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.     

Construction of 1D/0D/2D Zn0.5Cd0.5S/PdAg/g-C3N4 ternary heterojunction composites for efficient photocatalytic hydrogen evolution

A high-efficiency and easy-available approach was developed to obtain a ternary heterojunction composites with advanced hydrogen evolution reaction (HER) performance under visible light by water split. PdAg bimetallic nanoparticles make a close contact interface between g-C₃N₄(CN) and Zn_0.5Cd_0.5S(ZCS). Under visible light irradiation, CN and ZCS are both excited to generate electron-hole pairs, PdAg bimetallic nanoparticles act as a bridge between CN and ZCS. Not only can the photogenerated electrons from CN be captured, but they can also be quickly transferred to the surface of ZCS and participate in the photocatalytic reaction to release H₂, and the recombination of charge carriers between the contact interface of ZCS and CN can be significantly inhibited. In addition, the thin CN layer reduces the photocorrosion of the ZCS and enhances the specific surface area of the composite material. After testing, the composite material with 30 wt% ZCS and 4 wt% PdAg demonstrates hydrogen evolution performance, up to 6250.7 μmol g^?1h^?1, which is 753 times the hydrogen evolution rate of single-component CN and 12.6 times of ZCS/CN. Compared with single-component and two-component photocatalysts, the ternary ZCS/PdAg/CN photocatalyst achieves significantly enhanced photocatalytic activity.     

Construction of carbon dots modified hollow g-C3N4 spheres via in situ calcination of cyanamide and glucose for highly enhanced visible light photocatalytic hydrogen evolution

In this work, a series of carbon dots (CDs) modified hollow g-C₃N₄ spheres (HCNS-C_x) were constructed via a double in situ approach using cyanamide and glucose as precursors, respectively. As HCNS-C_x was synthesized by one-step in situ thermal polymerization of two precursors, which could make CDs and g-C₃N₄ keep tight connection and increase the separation of the photogenerated electron-hole pairs. The average diameter and wall thickness of the HCNS-C_x are about 355 nm and 55 nm, respectively. Under the visible light irradiation, the H₂ evolution rate (HER) of HCNS-C_1.0 (2322 μmol g^?1 h^?1) was 19 times that of bulk g-C₃N₄ (122 μmol g^?1 h^?1) and 1.8 times that of HCNS without CDs modification (1289 μmol g^?1 h^?1), respectively. And its apparent quantum efficiency is 17.93% at 420 nm. The specific surface area, light absorption capacity, and charge carrier mobility of HCNS-C_x could be dramatically improved due to the introduction of CDs and hollow structures of g-C₃N₄ spheres, resulting in a significant improvement of photocatalytic activity.     

g-C3N4/B doped g-C3N4 quantum dots heterojunction photocatalysts for hydrogen evolution under visible light

Developing high activity and eco-friendly photocatalysts for water splitting is still a challenge in solar energy conversion. In this paper, B doped g-C₃N₄ quantum dots (BCNQDs) were prepared via a facile molten salt method using melamine and boron oxide as precursors. By introducing BCNQDs onto the surface of g-C₃N₄, g-C₃N₄/BCNQDs heterojunction was constructed via hydrothermal treatment. The resulting g-C₃N₄/BCNQDs heterojunction exhibits enhanced hydrogen evolution performance for water splitting under visible light irradiation. The mechanism underlying the improved photocatalytic activity was explored and discussed based on the formation of heterojunction between g-C₃N₄ and BCNQDs with well-matched band structure.     

