Search Results (104)

The oxidative dehydrogenation of propane (ODHP) catalyzed by oxygen offers several advantages, including resistance to carbon deposition and low energy consumption. However, achieving high propylene selectivity at industrially relevant conversions remains challenging, as existing catalysts typically require temperatures exceeding 500 °C, promoting over-oxidation to CO_x. In this study, we developed a NiO nanoparticle-decorated graphitic carbon nitride catalyst (NiO@CN-600) via thermal polymerization–oxidation for photo-thermal synergistic ODHP. At 430 °C, thermal catalysis achieved a propane conversion of 14%. Remarkably, introducing light irradiation boosted conversion to 24%, a 10% increase. Further experimental results reveal that the photo-thermal synergistic catalysis can be described by the following mechanism: initial thermal energy provides sufficient activation energy, enabling the reaction to overcome the energy barrier and proceed smoothly. Simultaneously, the introduction of light energy enhances the activity of lattice oxygen, making it more likely to detach from the lattice and form oxygen vacancies, which in turn boosts the efficiency of the oxidation reaction on the catalyst surface. Full article

The metal-free polymeric semiconductor graphitic carbon nitride (g-C₃N₄) has emerged as a promising material for photocatalytic applications due to its responsiveness to visible light, adjustable electronic structure, and stability. This review systematically summarizes recent advances in preparation strategies, including thermal polycondensation, solvothermal synthesis, and template methods. Additionally, it discusses modification approaches such as heterojunction construction, elemental doping, defect engineering, morphology control, and cocatalyst loading. Furthermore, it explores the diverse applications of g-C₃N₄-based materials in photocatalysis, including hydrogen (H₂) evolution, carbon dioxide (CO₂) reduction, pollutant degradation, and the emerging field of piezoelectric photocatalysis. Particular attention is given to g-C₃N₄ composites that are rationally designed to enhance charge separation and light utilization. Additionally, the synergistic mechanism of photo–piezocatalysis is examined, wherein a mechanically induced piezoelectric field facilitates carrier separation and surface reactions. Despite significant advancements, challenges persist, including limited visible-light absorption, scalability issues, and uncertainties in the multi-field coupling mechanisms. The aim of this review is to provide guidelines for future research that may lead to the development of high-performance and energy-efficient catalytic systems in the context of environmental and energy applications. Full article

Element doping and functional group modification engineering serve as efficient approaches that contribute to the improvement of the functional efficiency in graphitic carbon nitride (CN) materials. A CN photocatalyst co-modified with sulfur (S) and cyano moieties was prepared through thermal condensation polymerization. The introduced S species modulated the band structure, increased charge carrier mobility, and significantly promoted charge separation and transport. Additionally, the introduction of cyano groups extended light absorption range and improved the material’s selective adsorption of reactant molecules. The as-prepared sulfur-modified CN photocatalyst obtained after a 6 h thermal treatment, which was capable of degrading organic pollutants and producing hydrogen (H₂) efficiently and stably, exhibited excellent catalytic performance. The photocatalyst’s photocatalyst exhibited a significantly enhanced photocatalytic activity, with a Rhodamine B (RhB) removal efficiency reaching 97.3%. Meanwhile, the H₂ production level reached 1221.47 μmol h⁻¹g⁻¹. Based on four-cycle experiments, the photocatalyst exhibited excellent recyclability and stability in both H₂ production processes and photocatalytic organic pollutant degradation. In addition, mechanistic studies confirmed the dominant role of ·OH and ·O₂⁻ as active species responsible for the reaction system’s performance. This study highlights that the co-decoration of heteroatoms and functional groups can markedly enhance the photocatalytic performance of CN-based materials, offering considerable potential for future applications in energy conversion and environmental remediation. Full article

Reactive oxygen species (ROS) are increasingly recognized as decisive actors in photocatalytic redox chemistry, dictating both the selectivity and efficiency of target reactions, while most photocatalytic systems generate a mixture of ROS under illumination. Recent studies have revealed that tailoring the generation of specific ROS, rather than maximizing the overall ROS yield, holds the key to unlocking high-performance and application-specific catalysis. In this context, the selective production of specific ROS has emerged as a critical requirement for achieving target-oriented and sustainable photocatalytic transformations. Among the various photocatalytic materials, polymeric carbon nitride (PCN) has garnered considerable attention due to its metal-free composition, visible-light response, tunable structure, and chemical robustness. More importantly, the tunable band structure, surface chemistry, and interfacial environment of PCN collectively make it an excellent scaffold for the controlled generation of specific ROS. In recent years, numerous strategies including molecular doping, defect engineering, heterojunction construction, and co-catalyst integration have been developed to precisely tailor the ROS profile derived from PCN-based systems. This review provides a comprehensive overview of ROS regulation in PCN-based photocatalysis, with a focus on type-specific strategies. By classifying the discussion according to the major ROS types, we highlight the mechanisms of their formation and the design principles that govern their selective generation. In addition, we discuss representative applications in which particular ROS play dominant roles and emphasize the potential of PCN systems in achieving tunable and efficient photocatalytic performance. Finally, we outline key challenges and future directions for developing next-generation ROS-regulated PCN photocatalysts, particularly in the context of reaction selectivity, dynamic behavior, and practical implementation. Full article

