Highly efficient photocatalytic H? evolution from water using visible light and structure-controlled graphitic carbon nitride.
ABSTRACT: The major challenge of photocatalytic water splitting, the prototypical reaction for the direct production of hydrogen by using solar energy, is to develop low-cost yet highly efficient and stable semiconductor photocatalysts. Herein, an effective strategy for synthesizing extremely active graphitic carbon nitride (g-C3N4) from a low-cost precursor, urea, is reported. The g-C3N4 exhibits an extraordinary hydrogen-evolution rate (ca. 20,000??mol?h(-1) g(-1) under full arc), which leads to a high turnover number (TON) of over 641 after 6?h. The reaction proceeds for more than 30?h without activity loss and results in an internal quantum yield of 26.5% under visible light, which is nearly an order of magnitude higher than that observed for any other existing g-C3N4 photocatalysts. Furthermore, it was found by experimental analysis and DFT calculations that as the degree of polymerization increases and the proton concentration decreases, the hydrogen-evolution rate is significantly enhanced.
Project description:The use of photocatalysts to purify wastewater and simultaneously convert solar energy into clean hydrogen energy is of considerable significance in environmental science. However, it is still a challenge due to their relatively high costs, low efficiencies, and poor stabilities. In this study, a metal-free carbon quantum dots (CQDs) modified graphitic carbon nitride photocatalyst (CCN) was synthesized by a facile method. The characterization and theoretical calculation results reveal that the incorporation of CQDs into the g-C3N4 matrix significantly improves the charge transfer and separation efficiency, exhibits a redshift of absorption edge, narrows the bandgap, and prevents the recombination of photoexcited carriers. The hydrogen production and simultaneous degradation of methylene blue (MB) or rhodamine B (RhB) in simulated wastewaters were further tested. In the simulated wastewater, the CCN catalyst showed enhanced photodegradation efficiency, accompanied with the increased hydrogen evolution rate (1291 µmol·h-1·g-1). The internal electrical field between the g-C3N4 and the CQDs is the main reason for the spatial separation of photoexcited electron-hole pairs. Overall, this work could offer a new protocol for the design of highly efficient photocatalysts for dye wastewater purification with simultaneous hydrogen production.
Project description:Due to low charge separation efficiency and poor stability, it is usually difficult for single-component photocatalysts such as graphitic carbon nitride (g-C3N4) and silver chromate (Ag2CrO4) to fulfill photocatalytic hydrogen production efficiently. Z-scheme charge transport mechanism that mimics the photosynthesis in nature is an effective way to solve the above problems. Inspired by photosynthesis, we report Ag2CrO4 nanoparticles-decorated g-C3N4 nanosheet as an efficient photocatalyst for hydrogen evolution reaction (HER) with methanol as sacrificial agent. The formation of Z-scheme g-C3N4/Ag2CrO4 nanosheets photocatalysts could inhibit the recombination of photogenerated electron-hole pairs, promote the generation of hydrogen by photosplitting of water. The experiment results indicate that g-C3N4/Ag2CrO4 nanocomposites present enhanced photocatalytic activity and stability in the H2 evolution of water splitting. And the nanocomposites g-C3N4/Ag2CrO4(23.1%) show the 14 times HER efficiency compared to that of bare g-C3N4.
Project description:The photoreduction of CO2 to hydrocarbon products has attracted much attention because it provides an avenue to directly synthesize value-added carbon-based fuels and feedstocks using solar energy. Among various photocatalysts, graphitic carbon nitride (g-C3N4) has emerged as an attractive metal-free visible-light photocatalyst due to its advantages of earth-abundance, nontoxicity, and stability. Unfortunately, its photocatalytic efficiency is seriously limited by charge carriers' ready recombination and their low reaction dynamics. Modifying the local electronic structure of g-C3N4 is predicted to be an efficient way to improve the charge transfer and reaction efficiency. Here, boron (B) is doped into the large cavity between adjacent tri-s-triazine units via coordination with two-coordinated N atoms. Theoretical calculations prove that the new electron excitation from N (2p x , 2p y ) to B (2p x , 2p y ) with the same orbital direction in B-doped g-C3N4 is much easier than N (2p x , 2p y ) to C 2p z in pure g-C3N4, and improves the charge transfer and localization, and thus the reaction dynamics. Moreover, B atoms doping changes the adsorption of CO (intermediate), and can act as active sites for CH4 production. As a result, the optimal sample of 1%B/g-C3N4 exhibits better selectivity for CH4 with ≈32 times higher yield than that of pure g-C3N4.
Project description:A one-dimensional (1D) nanostructure having a porous network is an exceptional photocatalytic material to generate hydrogen (H2) and decontaminate wastewater using solar energy. In this report, we synthesized nanoporous 1D microrods of graphitic carbon nitride (g-C3N4) via a facile and template-free chemical approach at room temperature. The use of concentrated acids induced etching and lift-off because of strong oxidation and protonation. Compared with the bulk g-C3N4, the porous 1D microrod structure showed five times higher photocatalytic degradation performance toward methylene blue dye (MB) under visible light irradiation. The photocatalytic H2 evolution of the 1D nanostructure (34??mol g(-1)) was almost 26 times higher than that of the bulk g-C3N4 structure (1.26??mol g(-1)). Additionally, the photocurrent stability of this nanoporous 1D morphology over 24?h indicated remarkable photocorrosion resistance. The improved photocatalytic activities were attributed to prolonged carrier lifetime because of its quantum confinement effect, effective separation and transport of charge carriers, and increased number of active sites from interconnected nanopores throughout the microrods. The present 1D nanostructure would be highly suited for photocatalytic water purification as well as water splitting devices. Finally, this facile and room temperature strategy to fabricate the nanostructures is very cost-effective.
