Fabrication of g-C3N4/TiO2 heterojunction composite for enhanced photocatalytic hydrogen production

In this study, graphitic carbon nitride (g-C₃N₄) was successfully coupled with TiO₂ using hydrothermal method, to develop an advanced heterojunction photocatalyst. The interaction between g-C₃N₄ and TiO₂ was confirmed through analysis of X-Ray spectroscopy (XPS) C 1s, N 1s, O 1s high resolution core level spectra of g-C₃N₄, TiO₂ and g–C₃N₄–TiO₂ heterojucntion. Further, through valence band spectra analysis, conduction band offset (0.12 eV) and valence band offset (0.28 eV) of g–C₃N₄–TiO₂ heterojunction were estimated. Also, composite material was identified as type II heterojunction between g-C₃N₄ and TiO₂. XRD, UV–vis, BET and HRTEM were employed to understand the changes in physicochemical properties. Photocatalytic hydrogen production rates were evaluated through water splitting experiments. Under visible light irradiation highest hydrogen production rate was achieved for g–C₃N₄–TiO₂ heterojunction sample with high content of TiO₂, and was about 1041 μmol/g.h. The improved photocatalytic activity of the heterojunction material was explained in detail.     

Enhanced photocatalytic hydrogen evolution over TiO2/g-C3N4 2D heterojunction coupled with plasmon Ag nanoparticles

2D heterojunction based on g-C₃N₄ nanosheets with other semiconductor nanosheets is a promising way to improve photocatalytic hydrogen evolution (PHE) activity over g-C₃N₄. However, current 2D heterojunction based on g-C₃N₄ are unsatisfactory due to their insufficient absorption of visible light and inefficient charge separation. In this work, Ag/TiO₂/g-C₃N₄ nanocomposites based on 2D heterojunction coupling with Ag surface plasmon resonance (SPR) were synthesized by a method combining facile wetness impregnation calcination. The PHE activity of Ag/TiO₂/g-C₃N₄ nanocomposites is attributed to the TiO₂/g-C₃N₄ 2D heterojunction and bare g-C₃N₄ nanosheet under visible light irradiation, indicating a cooperative effect between Ag and TiO₂/g-C₃N₄ 2D heterojunction. As a result of SPR effect, the composites strongly absorb visible light. In addition, the oscillating hot electrons from Ag can easily transfer to 2D heterojunction. This synergistic effect lead to sufficient visible light absorption and efficient charge separation of 2D heterojunction, which improved the PHE activity of g-C₃N₄. This work indicates that loading metal nanoparticles on 2D heterojunction as metal SPR-2D heterojunction nanocomposites may be a potential method for harvesting visible light for PHE.     

Constructing 0D/1D/2D Z-scheme heterojunctions of Ag nanodots/SiC nanofibers/g-C3N4 nanosheets for efficient photocatalytic water splitting

Efficiently constructing nanostructured Z-scheme heterojunctions with good interface contact is a desired route to optimize the photocatalytic property of the materials. In this work, novel 0D/1D/2D Z-scheme silver/silicon carbide/graphitic carbon nitride (Ag/SiC/CN) photocatalysts were prepared from Ag nanodots loaded on SiC nanofibers/CN nanosheets (SiC/CN) composite, using the calcination and chemical reduction routes. The Ag/SiC/CN composite with an optimal 3% Ag loading dose performs the best H₂ evolution rate of 2971 μmol g^?1 h^?1, which is approximately 8.8, 1.5 and 4.5 times compared to CN, SiC/CN and 3% Ag/CN, respectively. Besides the Ag/SiC/CN composite presents a high apparent quantum efficiency (7.3%) and outstanding photo-corrosion resistance stability. The Ag nanodots are served as efficient carriers transfer center and cocatalyst to construct Z-scheme heterojunction interface, which can help to generate more photo-generated carries, shorten the electron transmission distance and increase the electron transfer rate, certifying that 0D/1D/2D Z-scheme photocatalytic system is high-efficiency and has great advantages in photocatalytic applications.     

