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.     

Photocorrosion-less stable heterojunction photoanode for efficient visible-light driven solar hydrogen generation

In this work, a heterostructure CdS/TiO₂ nanotubes (TNT) photoelectrode is decorated with Ni nanoparticles (NPs) to enhance hydrogen generation via the photoelectrochemical method. Herein, we report a systematic study of the effect of Ni NPs heterostructure photoelectrode to improve light absorption and photoelectrochemical (PEC) performance. The fabricated photoelectrodes were evaluated for photoelectrochemical hydrogen generation under simulated sunlight. The optimized Ni/CdS/TNT photoelectrode exhibited an improved photocurrent density of 6.5 mA cm^?2 in poly-sulfide aqueous media at a low potential of 0 V. Owing to the enhanced photocurrent density, Ni NPs also played a significant role in improving the stability of the photoelectrode. The synergistic effect with semiconductor ternary junction incites the surface plasmon resonance (SPR) for light-harvesting to enhance photoelectrochemical hydrogen generation.     

Ag2CO3-derived Ag/g-C3N4 composite with enhanced visible-light photocatalytic activity for hydrogen production from water splitting

In this paper, Ag-based g-C₃N₄ composites have been successfully fabricated through two deferent synthetic methods: (i) a facile and efficient precipitation-calcination strategy (denoted as D–CN–xAg, x represents the dosage of Ag₂CO₃, the same below), (ii) a calcination method (denoted as Z–CN–xAg). All Ag-based g-C₃N₄ composites exhibit the enhanced photocatalytic activities under visible-light irradiation. Moreover, the optimal dosage of Ag₂CO₃ in the D–CN–xAg composite is found to be 5%, the corresponding hydrogen production capacity is 153.33 μmol g⁻¹ h⁻¹, which is 4.6 times higher than that of Z–CN–5%Ag composite. This might be attributed to appropriate content of metallic Ag and more active sites exposed on the surface of D–CN–5%Ag composite. Meanwhile, combining with photoelectrochemical results, it could be inferred that LSPR effect and the intimate interfacial between metallic Ag and g-C₃N₄ in the system play also important role for the improvement of photocatalytic activity. These results demonstrate that the appropriate loading of metallic Ag originated from Ag₂CO₃ into g-C₃N₄ could accelerate the separation and transfer of photogenerated electron-hole pairs, leading to the improvement of photocatalytic activity for hydrogen production from water splitting. Finally, a possible photocatalytic mechanism is proposed.     

SnO2 promoted carrier separation in superior thin g-C3N4 nanosheets for enhanced photocatalytic degradation and H2 generation

The construction of heterostructures is an efficient approach to improve the photocatalystic performance of semiconductors. In this paper, SnO₂-g-C₃N₄ (SnO₂–CN) nanocomposites were created via thermal polymerization using SnO₂ nanoparticles and layered g-C₃N₄ nanosheets. A mechano-chemical pre-reaction and the second thermal polymerization of bulk g-C₃N₄ play important roles for the formation of SnO₂/g-C₃N₄ heterostructures with improved interface nature. The heterostructures with an optimized SnO₂ weight ratio of 10% was obtained by adjusting parameters for enhanced photocatalytic reactions in visible light region. Hydrogen generation and the degradation of rhodamine B (Rh B) were tested to characterize the photocatalytic performance of the SnO₂–CN nanocomposites. The degradation of a 20 mg/L Rh B solution was finished within 15 min, in which the degradation rate was about twice compared with superior thin g-C₃N₄ nanosheets prepared by a two-step polymerization procedure. The SnO₂–CN nanocomposite with 10% SnO₂ revealed a H₂ generation rate of 2569.5 μmol g⁻¹L⁻¹. The enhanced photocatalytic performance is ascribed to a type II heterostructure formed and improved interface properties between g-C₃N₄ and SnO₂. In addition, the improved conductivity of SnO₂ promoted the photogenerated carrier separation and transfer. The result provided a new idea for the construction of g-C₃N₄ heterostructures with improved interface characterization and the improvement of photocatalytic properties.     

