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The design and development of efficient nitride photocatalysts have attracted much attention. Herein, two-dimensional mesoporous Ta 3 N 5 is successfully synthesized through a simple sol-gel process with filter paper as a biological template and a combination of vacuum nitriding reactions. The prepared Ta 3 N 5 shows a wide light response range up to the near infrared (NIR) region due to the nitrogen vacancies generated from substitution of N3− for O2− ions during vacuum nitridation. Significantly, such a narrow bandgap (∼1.99 eV) still satisfies the redox potential of water splitting in thermodynamics. The experimental results show that the Ta 3 N 5 photocatalyst exhibits an enhanced hydrogen production rate of 34.6 μmol h−1 g−1, which is 3.9 and 2.1 times higher than that of Ta 2 O 5 and partial nitridation of Ta 2 O 5 (N–Ta 2 O 5), respectively. This enhanced photocatalytic performance could be attributed to the high specific surface area to provide reactive active sites, substitution of N3− for O2− ions to optimize the band structure, and special two-dimensional mesoporous structure to shorten the charge transfer distance. This work provides a new perspective for the preparation of two-dimensional nitride materials by a biological template method combining vacuum nitriding with enhanced photocatalytic performance. Two-dimensional mesoporous Ta 3 N 5 is synthesized by a simple sol-gel process with filter paper as a biological template and vacuum nitriding reaction, leading to an efficient photocatalytic performance. [Display omitted] • Two-dimensional mesoporous Ta 3 N 5 was prepared by a biological template. • The prepared Ta 3 N 5 shows a wide light response range up to the near infrared region. • The special two-dimensional structure shortens the charge transfer distance. • The Ta 3 N 5 photocatalyst shows a superior hydrogen production performance. [ABSTRACT FROM AUTHOR]

Photoreforming (PR) of biomass can be considered a viable technology under mild experimental conditions to produce hydrogen with a high reaction rate using compounds from renewable resources and waste materials. The application of biomass PR gives rise to both hydrogen generation and biomass waste valorization. The process could be scaled up to obtain hydrogen under natural sunlight irradiation, and research on polymeric carbon nitride (g-C3N4)-based photocatalysts has been widely carried out in recent years. The non-metallic-based carbon nitride materials are economical and (photo)stable polymer semiconductors, and their physicochemical surface and electronic properties are optimal for obtaining H2, which can be considered a gas that does not cause major environmental problems. Some hindrances related to their structure, such as the low absorption of visible light and the relatively high recombination rate of electron-hole pairs, restrict the performance; therefore, it is necessary to improve their activity and the yield of the reaction by modifying them in various ways. Various types of solutions have been proposed in this regard, such as, for example, their coupling with other semiconductors to form composite materials. The current mini-review aims to overview the PR field, reporting some of the most interesting papers devoted to understanding the role of g-C3N4 in biomass PR. Information on many physico-chemical aspects related to the performance of the process and possible ways to obtain better results than those present up to now in the literature will be reported. [ABSTRACT FROM AUTHOR]

Summary: There are various methods to produce hydrogen from water splitting as a substitute energy resource for fossil fuels in accordance with the global environmental crisis. Among these, water photocatalysis is considered one of the most renewable and sustainable processes simulated the solar energy utilized system in nature. During a half century, different kinds of photocatalysts were developed to convert photon energy into chemical energy to induce redox potential under visible light irradiation condition. In the beginning step, semiconductor materials, such as transition metal oxides, were explored extensively to use as a photocatalyst for hydrogen generation. However, semiconductor has limitations to act as an effective photocatalyst for water splitting due to the large band gap and recombination of charge carriers. Therefore, several kinds of modifications of structure or components have been studied to design visible light active photocatalysts for water splitting to generate hydrogen. Their performance was improved substantially by adding a noble metal or sensitizer to adjust the band gap and reduce the recombination of photoinduced charge carriers. Considering solar light‐induced photocatalytic hydrogen generation, various visible light active photocatalysts have been derived from carbon chain organic compounds and lattice crystals. This review classifies the visible light active photocatalysts as follows: (a) structural and chemical components of modified graphitic carbon nitride (g‐C3N4), (b) exfoliated perovskites, and (c) π‐bond conjugated polymers to produce hydrogen from water splitting. The hydrogen evolution efficiency of photocatalysts shows a great difference under visible light (λ > 400 nm) irradiation according to the three‐dimensional structure and electron transfer pathway. This is because the capability of restricting the recombination of photoinduced charge carriers and the band gap between the valence band and the conduction band of photocatalysts is dependent on the morphology and electrostatic interactions among components. This paper reviews visible light photocatalysts, that is, g‐C3N4 based materials, layered perovskites, and conjugated polymers, to provide integrated insight into photocatalytic water splitting to obtain hydrogen. [ABSTRACT FROM AUTHOR]