Novel up-conversion N,S co-doped carbon dots/g-C3N4 photocatalyst for enhanced photocatalytic hydrogen evolution under visible and near-infrared light

In photocatalytic splitting water for hydrogen evolution, narrow light response range and fast electron-hole recombination of g-C₃N₄ (CN) limit its photocatalytic activity. In this article, the N, S co-doped carbon dots (NSCDs) with up-converted property were loaded on CN nanosheets by thermal polymerization to obtain NSCDs/CN composite catalyst. Characterization, electrochemical researches and hydrogen evolution tests suggest that the photocatalytic activity of CN is greatly promoted by the introduction of NSCDs. Under visible and near-infrared irradiation, the hydrogen evolution rate is 5033.1 μmol g^?1 h^?1 of NSCDs-5/CN, which is 8.3 times higher than that of CN. The performance improvement is mainly attributed to the increased specific surface area, elevated hydrophilic surface, increased light absorption and suppressed carrier recombination of CN after the introduction of NSCDs. This work unveils the mechanism of the hydrogen evolution activity improvement in NSCDs-5/CN, and also offers a new prospect in the design of high-performance CN-based photocatalysts.     

Active-center-enriched Ni0.85Se/g-C3N4 S-scheme heterojunction for efficient photocatalytic H2 generation

Photocatalysts with abundant active sites are essential for photocatalytic H₂ evolution from water. Herein, Ni_0.85Se-deposited g-C₃N₄ was obtained by a physical solvent evaporation method. The investigation shows that Ni_0.85Se with unsaturated active Se atoms can significantly improve the photocatalytic activity of g-C₃N₄, and the H₂ production rate of Ni_0.85Se/g-C₃N₄ can reach 8780.3 μmol g^?1 h^?1, which is 3.5 and 92.9 times higher than that of Ni_0.85+xSe/g-C₃N₄ (2497.9 μmol g^?1 h^?1) and pure g-C₃N₄ (94.5 μmol g^?1 h^?1), respectively. This improvement can be attributed to the quick charge transfer between Ni_0.85Se and g-C₃N₄ with S-scheme heterojunction feature based on a series of trapping experiments and photoelectrochemical analysis. Moreover, abundant unsaturated Se atoms could provide more H₂ evolution active sites. This work sheds light on the construction of heterojunctions with abundant active sites for H₂ production.     

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.     

Facile synthesis of noble-metal free polygonal Zn2TiO4 nanostructures for highly efficient photocatalytic hydrogen evolution under solar light irradiation

Designing of noble-metal free and morphologically controlled advanced photocatalysts for photocatalytic water splitting using solar light is of huge interest today. In the present work, novel polygonal Zn₂TiO₄ (ZTO) nanostructures have been synthesized by citricacid assisted solid state method for the first time and synthesized nanostructures were characterized by using various techniques like PXRD, UV-Vis-DRS, PL, FT-IR, BET, FE-SEM and TEM for their structural, optical, chemical, surface and morphological properties. The PXRD and UV-Vis-DRS analysis show the existence of cubic and tetragonal phases. FE-SEM and TEM results confirm the formation of polygonal ZTO nanostructures. Synthesised ZTO nanostructures have been potentially applied for solar light-driven photocatalytic hydrogen evaluation from water splitting and compare the photocatalytic activity with synthesized conventional Zn₂TiO₄ and commercially available TiO₂, ZnO photocatalysts. A high rate of 529 μmolh^?1g^?1 solar light-driven photocatalytic H₂ evolution has been achieved by using a small amount (5 mg) of polygonal Zn₂TiO₄ nanostructures from glycerol-water solution. The enhanced photocatalytic performance of the polygonal Zn₂TiO₄ nanostructures compare to conventional Zn₂TiO₄ under solar light irradiation is due to the large surface area and low recombination rate. However having the same bandgap, the polygonal Zn₂TiO₄ nanostructures have shown enhanced photocatalytic performance than that of commercially available TiO₂, ZnO photocatalysts.     