Carbon vacancies improved photocatalytic hydrogen generation of g-C3N4 photocatalyst via magnesium vapor etching

Vacancies engineering was widely reported as the promising strategy for the improvement of the photocatalytic performance of semiconductor photocatalysts. In current work, carbon vacancies are constructed successfully in graphitic carbon nitride (g-C₃N₄) photocatalyst via magnesium vapor etching. Experimental results show that the formed carbon vacancies in g-C₃N₄ photocatalyst can significantly improve the photocatalytic H₂ generation performance. XRD, FTIR, SEM/TEM, XPS and PL characterization data are employed to evidence the construction of carbon vacancies, which are revealed to be the reason for the enhancement of photocatalytic H₂ evolution. This work develops an alternative route to construct carbon vacancies in g-C₃N₄ materials and gives an insight into the influence of vacancies on the photocatalytic performance of photocatalysts.     

Shape-dependent localized surface plasmon enhanced photocatalytic effect of ZnO nanorods decorated with Ag

We report shape-dependent localized surface plasmon enhanced photocatalytic effect of ZnO nanorods decorated with Ag nanostructures. The plasmonic ZnO photoelectrode modified by Ag nanoprisms exhibits a significant enhancement in photoelectric conversion with a maximum photoconversion efficiency of 1.45%. The photocurrent intensity (at 0.5 V vs. Ag/AgCl) of ZnO–Ag nanoprisms is 3.1 and 10 times greater than that of ZnO–Ag nanoparticles and as-grown ZnO nanorods, respectively. Moreover, ZnO–Ag nanoprisms showed a fast photoresponse due to the fast transport of photogenerated charge carriers in ZnO nanorods with a low recombination rate. It is suggested that the mechanism of photocatalytic enhancement by Ag nanoprisms is mainly ascribed to the significantly enhanced plasmonic ‘hotspots’ in sharp tips of nanoprisms. Such shape-dependent localized surface plasmon effect is further confirmed by FDTD simulation, which revealed that Ag nanoprisms showed stronger electromagnetic field intensity than that of Ag nanoparticles.     

Construction of Au/g-C3N4/ZnIn2S4 plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture for visible-light-driven hydrogen production

In this paper, a novel Au/g-C₃N₄/ZnIn₂S₄ plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture has been successfully constructed by integrating Au/g-C₃N₄ plasmonic photocatalyst composite with 3D ZnIn₂S₄ nanosheet through a simple hydrothermal process. The Au nanoparticles were firstly anchored on the surface of pristine g-C₃N₄ material to get Au/g-C₃N₄ plasmonic photocatalyst. Ascribing to the surface plasmon resonance of Au nanoparticles, the obtained Au/g-C₃N₄ plasmonic photocatalyst shows a significant improved photocatalytic activity toward hydrogen production from water with visible light response comparing with pristine g-C₃N₄. Further combining Au/g-C₃N₄ plasmonic photocatalyst with 3D ZnIn₂S₄ nanosheet to construct a heterojunction composite. Owing to the synergistic effect of the surface plasmon resonance of Au nanoparticles in Au/g-C₃N₄ and the heterojunction structure in the interface of Au/g-C₃N₄ and ZnIn₂S₄, the prepared Au/g-C₃N₄/ZnIn₂S₄ plasma photocatalyst heterojunction composite shows an excellent photocatalytic activity toward hydrogen production from water with visible light response, which is around 7.0 and 6.3 times higher than that of the pristine C₃N₄ and Znln₂S₄ nanosheet, respectively. The present work might provide some insights for exploring other efficient heterojunction photocatalysts with excellent properties.     

Increasing electron transfer and light absorption in graphited nanocarbon-conjugated g-C3N4 nanosheet heterostructure for photocatalytic hydrogen evolution

Accelerating the charge separation and transfer as well as increasing the visible light absorption is of great importance for photocatalysts to realize efficient photocatalytic hydrogen evolution via water splitting. Herein, for the first time, we fabricated in-plane graphited nanocarbon-conjugated polymeric carbon nitride (GNC-C₃N₄) nanosheet heterostructure photocatalyst from melamine and hexaketocyclohexane octahydrate mixture via an amino-carbonyl reaction. The incorporation of GNC into conjugate network of C₃N₄ can not only dramatically enhance the light harvesting but also significantly promote the charge separation and transfer by the built-in electric field and intimate interface in the coplanar GNC-C₃N₄ heterostructure. Accordingly, the optimal GNC-C₃N₄ photocatalyst demonstrates a more than 15-fold enhancement for photocatalytic hydrogen evolution from water under visible light irradiation, compared to C₃N₄.     