[Display omitted] Construction of Z-scheme heterojunctions has been considered one superb method in promoting solar-assisted charge carrier separation of carbon-based materials to achieve efficient utilization of solar energy in hydrogen production and CO 2 reduction. One interesting concept in nanofabrication that has become trend recent years is nanoarchitectonics. A heterostructure photocatalyst constructed based on the idea of nanoarchitectonics using the combination of g-C 3 N 4 , metal and an additional semiconducting nanocomposite is investigated in this paper. Z-scheme tungsten oxide incorporated copper modified graphitic carbon nitride (WO x /Cu-g-C 3 N 4) heterostructures are fabricated via immobilization of WO x on Cu nanoparticles modified superior thin g-C 3 N 4 nanosheets. Mechano-chemical pre-reaction and a two-step high-temperature thermal polymerization process are the keys in attaining homogeneous distribution of Cu nanoparticles in g-C 3 N 4 nanosheets. The horizontal growth of homogeneously distributed WO x nanobelts on Cu modified g-C 3 N 4 (Cu-g-C 3 N 4) base via solvothermal synthesis is achieved. The photocatalytic performances of the heterostructures are evaluated through water splitting and CO 2 photoreduction measurements in full solar spectrum irradiation condition. The presence of Cu nanoparticles in the composite system improves charge transport between g-C 3 N 4 and WO x and thus enhances the photocatalytic performances (H 2 generation and CO 2 photoreduction) of the composite material, while the presence of WO x nanocomposites enhances light absorption of the composite material in the near infrared range. The synthesized heterostructure with optimized WO x to Cu-g-C 3 N 4 ratio and in case of no co-catalyst addition exhibits enhanced photocatalytic H 2 evolution (4560 μmolg-1h−1) as well as excellent CO 2 reduction rate (5.89 μmolg-1h−1 for CO generation). [ABSTRACT FROM AUTHOR]

Atomically precise Ni 6 (SC 2 H 4 Ph) 12 nanoclusters (Ni 6 NCs) supported on g-C 3 N 4 nanosheets were constructed to enhance the photocatalytic hydrogen evolution performances. [Display omitted] Much effort has been devoted to improving the photocatalytic capacity of graphitic carbon nitride (g-C 3 N 4). In this paper, we reported the successful synthesis of a hybrid photocatalyst with superb photocatalytic hydrogen production activity through decorating atomically precise Ni 6 (SC 2 H 4 Ph) 12 nanoclusters on g-C 3 N 4 nanosheets (labeled as Ni 6 /g-C 3 N 4) at room temperature. Zeta potential experiments demonstrated that the electrostatic interaction between Ni 6 and g-C 3 N 4 led to the formation of Ni 6 /g-C 3 N 4. The photocatalytic measurements revealed that the 5 %-Ni 6 /g-C 3 N 4 prepared with the original mass ratio of m(Ni 6)/m(g-C 3 N 4) = 1/20 exhibited the strongest hydrogen production activity. In the system with triethanolamine (TEOA) as the sacrifice agent, the visible-light hydrogen production rate reached up to 5.87 mmol h−1 g−1, approximately 290 times higher than that of pure g-C 3 N 4 (0.02 mmol h−1 g−1). Density functional theory (DFT) calculations testified that the above significant enhancement of photocatalytic hydrogen evolution of the hybrid photocatalyst arose from the photogenerated electrons transfer from Ni 6 to g-C 3 N 4. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride is considered as an ideal semiconductor material for photocatalytic hydrogen evolution due to its suitable energy band structure, durability and environmental friendliness. To further improve the catalytic performance of g-C3N4, nickel phosphide-loaded one-dimensional tubular carbon nitride (Ni2P/TCN) was prepared by thermal polymerization and photo deposition. The beneficial effect of the one-dimensional tubular structure on hydrogen generation was mainly attributed to its larger specific surface area (increased light absorption) as well as the linear movement of the carriers, which reduced their diffusion distance to the surface and facilitated the separation of photogenerated carriers. The loading of Ni2P co-catalyst improved the visible light utilization efficiency and enabled the migration of photogenerated electrons towards Ni2P, which ultimately reacted with the enhanced adsorbed H+ on the Ni2P surface to facilitate the photocatalytic hydrogen evolution process. This study provides new clues for the further development of efficient, environmentally friendly and low-cost g-C3N4 catalysts. [ABSTRACT FROM AUTHOR]