NiS2 Co-catalyst decoration on CdLa2S4 nanocrystals for efficient photocatalytic hydrogen generation under visible light irradiation

NiS₂ nanoparticles as noble metal-free co-catalysts were deposited onto the CdLa₂S₄ nanocrystals through a hydrothermal process. The loading of NiS₂ co-catalyst resulted in remarkable enhancement for H₂ production over the CdLa₂S₄ photocatalyst under visible light irradiation. The optimal hybrid photocatalyst with 2 wt% NiS₂ loading exhibited a H₂ production rate of 2.5 mmol h⁻¹ g⁻¹, which was more than 3 times higher than that of the pristine CdLa₂S₄ photocatalyst. The promoted photocatalytic H₂ production by NiS₂-loading is attributed to the enhanced separation of photogenerated electrons and holes as well as the activation effect of NiS₂ for H₂ evolution.     

Dye-sensitized black phosphorus nanosheets decorated with Pt cocatalyst for highly efficient photocatalytic hydrogen evolution under visible light

Although black phosphorous (BP) and its derived materials have shown great potential for application in photocatalytic H₂ evolution reaction (HER), their HER activity and stability still remains unsatisfied mainly due to the insufficient charge separation, the lack of surface active sites, and the defect-riched nature of BP. Herein, we report that BP nanosheets decorated with in situ grown Pt (BP NSs/Pt) could act as a highly efficient catalyst for photocatalytic H₂ evolution in an Erythrosin B (ErB)-sensitized system under visible light irradiation (≥450 nm) in the presence of triethanolamine (TEOA) as sacrificial electron donor. It is found that BP NSs can provide large surface area for the confined growth of Pt nanoparticles with a high dispersion and a reduced size but also stabilize the loaded Pt nanoparticles by covalent bonds at the BP NSs/Pt interfaces. Moreover, BP NSs offer a fast electron transfer pathway to facilitate the photocatalytic HER over in situ grown Pt catalyst. As a result, BP NSs/Pt catalyst exhibits ∼6 times higher H₂ evolution activity than free Pt nanoparticles and an apparent quantum yield (AQY) of 0.57% at 500 nm irradiation in ErB-TEOA system. This work indicates the potential of BP NSs as an effective 2D matrix to construct numerous high performance photocatalysts and photocatalytic systems.     

One-step preparation of halogenated aminobenzonitrile modified g-C3N4 via copolymerization and in situ halogen doping for highly enhanced visible light hydrogen evolution

A series of halogenated aminobenzonitrile modified graphitic carbon nitride (g-C₃N₄) was prepared by a one-step calcination of dicyandiamide and 2-amino-5-halogen-benzonitriles (X-ABN, X = F, Cl, Br or I, 1.67 wt% of dicyandiamide) together, and named as X-ABN-CN. The resulting X-ABN-CN photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ultraviolet–visible diffuse reflection spectroscopy, and photoluminescence spectroscopy. The characterization results indicated that X-ABN-CN have been successfully prepared, and the π-conjugated system and electronic structure of X-ABN-CN could be improved via copolymerization, Ullmann reaction and in situ halogen doping. Under visible light irradiation (λ > 400 nm), the photocatalytic activity of X-ABN-CN were much higher than that of pure g-C₃N₄ and increase with the increase of halogen atomic number. The hydrogen evolution rate of I-ABN-CN (131.4 μmol h⁻¹) was 7.4 times that of g-C₃N₄ (17.7 μmol h⁻¹). Furthermore, the corresponding mesoporous X-ABN-CN (X-ABN-MCN, X = F, Cl, Br or I) were prepared by using SiO₂ nanoparticles as template. As expected, I-ABN-MCN showed the highest photocatalytic activity in all mesoporous samples, which is about 8.8 times that of g-C₃N₄. The results manifest that the copolymerization, Ullmann reaction, in situ halogen doping and mesoporous structure could be integrated together to modify g-C₃N₄ by a simple one-step calcination process.     