Facile construction Z-scheme anatase/rutile TiO2/g-C3N4 hybrid for efficient photocatalytic H2 evolution under visible-light irradiation

Z-scheme anatase/rutile TiO₂/g-C₃N₄ hybrids (denoted as LTARCN-x, x represents calcination temperature) were designed and synthesized by growing TiO₂ nanorods on the surface of g-C₃N₄ utilizing impregnation-calcination method. Furthermore, through the etched effect of hydrochloric acid and calcination treatment, the as-prepared LTARCN-x possessed abundant pore structure and larger surface area, and the surface area of LTARCN-425 was 8.5 times than that of bulk g-C₃N₄. Meanwhile, the g-C₃N₄ would play a role of carrier to prevent from the aggregation of TiO₂ nanorods. In addition, under visible light irradiation, the Z-scheme heterostructure would be constructed between the rutile TiO₂ nanorod and g-C₃N₄ nanosheet, respectively. The optimized photocatalyst LTARCN-425 exhibited a preferable activity, the photocatalytic hydrogen production rate of LTARCN-425 was about 1031 μmol g^?1 h^?1, and it was about 6.3 and 13.6 times than that of g-C₃N₄ and TiO₂, respectively. Moreover, the photocatalytic mechanism of the hydrogen production was studied intensively via designing fluorescent probe, Pt and PbO₂ deposition experiment, and the characterizations of EPR, TEM, HRTEM and XPS.     

Dual Z-scheme heterojunction g-C3N4/Ag3PO4/AgBr photocatalyst with enhanced visible-light photocatalytic activity

Recently, there has been a significant interest in developing high-performance photocatalysts for removing organic pollutants from water environment. Herein, a ternary graphitic C₃N₄ (g-C₃N₄)/Ag₃PO₄/AgBr composite photocatalyst is synthesized using an in-situ precipitation-anion-exchange process and characterized by several spectroscopic and microscopic techniques. During the photocatalytic reaction, X-ray photoelectron spectroscopy clearly illustrated the formation of metallic Ag on the g-C₃N₄/Ag₃PO₄/AgBr composite surface. The ternary composite photocatalyst demonstrated an increased photoactivity under visible light (>420 nm), achieving a complete decolorization of methyl orange (MO) in 5 min. The ternary g-C₃N₄/Ag₃PO₄/AgBr hybrid was also applied to the 2-chlorophenol degradation under visible light, further confirming its excellent photocatalytic activity. In addition, quenching experiments revealed that holes (h⁺) and O₂^?– were the major attack species in the decolorization of MO. The enhanced photoactivity of g-C₃N₄/Ag₃PO₄/AgBr results from the efficient transfer/separation of photoinduced charges with the dual Z-scheme pathway and the charge recombination sites on the formed Ag particles.     

Z-scheme AgSCN/Ag3PO4/C3N4 heterojunction with excellent photocatalytic degradation of ibuprofen

To develop a novel photocatalyst with high catalytic performance under sunlight, AgSCN/Ag₃PO₄/C₃N₄ heterojunction photocatalyst with Z-mechanism has been prepared, which demonstrates excellent photocatalytic performance for ibuprofen degradation. The catalytic activity of AgSCN/Ag₃PO₄/C₃N₄ is 1.5 and 3.3 times that of AgSCN/Ag₃PO₄ and Ag₃PO₄, respectively. The cyclic degradation number of AgSCN/Ag₃PO₄/C₃N₄ increases to seven because of the protection of AgSCN and C₃N₄ to Ag₃PO₄. The excellent photocatalytic performance of the AgSCN/Ag₃PO₄/C₃N₄ is attributed from the Z-mechanism with efficient separation efficiency of electron hole pair.     

S-scheme g-C3N4/TiO2/CFs heterojunction composites with multi-dimensional through-holes and enhanced visible-light photocatalytic activity

A novel multi-dimensional through-holes structure of g-C₃N₄ with adjustable pore size was prepared by controlling the mass ratio of oxamide (OA, structure guiding agent) to urea during one-step calcination process, and a break-rearrangement mechanism was explored. Then, a series of porous g-C₃N₄/TiO₂ (CT) composites with uniformly deposited TiO₂ nanoparticles were prepared based on the multi-dimensional framework by a facile hydrothermal method. The results show that a new S-scheme heterojunction with multi-dimensional through-channel structure was obtained, which is particularly desired for enhancing the visible-light utilization, reducing the carrier recombination rate and enhancing redox capacity. The CT composite obtained at hydrothermal treatment time of 2 h has a specific surface area of 180.15 m² g^-1, which shows high degradation capability (99.99%) for tetracycline hydrochloride (TC·HCl) under 350 W Xe lamp irradiation for 90 min. In addition, CT nanostructures was in-situ growth on carbon fiber (CFs), the degradation rate constant is 0.1566 min^-1, and 90% of the degradation efficiency can be maintained even after 5 consecutive cycles. It is expected to provide an effective reference for solving the problems of recovery difficulty and low reuse rate of powder photocatalytic materials.     