Two dimensional (2D)/2D heterostructures with much interface is advantage to improve the transfer of photogenerated carriers. In this paper, SnS 2 nanosheets were horizontally grown on superior thin graphic carbon nitride (g-C 3 N 4) nanosheets to construct 2D/2D heterostructures with enhanced photocatalytic performance. The g-C 3 N 4 nanosheets (CN) were obtained by a two-step thermal polymerization at 600 and 700 °C. the growth of SnS 2 nanosheets was then carried out using a solvothermal synthesis. Preparation parameters including temperature, reaction time, and precursor components were tested to get optimized SnS 2 /g-C 3 N 4 composite sample 8SnS 2 -CN. A Z-scheme mechanism was proposed for the discussion of photocatalytic process. The degradation test of Rhodamine B (Rh B) indicated that the degradation rate of Rh B using sample 8SnS 2 -CN was twice quick compared with g-C 3 N 4 nanosheets, in which Rh B degradation was completed within 15 min. The photocatalytic hydrogen production rate of sample 8SnS 2 -CN was about 6 times that that of sample CN, which is 1818.75 μmol g−1 L−1. Enhanced photocatalytic performance is ascribed to SnS 2 deposited to form well-developed interface which improved the separation and transfer of photogenerated carriers. In addition, the growth of SnS 2 was also expended the photo adsorption. [Display omitted] [ABSTRACT FROM AUTHOR]

Black phosphorus (BP) and heptazine-based crystalline carbon nitride (KPHI) composite photocatalysts were synthesized by molten salt and ultrasound-assisted liquid phase exfoliation methods. The structure, morphology and optical properties of the as-prepared BP/KPHI composites were evaluated by various characterization techniques. In addition, the photocatalytic performance of BP/KPHI composites for hydrogen production was investigated. The photocatalytic activity of BP/KPHI composite catalysts could be modulated by changing the loading mass ratio of BP. The BP/KPHI composite photocatalyst with a mass ratio of 10% exhibited the highest photocatalytic activity with the hydrogen production rate of 4.3 mmol g−1 h−1, about three times higher than that of pristine KPHI. Benefiting from the advantages of simplicity, rapidity, high yield and good controllability, this nanocomposite photocatalyst has the potential to serve as an excellent photocatalytic material for solar energy conversion. [ABSTRACT FROM AUTHOR]

Exfoliated graphitic carbon nitride (ex-g-CN) was synthesized and loaded with non-noble metals (Ni, Cu, and Co). The synthesized catalysts were tested for hydrogen production using a 300-W Xe lamp equipped with a 395 nm cutoff filter. A noncommercial double-walled quartz-glass reactor irradiated from the side was used with a 1 g/L catalyst in 20 mL of a 10 vol% triethanolamine aqueous solution. For preliminary screening, the metal-loaded ex-g-CN was synthesized using the incipient wetness impregnation method. The highest hydrogen production was observed on the Ni-loaded ex-g-CN, which was selected to assess the impact of the synthesis method on hydrogen production. Ni-loaded ex-g-CN was synthesized using different synthesis methods: incipient wetness impregnation, colloidal deposition, and precipitation deposition. The catalysts were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption using the Brunauer–Emmett–Teller method, and transmission electron microscopy. The Ni-loaded ex-g-CN synthesized using the colloidal method performed best with a hydrogen production rate of 43.6 µmol h−1 g−1. By contrast, the catalysts synthesized using the impregnation and precipitation methods were less active, with 28.2 and 10.1 µmol h−1 g−1, respectively. The hydrogen production performance of the suspended catalyst (440 µmol m−2 g−1) showed to be superior to that of the corresponding immobilized catalyst (236 µmol m−2 g−1). [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (C3N4) was synthesised from melamine at 550 °C for 4 h in the argon atmosphere and then was reheated for 1–3 h at 500 °C in argon. Two band gaps of 2.04 eV and 2.47 eV were observed in all the synthetized materials. Based on the results of elemental and photoluminescence analyses, the lower band gap was found to be caused by the formation of vacancies. Specific surface areas of the synthetized materials were 15–18 m2g−1 indicating that no thermal exfoliation occurred. The photocatalytic activity of these materials was tested for hydrogen generation. The best photocatalyst showed 3 times higher performance (1547 μmol/g) than bulk C3N4 synthetized in the air (547 μmol/g). This higher activity was explained by the presence of carbon (VC) and nitrogen (VN) vacancies grouped in their big complexes 2VC + 2VN (observed by positron annihilation spectroscopy). The effect of an inert gas on the synthesis of C3N4 was demonstrated using Graham´s law of ammonia diffusion. This study showed that the synthesis of C3N4 from nitrogen-rich precursors in the argon atmosphere led to the formation of vacancy complexes beneficial for hydrogen generation, which was not referred so far. [ABSTRACT FROM AUTHOR]