Highly efficient hydrogen generation of BiI3 nanoplates decorated with Ag nanoparticles

This work presents the photocatalytic hydrogen generation of BiI₃ films when they are exposed under simulated solar irradiation. Those films were fabricated by a simple bath chemical deposition method. The images of Scanning electron microscopy show that the BiI₃ films are formed by polycrystalline particles with hexagonal shape and a closer inspection shows that nanoplates grown into them. The performance for the hydrogen generation of BiI₃ films synthesized with different times (from 1 to 3 h), BiI₃ films decorated with silver nanoparticles (BiI₃-Ag) and BiI₃ powders were compared. We found that the presence of Ag nanoparticles in the BiI₃ films increased the hydrogen generation from 9 mmol/g·h to 14 mmol/g·h because these nanoparticles improved electron conductivity, reduced the amount of defects in the BiI₃ films, raised the optical absorption, and produced higher photocurrents (with respect to the BiI₃ films without nanoparticles) as confirmed by electrochemical experiments. On the contrast, the BiI₃ powders had a poor hydrogen generation rate of only 0.5 mmol/g·h, this was due to the fact that they are formed by nanoplates 10 times bigger than these ones grown on the BiI₃ films, consequently, they had lower surface area than the nanoplates in the BiI₃ films. A possible mechanism for the hydrogen generation by the BiI₃ and BiI₃-Ag films is also discussed.     

Hierarchical TiO2 spheroids decorated g-C3N4 nanocomposite for solar driven hydrogen production and water depollution

A novel hierarchical TiO₂ spheroids embellished with g-C₃N₄ nanosheets has been successfully developed via thermal condensation process for efficient solar-driven hydrogen evolution and water depollution photocatalyst. The photocatalytic behaviour of the as-prepared nanocomposite is experimented in water splitting and organic pollutant degradation under solar light irradiation. The optimal ratio of TiO₂ spheroids with g-C₃N₄ in the nanocomposite was found to be 1:10 and the resulting composite exhibits excellent photocatalytic hydrogen production of about 286 μmol h^?1g^?1, which is a factor of 3.4 and 2.3 times higher than that of pure TiO₂ and g-C₃N₄, respectively. The outstanding photocatalytic performance in this composite could be ascribed as an efficient electron-hole pair's separation and interfacial contact between TiO₂ spheroids with g-C₃N₄ nanosheets in the formed TiO₂/g-C₃N₄ nanocomposite. This work provide new insight for constructing an efficient Z-scheme TiO₂/g-C₃N₄ nanocomposites for solar light photocatlyst towards solar energy conversion, solar fuels and other environmental applications.     

Achieving highly efficient hydrogen generation and uniform Ag nanoparticle preparation via hydrolysis of Mg9Ag alloy milled under hydrogen gas

A Mg₉Ag alloy is employed as a medium for both production of hydrogen and preparation of Ag nanoparticles through hydrolysis. Mg₉Ag milled under H₂ exhibits very favorable structural characteristics, i.e., yielding a fine nanocrystal powder and partial hydrogen-induced phase decomposition. As a result, a hydrogen yield of 730 mL g⁻¹ is obtained in 25 min at 298 K, a much higher rate than produced by samples not milled or milled under argon. Moreover, the hydrolysis by-product can be recycled to obtain Ag nanoparticles by removing insoluble Mg(OH)₂ using an added HCl solution. These results show that this process provides a highly efficient method for economically produce hydrogen and Ag nanoparticles.     

Z-scheme MoO3-2D SnS nanosheets heterojunction assisted g-C3N4 composite for enhanced photocatalytic hydrogen evolutions

In this work, the 2D SnS/g-C₃N₄ nanosheets have been successfully prepared by a facile ultrasonic and microwave heating approach, which formed intimate interfacial contact and suitable energy band structure. The optimized sample displayed enhanced photocatalytic hydrogen evolution from water assisted with Pt co-catalyst, which is much higher than that of pure g-C₃N₄. After loaded with MoO₃ particles, the stability of photocatalysts displayed significate improvement due to the formed Z-scheme heterojunction. With the characterization, the enhanced hydrogen evolution reaction (HER) performance might be ascribed to the improved light-harvesting capability of the composite, lowered charge-transfer resistance, increased electrical conductivity and the co-catalyst effect of SnS. This study provides insights about SnS assisted HER photocatalysts and a new strategy to improve the stability of metal sulfides photocatalysts.     