A facile and novel construction of attapulgite/Cu2O/Cu/g-C3N4 with enhanced photocatalytic activity for antibiotic degradation

A high-performance photocatalyst, attapulgite/Cu₂O/Cu/g-C₃N₄ (ATP/Cu₂O/Cu/g-C₃N₄), was constructed via a one-pot redox strategy under anoxic calcination. The as-prepared composites were characterized by Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂ adsorption-desorption isotherms (BET), photoluminescence emission (PL), and electrochemical impedance spectra (EIS). Results indicate that ultra-fine CuO nanoparticles on the surface of rod-like attapulgite are in-situ reduced by NH₃ gas to generate Cu and minority Cu₂O during the pyrocondensation of melamine. Meanwhile, the generated g-C₃N₄ membrane is uniformly encapsulated on the surface of attapulgite/Cu₂O/Cu to assemble Z-scheme Cu₂O/Cu/g-C₃N₄ heterostructure. ATP/Cu₂O/Cu/g-C₃N₄ shows improved visible light response ability and hole-electron suppression compared with ATP/g-C₃N₄. The photocatalytic performance and mechanism of the obtained photocatalyst for antibiotic degradation were evaluated by UV–Vis spectrometer and liquid chromatograph. ATP/Cu₂O/Cu/g-C₃N₄ can exhibit favorable photocatalytic activity and reusability for chloramphenicol. In addition, h⁺ and·OH radicals are the main active sites in the photocatalytic process, and Cu species play a vital role in separation and retarding recombination of electron-hole pairs.     

Facile fabrication of ordered assembled TiO2/g-C3N4 nanosheets with enhanced photocatalytic activity

A series of assembled porous TiO₂/g-C₃N₄ (TC) powders composed of spherical nanoparticles were synthesized by controlling the molar ratio of urea to tetrabutyl titanate (TBOT) in a facile hydrothermal process. A nanosheets-constructed hierarchical structure was obtained at the molar ratio of urea to TBOT of 10:1, which possessed uniform mesopores with bimodal distribution (0.5–1.5 nm and 2–20 nm) and interconnected macropores between TC nanosheets. The specific surface area achieved 98.4 m² g^?1. X-ray diffraction (XRD) patterns and high resolution transmission electron microscope (HRTEM) analysis proved that the nanosheets are made of overlapping TC nanocomposite. Photoluminescence (PL) spectra results illustrated that a well-defined hierarchical porous structure is particularly desired for the low recombination rate of carriers. Further, the TC-decorated carbon fiber (CF) cloth was obtained based on the nanosheets assembled hierarchical structure, which showed more outstanding photocatalytic behavior with high degradation capability for Rhodamine B (RhB) (99.9%) and tetracycline hydrochloride (89.8%) at 60 min by 500 W Xe lamp irradiation. After five consecutive cycles, the degradation efficiencies of TC/CF cloth for both RhB and tetracycline hydrochloride all remained above 90% of the initial value.     

Construction of g-C3N4/TiO2/Ag composites with enhanced visible-light photocatalytic activity and antibacterial properties

In this study, the multifunctional carbon nitride based composite graphitic-C₃N₄ (g-C₃N₄)/TiO₂/Ag was prepared through a simple and efficient vacuum freeze-drying route. TiO₂ and Ag nanoparticles were demonstrated to decorate onto the surface of g-C₃N₄ sheet. In the ultraviolet–visible absorption test, a narrower band gap and red-shift of light absorption edge were observed for g-C₃N₄/TiO₂/Ag compared to pristine g-C₃N₄ and single-component modified g-C₃N₄/TiO₂. The photodegradation property of g-C₃N₄/TiO₂/Ag was investigated toward the degradation of methylene blue (abbreviated as MB) under the irradiation of visible light. These results indicated that the degradation performance of organic dyes for g-C₃N₄/TiO₂/Ag was obviously improved compared with g-C₃N₄/TiO₂ and g-C₃N₄. The reaction rate constant of MB degradation for g-C₃N₄/TiO₂/Ag was 4.24 times higher than that of pristine g-C₃N₄. In addition, such rationally constructed nanocomposite presented evidently enhanced antibacterial performance against the Gram-negative Escherichia coli. Concentration dependent antibacterial performance was systematically investigated. And 84% bacterial cell viability loss had been observed at 500 μg/mL g-C₃N₄/TiO₂/Ag within 2 h visible light irradiation.     