Wet chemistry synthesis of CuFe2O4/CdSe heterojunction for enhanced efficient photocatalytic H2 evolution under visible irradiation

A heterostructure of CuFe₂O₄/CdSe was synthesized as H₂ evolution photocatalyst under visible light. The optical absorption onset of the CuFe₂O₄/CdSe heterostructures was red-shifted to 2.30–2.48 eV, compared to that of the bare CuFe₂O₄ (2.55 eV), leading to better utilization of visible light. Furthermore, the CuFe₂O₄/CdSe samples exhibited a higher specific surface area than the bare CuFe₂O₄, due to the introduction of CdSe nanospheres. Compared to the bare CuFe₂O₄, the CuFe₂O₄/CdSe heterostructure promoted H₂ production from water splitting. The enhanced photocatalytic performance of the CuFe₂O₄/CdSe catalyst was attributed to the more efficient charge separation and lower charge transfer resistance, confirmed by fluorescence decay measurements and Nyquist plots, respectively. The band alignment between CuFe₂O₄ and CdSe resulted in an interfacial p-n junction, which directed the electron transfer from CdSe to CuFe₂O₄ and the hole transfer from CuFe₂O₄ to CdSe, achieving improved spatial separation of charge carriers.     

Construction of Cu7.2S4/g-C3N4 photocatalyst for efficient NIR photocatalysis of H2 production

Graphite-like carbon nitride (g-C₃N₄) has been regarded as a promising photocatalyst for solar-to-chemical conversion. Nevertheless, the narrow absorption of light extremely limited its photocatalytic performance under near-infrared (NIR) irradiation. Herein, the Cu₇.₂S₄ with outstanding NIR absorption was successfully introduced to g-C₃N₄ nanosheets through a simple in-situ growth procedure. As expected, the constructed Cu_7.2S₄/g-C₃N₄ (CSCN) photocatalysts exhibit superior H₂ production activity of 82 μmol g⁻¹ h⁻¹ under NIR light irradiation (λ > 800 nm), which outperforms currently reported g–C₃N₄–based NIR-driven H₂ production systems. Especially, the optimal sample CSCN-5 displays a robust activity of 66 μmol g⁻¹ h⁻¹ at λ = 850 nm monochromatic light irradiation. The excellent photocatalytic performance is linked to the extended optical absorption as well as the efficient separation efficiency of photoinduced carriers, which are evidenced by the UV-visible absorption spectroscopy and photoelectrochemical test. This work provides an effective approach for constructing a Cu_7.2S₄/g-C₃N₄ photocatalytic system for the transformation of NIR solar energy into hydrogen.     

Construct organic/inorganic heterojunction photocatalyst of benzene-ring-grafted g-C3N4/CdSe for photocatalytic H2 evolution

Photocatalytic water splitting to produce hydrogen is a vital research direction for alleviating the energy crisis. Herein, benzene-ring grafted g-C₃N₄ nanotubes (Ph-g-C₃N₄) were prepared skillfully and coupled with CdSe nanoparticles which was realized efficiently hydrogen production. The addition of CdSe nanoparticles enhanced the stability of the catalytic system dispersion in water, and the absorbance of the composites catalyst CdSe/Ph-g-C₃N₄ (CPG) was enhanced. In addition, the CPG had been characterized to have low resistance and efficient photogenerated electron separation efficiency. The Ph-g-C₃N₄ nanotubes with a three-dimensional structure can provide an anchoring platform for CdSe nanoparticles and effectively prevent the agglomeration of CdSe. The constructed composites catalyst achieved the efficient transfer of photogenerated electrons as known from photoluminescence spectroscopy test analysis. When CdSe nanoparticles were anchored to Ph-g-C₃N₄, the electron transfer rate of the constructed composite was about twice that of the Ph-g-C₃N₄, which facilitates the hydrogen evolution reaction. The character and electron transfer pathways of the photocatalysts were investigated theoretically by performing density functional calculations. The finding provides a new idea for the doping of photocatalysts and the design of organic/inorganic heterojunction composites photocatalyst to achieve an efficient hydrogen production system.     