In situ loading amorphous CoSx on N-doped g-C3N4 through light assisted synthesis for enhanced photocatalytic hydrogen generation

Loading co-catalysts are an effective strategy to break the confinement of bulk carbon nitride in photocatalysis. Employing this strategy, N-doped g-C₃N₄ decorated with CoS_x was successfully prepared through a photochemical synthesis route. The optimum hydrogen evolution performance of N-CN-CoS_x-4 was 1757 μmol g⁻¹ h⁻¹ under visible light irradiation. Superior interfacial carrier transfer properties and improved light absorption of N-CN-CoS_x-4 could elucidate its better photocatalytic activity. This research offers a reference for the construction of high-efficiency, stable and low-priced photocatalysts.     

Exfoliated and plicated g-C3N4 nanosheets for efficient photocatalytic organic degradation and hydrogen evolution

Exfoliated and plicated g-C₃N₄ nanosheets (CNsF) were prepared through a thermal-chemical exfoliation in which the bulk g-C₃N₄ was obtained first under thermal exfoliation, and then was exposed to an acidic etching using hydrofluoric acid under hydrothermal condition. The acidic etching not only exfoliated g-C₃N₄ nanosheets by disrupting weak van der Waals forces between layers, which led to formation of a monolayer or a few layers of g-C₃N₄ nanosheets, but also made disordered defects on its surface and created plicated g-C₃N₄ nanosheets. Under visible-light illumination, the optimized sample (CNsF-6%) showed a hydrogen evolution rate of 54.13 μmol h^?1g^?1 (without co-catalyst) and a specific surface area of 121.4 m² g^?1, which were about 4.7 and 2.5 times, respectively, higher than pristine g-C₃N₄. It also showed remarkably enhanced photocatalytic performance in removing various organic pollutants. This remarkable improvement probably arises from the porous nanosheets and an increased number of active sites resulting from the CNsF, which subsequently enhanced the charge separation efficiency. This work provided an alternative way to obtain highly active g-C₃N₄ photocatalysts.     

A one-pot sealed ammonia self-etching strategy to synthesis of N-defective g-C3N4 for enhanced visible-light photocatalytic hydrogen

Photocatalytic hydrogen (H₂) evolution from water is considered as a prospective approach, which can convert inexhaustible solar energy into chemical energy to alleviate energy crisis and environmental problems. Herein, the N-defective g-C₃N₄ with porous structure was firstly synthesized in a sealed crucible by one-step thermal polymerization method. The experimental data showed that the yield of the catalyst was obviously increased under sealing condition. Moreover, the N-defective g-C₃N₄ prepared from urea precursor under sealed condition reached an optimum photocatalytic H₂ production rate of 597.4 μmol/h and an apparent quantum efficiency of 15.6% at wavelength of 420 nm. This enhanced photocatalytic H₂ production performance is mainly ascribed to the introduction of N-defects, which not only extended of the visible light absorption, but also acted as the electron trap centers to suppress the recombination of the photogenerated electron and hole pairs. This work offers one-step facile strategy for the introduction of N-defects to prepare N-defective g-C₃N₄ with superior photocatalytic activity, which is also a great substitute for the high-energy consuming and complicated synthetic routes.     

Guanidine carbonate assisted supramolecular self-assembly for synthesizing porous g-C3N4 for enhanced photocatalytic hydrogen evolution

Graphitic carbon nitride (g-C₃N₄) is taken as one of the most promising polymer semiconductor photocatalysts for energy conversion. However, the photocatalytic activity of g-C₃N₄ is usually impeded by the low light absorption and fast recombination of photogenerated carriers. Herein, three-dimensional porous g-C₃N₄ with controllable morphology are synthesized by thermal polycondensation of supramolecular preorganization assembly of melamine, cyanuric acid and guanidine carbonate (1:1:x, x means the ratio of guanidine carbonate). By adjusting the amount of guanidine carbonate in the assembly, the precursors’ morphology can be changed from microrods to polyhedrons, which affects the g-C₃N₄ structure accordingly. The optimized hollow porous polyhedral g-C₃N₄ shows the enhanced light absorption and improved photogenerated carriers separation efficiency, thus exhibiting a 7.7-fold hydrogen evolution activity and 9-fold apparent quantum efficiency (AQE) higher than microtube without addition of guanidine carbonate. This work paves a complementary way towards synthesizing highly efficient photocatalysts through the guanidine carbonate-assisted supramolecular assembly.     