Preparation and photocatalytic activity of g-C3N4/TiO2 heterojunctions under solar light illumination

The solar light sensitive g-C₃N₄/TiO₂ heterojunction photocatalysts containing 20, 50, 80, and 90 wt% graphitic carbon nitride (g-C₃N₄) were prepared by growing Titania (TiO₂) nanoparticles on the surfaces of g-C₃N₄ particles via one step hydrothermal process. The hydrothermal reactions were allowed to take place at 110 °C at autogenous pressure for 1 h. Raman spectroscopy analyses confirmed that an interface developed between the surfaces of TiO₂ and g-C₃N₄ nanoparticles. The photocatalyst containing 80 wt% g-C₃N₄ was subsequently heat treated 1 h at temperatures between 350 and 500 °C to improve the photocatalytic efficiency. Structural and optical properties of the prepared g-C₃N₄/TiO₂ heterojunction nanocomposites were compared with those of the pristine TiO₂ and pristine g-C₃N₄ powders. Photocatalytic activity of all the nanocomposites and the pristine TiO₂ and g-C₃N₄ powders were assessed by the Methylene Blue (MB) degradation test under solar light illumination. g-C₃N₄/TiO₂ heterojunction photocatalysts exhibited better photocatalytic activity for the degradation of MB than both pristine TiO₂ and g-C₃N₄. The photocatalytic efficiency of the g-C₃N₄/TiO₂ heterojunction photocatalyst heat treated at 400 °C for 1 h is 1.45 times better than that of the pristine TiO₂ powder, 2.20 times better than that of the pristine g-C₃N₄ powder, and 1.24 times better than that of the commercially available TiO₂ powder (Degussa P25). The improvement in photocatalytic efficiency was related to i) the generation of reactive oxidation species induced by photogenerated electrons, ii) the reduced recombination rate for electron-hole pairs, and iii) large specific surface area.     

Novel 0D/2D Bi2WO6/MoSSe Z-scheme heterojunction for enhanced photocatalytic degradation and photoelectrochemical activity

The catalytic activity of a single catalyst could be optimized by constructing a Z-scheme heterojunction structure with another adaptive material. 0D Bi₂WO₆ nanoparticles exhibit good oxidation ability, while 2D MoSSe nanoplates with low internal resistance show excellent reduction ability. Herein, novel 0D/2D Bi₂WO₆/MoSSe Z-scheme heterojunction catalysts (BMSS) with different Mo: Bi molar ratios were developed by combining the advantages of pure Bi₂WO₆ and MoSSe. The matched energy bands may provide the possibility to construct heterojunction, and the internal electric fields could facilitate the separation and transmission of internal carriers. Energy band structure analyses and electron spin resonance (ESR) results have further confirmed the existence of the above Z-scheme heterojunction structure and internal electric field. More importantly, as-prepared BMSS catalysts were proved to have excellent oxidation and reduction ability from photocatalytic and photoelectrochemical results. With an optimized MoSSe loading ratio of 3.66%, the BMSS3 catalyst showed 4.13 times of photocurrent density than that of pure Bi₂WO₆ and displayed an excellent degradation rate (0.0377 min^?1). It can be concluded that BMSS catalysts will have promising applications in photoelectrochemistry and photocatalysis.     

CdS nanoparticles decorated hexagonal Fe2O3 nanosheets with a Z-scheme photogenerated electron transfer path for improved visible-light photocatalytic hydrogen production

Photocatalytic water splitting for hydrogen production (H₂) is one of the main potential applications of photocatalytic technology, which can use solar energy as the energy required for chemical reactions to alleviate the energy crisis. In this work, zero-dimensional/two-dimensional (0D/2D) contact surface CdS/α-Fe₂O₃ (CF) heterojunction photocatalyst was synthesized via a simple solvothermal method. Photocatalytic hydrogen production experiments revealed that the CF-15 sample shows the optimal photocatalytic H₂ rate (1806 (μmol·h^-1·g^-1)) and apparent quantum efficiency (AQE = 13.7% at λ = 420 nm). The enhancement of photocatalytic performance is mainly attributed to the contact of 0D/2D interface and the synergistic effect of Z-scheme electron transfer mechanism. This work provides an effective way for modified composite semiconductor photocatalyst by constructing special interface heterojunction to achieve highly efficiently catalysis.     