Heterostructured boron doped nanodiamonds@g-C3N4 nanocomposites with enhanced photocatalytic capability under visible light irradiation

Boron doped nanodiamonds (BDND) were coupled with graphitic carbon nitride (g-C₃N₄) nanosheets to form a heterojunction via a facile pyrolysis approach. The BDND@g-C₃N₄ heterojunction exhibits enhanced visible-light absorbance, improved charge generation/separation efficiency and prolonged lifetime of carriers, which lead to the enhanced photocatalytic activities for the hydrogen evolution and organic pollution under visible-light irradiation. The optimal H₂ evolution rate and apparent quantum efficiency at 420 nm of the BDND@g-C₃N₄ heterojunction is 96.3 μmol h⁻¹ and 6.91%, which is about 5 and 2 times higher than those of pristine g-C₃N₄ nanosheets (18.2 μmol h⁻¹ and 3.92%). No obvious decrease in hydrogen generation rate is observed in the recycling experiment due to the high photo-stabilization of the BDND@g-C₃N₄ composite. The degradation kinetic rate constant of organic pollution of the BDND@g-C₃N₄ structure is 0.1075 min⁻¹, which is 3 times higher compared to pristine g-C₃N₄. This work may provide a promising route to construct highly efficient non-metal photocatalysts for hydrogen evolution and organic pollution degradation under visible light irradiation.     

Boosted photogenerated carriers separation in Z-scheme Cu3P/ZnIn2S4 heterojunction photocatalyst for highly efficient H2 evolution under visible light

Developing low-cost, highly efficient and robust photocatalystic hydrogen evolution system is a promising solution to environmental and energy crisis. Herein, a Z-scheme Cu₃P/ZnIn₂S₄ heterojunction photocatalyst was successfully constructed for the first time via a facile solution-phase hybridization method. The optimized Cu₃P/ZIS composite exhibited the highest H₂ production rate of 2561.1 μmol g⁻¹ h⁻¹ under visible light irradiation (>420 nm), which was 5.2 times greater than that of bare ZnIn₂S₄ and even exceeded the photocatalytic performance of Pt/ZIS composite. The apparent quantum yield of 10 wt% Cu₃P/ZnIn₂S₄ can reach 22.3% at 420 nm. The huge boost of photocatalytic hydrogen evolution activity is ascribed to the formation of heterojunction with the built in electric field within Cu₃P/ZnIn₂S₄ and Z-scheme charge carriers transfer pathway, which result in efficient separation and migration of charge carriers. In addition, both experimental and theoretical calculation confirmed that the charge-carriers transfer pathway of Cu₃P/ZnIn₂S₄ photocatalyst follows the Z-scheme mechanism instead of conventional type-Ⅱ heterojunction mechanism. This work is considered helpful for getting a great deal of insight into constructing high-activity and cost-effective transition metal phosphides (TMPs) based photcatalytic hydrogen production system and rationally designing Z-scheme heterojunction photocatalyst.     

Fabrication of the SnS2/ZnIn2S4 heterojunction for highly efficient visible light photocatalytic H2 evolution

A series of SnS₂/ZnIn₂S₄ (x-SS/ZIS) photocatalysts with different mass ratios of SnS₂ were prepared by a hydrothermal method. The resulted composites were used for photocatalytic hydrogen evolution under visible light excitation. All the SS/ZIS composites exhibited significantly enhanced photocatalytic activity for H₂ evolution. Obviously, the highest H₂ evolution rate of 769 μmol g^?1 h^?1 was observed over 2.5-SS/ZIS, which was approximately 10.5 times that of the ZnIn₂S₄ (73 μmol g^?1 h^?1). The enhanced photocatalytic performance was attributed to the successful construction of SnS₂/ZnIn₂S₄ heterojunctions, leading to rapid charge separation and fast transfer of the photo-generated electrons and holes under light irradiation. On the basis of PL, electrochemical impedance spectroscopy (EIS), photocurrent measurements and the H₂ evolution tests, a plausible photocatalytic mechanism was proposed.     