Rich carbon vacancies facilitated solar light-driven photocatalytic hydrogen generation over g-C3N4 treated in H2 atmosphere

Graphite carbon nitride (g-C₃N₄) has caught far-ranging concern for its masses of advantages, for instance, the unique graphite-like two-dimensional lamellar structure, low cost, nontoxic, suitable bandgap of 2.7 eV and favorable stability. Whereas owing to the shortcomings of low solar absorptivity and fast recombination of photo-induced charge pairs, the overall quantum efficiency of photocatalysis for g-C₃N₄ is suboptimal, resulting in limited practicality of g-C₃N₄ (GCN). In our study, modified g-C₃N₄ materials (HCN) with ample carbon vacancies (CVs) were obtained through calcinating of g-C₃N₄ in H₂ atmosphere. Higher specific surface area and more active sites of HCN were induced by roasting of g-C₃N₄ in H₂. CVs that occurred in the N-(C₃) bond lead to the reduction of electron density around N, thus narrowing the bandgap of HCN-3h and enlarging corresponding light response capability. Under the synergistic function of abundant pore construction and CVs on HCN, the photo-excited e^?/h⁺ pairs can be memorably separated and transferred, which is favorable to photocatalytic efficiency. Among HCN, the HCN-3h sample has the highest H₂ generation rate of 4297.9 μmol h^?1 g^?1, which achieves 2.3-fold higher than that of GCN (1291.7 μmol h^?1 g^?1). This paper brings forward a meaningful method of boosting the photocatalytic performance of photocatalysts by constructing abundant CVs.     

In-situ synthesis of Pd nanocrystals with exposed surface-active facets on g-C3N4 for photocatalytic hydrogen generation

Engineering surface-active facets of metal cocatalysts is one of the most widely explored strategies to develop advanced photocatalysts and promote photocatalytic solar energy conversion. Here, the surface-active facets of Pd nanocrystals in Pd/g-C₃N₄ photocatalyst was related to the injection flow rate of PdCl₂. When PdCl₂ was injected at a low flow rate of 7.5 mL/h (7.5-Pd/g-C₃N₄), the Pd nanocrystals were uniformly dispersed onto the g-C₃N₄ with exposed low-index {100} and {111} surface-active facets. However, increasing the injection flow rate to 150 mL/h (150-Pd/g-C₃N₄) formed Pd nanocrystals where only the {100} surface-active facet was exposed. Under visible light irradiation, the 7.5-Pd/g-C₃N₄ nanocomposite exhibited excellent water splitting activity for hydrogen production (7.61 mmol g⁻¹ h⁻¹), which was significantly better than with the 150-Pd/g-C₃N₄ nanocomposite (3.3 mmol g⁻¹ h⁻¹). Theoretical calculations and experimental results confirm the importance of the {111} surface-active facets in the 7.5-Pd/g-C₃N₄ nanocomposite for promoting photocatalytic activity.     

Oxygen vacancies mediated in-situ growth of noble-metal (Ag,Au, Pt) nanoparticles on 3D TiO2 hierarchical spheres for efficient photocatalytic hydrogen evolution from water splitting

Defect engineering is effective to extend the light absorption range of TiO₂. However, the oxygen vacancy defects in TiO₂ may serve as recombination centers, hampering the separation and transfer of photo-generated charges. Here, we present a strategy of in-situ depositing noble-metal (M = Ag, Au or Pt) nanoparticles (NPs) on defective 3D TiO₂ hierarchical spheres (THS) with large surface area through the redox reaction between metal ions in solution and the electrons trapped at oxygen vacancies in THS. The oxygen vacancies at the THS surface are consumed, resulting in direct contact between TiO₂ and noble-metal NPs, while the other oxygen vacancies in the bulk are retained to promote visible light absorption. The noble-metal NPs with well-controlled size and distribution throughout the porous hierarchical structure not only facilitate the generation of electron-hole pairs in THS due to the effect of surface plasmon-induced resonance energy transfer (SPRET) from noble-metal NPs to TiO₂, but also expediate the electron transfer from TiO₂ to noble-metal NPs due to the Schottky junction at the TiO₂/M interface. Therefore, THS-M shows improved photocatalytic performance in water splitting compared to THS. The optimum performance is achieved on THS-Pt (13.16 mmol h⁻¹g⁻¹) under full-spectrum (UV–Vis) irradiation but on THS-Au (1.49 mmol h⁻¹g⁻¹) under visible-light irradiation. The underlying mechanisms are proposed from the surface plasmon resonance of noble-metal NPs as well as the Schottky junction at the TiO₂/M interface.