothermal process. The crystal structure, morphology and light absorption property of the products were studied in detail. The CG composites showed excellent photocatalytic hydrogen production performance upon visible light illumination. Especially, the CG-3 composite displayed the highest H₂ evolution rate of 1719.8 μmol h⁻¹ g⁻¹, which was about 3.80 and 4.28 times higher than the pure CdS and Zn₂GeO₄. Besides, the cyclic stability of the CG-3 composite was also excellent. The PL, photocurrent response and EIS spectra results testified that the efficient separation and transfer of photoinduced charge carriers achieved between CdS and Zn₂GeO₄, which could result in the promotion of photocatalytic performance. Moreover, a possible mechanism of H₂ generation over CdS/Zn₂GeO₄ heterojunction was discussed. The practicable way to construct heterojunction composites would be helpful for the design of other systems with excellent photocatalytic property.     

Two-dimensional carbon nitride-based composites for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution plays a critical role in the exploration of the clean and sustainable energy. Owing to its special structure and features, two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) has attracted tremendous attention. However, some deficiencies of pristine g-C₃N₄ inhibit its photocatalytic application, particularly the low quantum efficiency of hydrogen evolution. Therefore, it is valuable to develop 2D new composites based on g-C₃N₄ so that the synergistic effects of the two original materials can be achieved. This article attempts to summarize the modification strategies of 2D g-C₃N₄-based composites, including the construction of heterojunctions, morphology control, doping method, surface modification and co-catalyst loading. The application and progress in photocatalytic hydrogen evolution are also highlighted. The limitations are taken into account to provide further information for the improvement in the quantum efficiency of hydrogen by 2D g-C₃N₄-based composites.     

Enhanced hydrogen production properties of a novel aluminum-based composite for instant on-site hydrogen supply at low temperature

Al-water reaction for hydrogen production faces the problems of long induction time and low conversion efficiency at low temperature (below 273.15 K), which has seriously limited its applications. To realize the instant hydrogen production of Al composites at low temperature, low melting point metals (Ga, In, Sn) and additives (NaCl, g-C₃N₄, LiH) were selected to prepare Al composites with high reactivity. Compared with the other Al composites, Al alloy/NaCl/LiH/g-C₃N₄ composites exhibit the enhanced low temperature hydrogen production performance in 23 wt% NaCl aqueous solution at 253.15 K. For all Al alloy/NaCl/LiH/g-C₃N₄ composites, the induction time of Al-water reaction at 253.15 K has completely eliminated. The highest hydrogen generation volume of 1095 mL·gAl^?1 and the maximum hydrogen generation rate of 120 mL·gAl^?1·s^?1 were obtained for Al alloy/NaCl/1.5%LiH/g-C₃N₄ composite. It is proposed that LiH can induce Al-water reaction instantly starting at 253.15 K. The released heat and micro alkaline environment further promote the Al-water reaction and enhance the hydrogen conversion efficiency. In particular, g-C₃N₄ additive can improve the antioxidant properties of Al composites. This study provides a novel way for the development and application of Al composites in real-time hydrogen production at low temperature.