P-doped graphitic carbon nitride tubes (P-CNTS) with different P concentrations were successfully fabricated via a pre-hydrothermal in combination with a calcination process under a nitrogen atmosphere. The as-prepared samples exhibited excellent photocatalytic performance with a hydrogen production rate (HPR) of 2749.3 μmol g−1 h−1, which was 17.5 and 6.6 times higher than that of the bulk graphitic carbon nitride (CNB) and graphitic carbon nitride tube (CNT). The structural and textural properties of the P-CNT samples were well-investigated via a series of characterization methods. Compared with the bulk g-C3N4, the tubular structure of the doped samples was provided with a larger specific surface area (SSA) and a relatively rough interior. Besides the above, surface defects were formed due to the doping, which could act as more active sites for the hydrogen production reaction. In addition, the introduction of the P element could effectively adjust the band-gap, strengthen the harvest of visible-light, and boost the effective separation of photogenerated charges. More interestingly, these findings can open up a novel prospect for the enhancement of the photocatalytic performance of the modified g-C3N4. [ABSTRACT FROM AUTHOR]

• The recent advances of graphitic carbon nitride for the hydrogen production and photocatalytic water splitting were summarized. • The drawbacks and the solution to overcome it have been discussed. • The advanced strategies to increase the performance of graphitic carbon nitride have been systematically discussed. The future energy crisis and environmental degradation can only mitigate by harvesting solar energy into renewable, safe, economical and clean technology like water splitting. The graphitic carbon nitride has an attractive band structure, good chemical stability, earth-abundant and significantly easily fabricated which makes an application for the generation of hydrogen by water splitting. In this paper, we try to critically focus on the current progress and future development of the different strategies of water splitting using graphitic carbon nitride (g-C 3 N 4) for hydrogen generation. In this context, we discuss recent strategies like metal and non-metal doping (electronic structure), morphology tuning (geometric structuring), use of mediators (Z-scheme technology), defects engineering, plasmonic materials, dye-sensitization, perovskite oxides, carbon nitrides, carbon dots, metal organic framework, and a bimetallic cocatalyst. Finally, we summarize the recent advances and future developments of g-C 3 N 4 bases photocatalysis. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride (g-C3N4) has been widely studied as a photocatalyst for the splitting of water to produce hydrogen. In order to solve the problems of limited number of active sites and serious recombination rate of charge-carriers, noble metals are needed as cocatalysts. Here, we selectively anchored Pt nanoparticles (NPs) to specific nitrogen species on the surface of g-C3N4 via heat treatment in argon–hydrogen gas mixture, thus achieving g-C3N4 photocatalyst anchored by highly dispersed homogeneous Pt NPs with the co-existed metallic Pt0 and Pt2+ species. The synergistic effect of highly dispersed metallic Pt0 and Pt2+ species makes the catalyst exhibit excellent photocatalytic performance. Under the full-spectrum solar light irradiation, the photocatalytic hydrogen production rate of the photocatalyst is up to 18.67 mmol·g−1·h−1, which is 5.1 times of the catalyst prepared by non-selective deposition of Pt NPs. [ABSTRACT FROM AUTHOR]

Solar-to-fuel conversion is an innovative concept for green energy, attracting many researchers to explore them. Solar-driven photocatalysts have become an essential solution to provide valuable chemicals like hydrogen, hydrocarbon, and ammonia. For sustainable stability under solar irradiation, titanium dioxide is regarded as an acceptable candidate, further showing excellent photocatalytic activity. Incorporating the photo-sensitizers, including noble metal nanoparticles and polymeric carbon-based material, can improve its photoresponse and facilitate the electron transfer and collection. In this study, we synthesized the graphitic carbon nitride (g-C3N4) nanosheet incorporated with high crystalline TiO2 nanofibers (NF) as 1D/2D heterostructure catalyst for photocatalytic water splitting. The microstructure, optical absorption, crystal structure, charge carrier dynamics, and specific surface area were characterized systematically. The low bandgap of 2D g-C3N4 nanosheets (NS) as a sensitizer improves the specific surface area and photo-response in the visible region as the incorporated amount increases. Because of the band structure difference between TiO2 and g-C3N4, constructing the heterojunction formation, the superior separation of electron-hole is observed. The detection of reactive oxygen species and photo-assisted Kelvin probe microscopy are conducted to investigates the possible charge migration. The highest photocatalytic hydrogen production rate of Pd/TiO2/g-C3N4 achieves 11.62 mmol·h−1·g−1 under xenon lamp irradiation. [ABSTRACT FROM AUTHOR]