Enhanced photocatalytic activity of g-C3N4 2D nanosheets through thermal exfoliation using dicyandiamide as precursor

g-C₃N₄ has received extensive attention because of its good chemical stability and environmental friendliness. Since g-C₃N₄ prepared from various precursors had different photocatalytic activities, g-C₃N₄ materials marked as U-gCN, D-gCN and M-gCN were synthesized from various precursors of urea, dicyandiamide and melamine, respectively. The D-gCN and M-gCN with smaller surface area were heated again to obtain exfoliated g-C₃N₄ with 2D nanosheet morphology and larger specific surface area named D-gCN-L and M-gCN-L, respectively. The synthesized bulk g-C₃N₄ and g-C₃N₄ 2D nanosheets were characterized by XRD, SEM, BET, PL, UV–Vis diffuse reflectance spectroscopy, XPS, zeta potential and TG. The photocatalytic degradation of methylene blue (MB) was carried out on U-gCN, D-gCN, M-gCN, D-gCN-L and M-gCN-L, and D-gCN-L shows the highest photocatalytic degradation performance because of its larger specific surface area, lower electron-hole recombination and wide light absorption range.     

Synthesis and photocatalytic activity of g-C3N4/ZnO composite microspheres under visible light exposure

In this paper, a novel g-C₃N₄/ZnO composite microspheres (CZCM) with enhanced photocatalytic activity under visible light exposure were successfully prepared by a self-assembly method followed by calcination in the air. A hierarchical structure in which ZnO microspheres were closely covered with g-C₃N₄ nanosheets was constructed. The microstructure and photocatalytic activities of the CZCM were characterized. The photocatalytic property of CZCM was evaluated by degrading solution Methyl Orange (MO) and Tetracycline (TC). The effects of varied contents of g-C₃N₄ on the photocatalytic capability of CZCM were systematically investigated and the results show that the optimized CZ-15% sample exhibit much higher photocatalytic degradation efficiency than that of bare g-C₃N₄ or ZnO under identical conditions. The analysis of Photoluminescence (PL) and photocurrent (PC) independently conformed that the photo-induced electron-hole (e^?-h⁺) pairs in the CZCM were effectively generated and responsible for the observed photocatalysis. The enhanced adsorption of visible-light and the effective charge separation on the surface of CZCM enabled significant improvement of photocatalytic performance. According to the experimental results and relative energy band levels of the two semiconductors, a possible photocatalysis mechanism for the reaction process is proposed.     

g-C3N4的改性策略以及g-C3N4/Ti3C2异质结研究进展

石墨相氮化碳（g-C₃N₄）禁带宽度约为2.7 eV,具有可见光响应能力。由于其良好的热和化学稳定性,且形貌和化学结构可调,在光催化领域应用广泛。但由于其带隙宽,对可见光响应范围窄,且光生载流子的复合率高,导致其光催化效率低,可通过改性来改善。本文综述了对g-C₃N₄形貌调控、掺杂和构建异质结等改性策略,以及g-C₃N₄/Ti₃C₂异质结的作用机理、制备方法和在光催化析氢、有机物降解及合成等领域的应用。     

Facile synthesis of WO3 nanorods/g-C3N4 composites with enhanced photocatalytic activity

In this paper, WO₃ nanorods (NRs)/g-C₃N₄ composite photocatalysts were constructed by assembling WO₃ NRs with sheet-like g-C₃N₄. The as-synthesized photocatalysts were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, UV–vis diffuse reflectance spectroscopy and photoluminescence. The photocatalytic activity of the photocatalysts was evaluated by degradation of Rhodamine B (RhB) under simulated sunlight irradiation. Compared to pristine WO₃ NRs and g-C₃N₄, WO₃ NRs/g-C₃N₄ composites exhibit greatly enhanced photocatalytic activities. The enhanced performance of WO₃ NRs/g-C₃N₄ composite photocatalysts was mainly ascribed to the synergistic effect between WO₃ NRs and g-C₃N₄, which improved the photogenerated carrier separation. A possible degradation mechanism of RhB over the WO₃ NRs/g-C₃N₄ composite photocatalysts was proposed.