Project description:Design and preparation of noble-metal-free photocatalysts is of great importance for photocatalytic water splitting harvesting solar energy. Here, we report the high visible-light-driven hydrogen evolution upon the hybrid photocatalyst system consisting of CdS nanocrystals and Ni@NiO nanoparticles grown on the surface of g-C3N4. The hybrid system shows a high H2-production rate of 1258.7??mol h(-1) g(-1) in the presence of triethanolamine as a sacrificial electron donor under visible light irradiation. The synergetic catalytic mechanism has been studied and the results of photovoltaic and photoluminescence properties show that efficient electron transfer could be achieved from g-C3N4 to CdS nanocrystals and subsequently to Ni@NiO hybrid.
Project description:Novel fibrous graphitic carbon nitride (g-C3N4) derivatives prepared from metal organic frameworks (MOFs) were doped with Ce3+ (Ce-C3N4) as photocatalytic materials. Ce-C3N4 was characterized using various techniques, revealing its high specific surface area, excellent photocatalytic activity, and stability for H2 evolution under visible light irradiation. The fluorine modified samples show superior photocatalytic activity under visible light irradiation, which is due to the presence of more active sites and enhanced absorption of solar energy. This work provides a new synthetic route for MOF-derived g-C3N4 that can be doped with different metal ions. The fluorine modified Ce-C3N4 is an efficient photocatalyst with potential for many applications related to energy and the environment.
Project description:The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant 'defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400?nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts.
Project description:Rapid recombination of photoinduced electron-hole pairs is one of the major defects in graphitic carbon nitride (g-C3N4)-based photocatalysts. To address this issue, perforated ultralong TiO2 nanotube-interlaced g-C3N4 nanosheets (PGCN/TNTs) are prepared via a template-based process by treating g-C3N4 and TiO2 nanotubes polymerized hybrids in alkali solution. Shortened migration distance of charge transfer is achieved from perforated PGCN/TNTs on account of cutting redundant g-C3N4 nanosheets, leading to subdued electron-hole recombination. When PGCN/TNTs are employed as photocatalysts for H2 generation, their in-plane holes and high hydrophilicity accelerate cross-plane diffusion to dramatically promote the photocatalytic reaction in kinetics and supply plentiful catalytic active centers. By having these unique features, PGCN/TNTs exhibit superb visible-light H2-generation activity of 1364 µmol h-1 g-1 (? > 400 nm) and a notable quantum yield of 6.32% at 420 nm, which are much higher than that of bulk g-C3N4 photocatalysts. This study demonstrates an ingenious design to weaken the electron recombination in g-C3N4 for significantly enhancing its photocatalytic capability.
Project description:The development of photocatalysts that efficiently degrade organic pollutants is an important environmental-remediation objective. To that end, we report a strategy for the ready fabrication of oxygen-doped graphitic carbon nitride (CN) with engendered nitrogen deficiencies. The addition of KOH and oxalic acid during the thermal condensation of urea led to a material that exhibits a significantly higher pseudo-first-order rate constant for the degradation of bisphenol A (BPA) (0.0225 min-1) compared to that of CN (0.00222 min-1). The enhanced photocatalytic activity for the degradation of BPA exhibited by the dual-defect-modified CN (Bt-OA-CN) is ascribable to a considerable red-shift in its light absorption compared to that of CN, as well as its modulated energy band structure and more-efficient charge separation. Furthermore, we confirmed that the in-situ-formed cyano groups in the Bt-OA-CN photocatalyst act as strong electron-withdrawing groups that efficiently separate and transfer photo-generated charge carriers to the surface of the photocatalyst. This study provides novel insight into the in-situ dual-defect strategy for g-C3N4, which is extendable to the modification of other photocatalysts; it also introduces Bt-OA-CN as a potential highly efficient visible-light-responsive photocatalyst for use in environmental-remediation applications.
Project description:Norovirus is one of the leading causes of gastroenteritis, acute vomiting, intense diarrhoea, acute pain in the stomach, high fever, headaches, and body pain. Conventional methods of detection gave us very promising results but had disadvantages such as low sensitivity, cost ineffectiveness, reduced specificity and selectivity, etc. Therefore, biosensors can be a viable alternative device which can overcome all setbacks associated with the conventional method. An electrochemical sensor based on oxidized graphitic carbon nitride (Ox-g-C3N4) modified electrochemical paper-based analytical device (ePAD) was fabricated for the detection of norovirus DNA. The synthesized Ox-g-C3N4 nanosheets were characterized by field emission scanning electron microscopy (FESEM), X-ray Diffraction (XRD), UV-Vis spectroscopy and X-Ray Photoelectron Spectroscopy. The capture probe DNA (PDNA) modified electrodes were characterized by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). These two characterization techniques were also employed to find the optimal scan rate, response time and temperature of the fabricated sensor. The fabricated biosensor showed a limit of detection (LOD) of 100 fM. Furthermore, the specificity of the reported biosensor was affirmed by testing the response of capture probe DNA with oxidized graphitic carbon nitride (PDNA/Ox-g-C3N4) modified ePAD on the introduction of a non-complimentary DNA. The fabricated ePAD sensor is easy to fabricate, cost effective and specific, and requires a minimum analysis time of 5 s.