Ternary Ni2P/reduced graphene oxide/g-C3N4 nanotubes for visible light-driven photocatalytic H2 production

Developing low cost co-catalysts is crucial for both fundamental research and practical application of g-C₃N₄. In this work, we prepared ternary Ni₂P/rGO/g-C₃N₄ nanotubes with different Ni₂P contents for visible-light-driven photocatalytic H₂ generation from triethanolamine aqueous solution. The optimal Ni₂P/rGO/g-C₃N₄ produced H₂ at a rate of 2921.9 μmol h⁻¹ g⁻¹, which is about 35, 16 and 9 times as large as that of g-C₃N₄, binary rGO/g-C₃N₄ and Ni₂P/g-C₃N₄, respectively. The apparent quantum efficiency of optimal Ni₂P/rGO/g-C₃N₄ was 5.6% at λ = 420 nm. We believe that the improved photocatalytic performance of Ni₂P/rGO/g-C₃N₄ originates from the synergistic effect of rGO as electron transfer medium and Ni₂P as reaction site, which is supported by photoelectrochemical and photoluminescence measurements. Cyclic experiment demonstrated an excellent stability of Ni₂P/rGO/g-C₃N₄. Moreover, we further studied the effect of other nickel-based compounds by replacing Ni₂P with NiS, Ni₃C, and Ni₃N, respectively. The order of the H₂-generation rate is Ni₂P/rGO/CNNT > NiS/rGO/CNNT > Ni₃C/rGO/CNNT > Ni₃N/rGO/CNNT, which could be reasonably explained based on Mott–Schottky plots. Our work reveals that Ni₂P can be used as a promising cocatalyst for photocatalytic H₂ evolution.     

Non-noble metal ultrathin MoS2 nanosheets modified Mn0.2Cd0.8S heterostructures for efficient photocatalytic H2 evolution with visible light irradiation

A series of non-noble metal ultrathin MoS₂ nanosheets modified Mn_0.2Cd_0.8S heterostructured composites were prepared by an ultrasonic assisted hydrothermal synthesis process. Comparing with the pristine Mn_0.2Cd_0.8S composite, the obtained ultrathin MoS₂/Mn_0.2Cd_0.8S composites exhibited a significantly improved photocatalytic activity for hydrogen evolution from water with visible light response. The optimized photocatalytic activity toward MoS₂/Mn_0.2Cd_0.8S composite is around 8 times of the pristine Mn_0.2Cd_0.8S composite. Moreover, the ultrathin MoS₂/Mn_0.2Cd_0.8S composites displayed good photocatalytic stability in the course of photochemical reaction. The excellent photocatalytic activity of the ultrathin MoS₂/Mn_0.2Cd_0.8S composites might be attributed to the formed heterojunctions in composites itself and the sufficient active edge sites in MoS₂ phase. A possible photocatalytic mechanism was tentatively proposed. Considering its excellent photocatalytic activity and good photochemical stability, the obtained ultrathin MoS₂/Mn_0.2Cd_0.8S composite has potential application in photocatalytic hydrogen evolution from water by using solar energy.     

Strong organic acid-assistant synthesis of holey graphitic carbon nitride for efficient visible light photocatalytic H2 generation

A facile and cost-effective method was developed for the synthesis of holey N-deficient graphitic carbon nitride nanosheets (FCN) using trifluoroacetic-acid-treated urea as a precursor. The role of trifluoroacetic acid on the composition, structure and photocatalytic performance of the prepared catalysts was carefully investigated. The obtained samples displayed laminated porous morphology with nitrogen defects, larger specific surface areas, extended range of spectral response and enhanced electron mobility of charge carriers. Consequently, the optimized catalyst FCN-400 exhibited superb photocatalytic performance and excellent cycling stability for hydrogen evolution. The hydrogen evolution rate over FCN-400 reached 309.3 μmol/h under visible light irradiation, which is 11.3-fold of that of urea-derived graphitic carbon nitride (27.3 μmol/h).