Graphitic carbon nitride (g-C₃N₄)-based materials hold significant promise for environmental remediation, particularly water purification, owing to their unique electronic structure, metal-free composition, and robust chemical stability. However, powdered g-C₃N₄ faces challenges such as particle aggregation, poor recyclability, and limited exposure of active sites. Structuring g-C₃N₄ into hydrogels or aerogels—three-dimensional porous networks offering high surface area, rapid mass transport, and tunable porosity—represents a transformative solution. This review comprehensively examines recent advances in g-C₃N₄-based gels, covering synthesis strategies such as crosslinking (physical/chemical), in situ polymerization, and the sol–gel and template method. Modification approaches including chemical composition and structural engineering are systematically categorized to elucidate their roles in optimizing catalytic activity, stability, and multifunctionality. Special emphasis is placed on environmental applications, including the removal of emerging contaminants and heavy metal ions, as well as solar-driven interfacial evaporation for desalination. Throughout, the critical interplay between gel structure/composition and performance is evaluated to establish design principles for next-generation materials. Finally, this review identifies current challenges regarding scalable synthesis, long-term stability, in-depth mechanistic understanding, and performance in complex real wastewater matrices. This work aims to provide valuable insights and guidance for advancing g-C₃N₄-based hydrogel and aerogel technologies in environmental applications. Full article

The development of efficient photocatalytic materials for waterborne pathogen inactivation and self-cleaning surfaces in biomedical applications remains a critical challenge due to the rising prevalence of antimicrobial-resistant bacteria. This study systematically investigates the structural, optical, and photocatalytic disinfection properties of graphitic carbon nitride (g-C₃N₄) synthesized at variable temperatures (450–600 °C) and doped with transition metals (Mn, Co, Cu). Through FTIR and UV/Vis spectroscopy, we demonstrate that synthesis temperatures between 450 and 550 °C yield a well-ordered polymeric network with enhanced π-conjugation and charge separation, while 600 °C induces structural degradation. Metal doping with Mn and Co significantly enhances photocatalytic disinfection, achieving complete E. coli inactivation (6-log reduction) within 6 h via optimized reactive oxygen species (ROS) generation. The best material (g-C₃N₄ synthesized at 500 °C and doped with Mn) was integrated into sodium alginate hydrogel surfaces, demonstrating reusable self-cleaning functionality with sustained bactericidal activity (5.9-log CFU/mL reduction after five cycles). This work provides a roadmap for tailoring metal-doped g-C₃N₄ composites for practical antimicrobial applications, emphasizing the interplay between synthesis parameters, ROS dynamics, and real-world performance. Full article

Herein, a bi-functional composite photocatalyst was synthesized by integrating carbon nanotubes (CNTs) and graphitic carbon nitride (GCN) via a facile electrostatic self-assembly strategy. The resulting CNTs/GCN composite served dual roles as both a solid emulsifier and a photocatalyst, enabling highly efficient photocatalytic benzyl alcohol oxidation within a Pickering emulsion system. The relationship between emulsion droplet size and solid emulsifier dosage was investigated and optimized. The enhanced photocatalytic function was supported by an improved photocurrent response and reduced charge-transfer resistance, attributed to superior charge separation efficiency. Consequently, the benzyl alcohol conversion efficiency achieved in the Pickering emulsion system (58.9%) was three-fold of that observed in a traditional oil–water non-emulsion system (19.0%). Key active species were identified as photoholes, and an interfacial reaction mechanism was proposed. This work provides a new approach for extending photocatalytic applications in aqueous environments to diverse organic conversion reactions through the construction of multifunctional photocatalysts. Full article

Over efficient photocatalysts, CO₂ photoreduction typically converts CO₂ into low-carbon chemicals, which serve as raw materials for downstream synthesis processes. Here, an efficient composite photocatalyst heterojunction (Cu₂O-u/g-C₃N₄) has been fabricated to reduce CO₂. Graphitic carbon nitride (g-C₃N₄) was synthesized via thermal polymerization of urea at 550 °C, while pre-dispersed Cu₂O derived from urea pyrolysis (Cu₂O-u) was prepared by thermal reduction of urea and CuCl₂·2H₂O at 180 °C. The heterojunction Cu₂O-u/g-C₃N₄ was subsequently constructed through hydrothermal treatment at 180 °C. This heterojunction exhibited a bandgap of 2.10 eV, with dual optical absorption edges at 485 nm and above 800 nm, enabling efficient harvesting of solar light. Under 175 W mercury lamp irradiation, the heterojunction catalyzed liquid-phase CO₂ photoreduction to formic acid, acetic acid, and methanol. Its formic acid production activity surpassed that of pristine g-C₃N₄ by 3.14-fold and TiO₂ by 8.72-fold. Reaction media, hole scavengers, and reaction duration modulated product selectivity. In acetonitrile/isopropanol systems, formic acid and acetic acid production reached 579.4 and 582.8 μmol·h⁻¹·g_cat⁻¹. Conversely, in water/triethanolamine systems, methanol production reached 3061.6 μmol·h⁻¹·g_cat⁻¹, with 94.79% of the initial conversion retained after three cycles. Finally, this work ends with the conclusions of the CO₂ photocatalytic reduction to formic acid, acetic acid, and methanol, and recommends prospects for future research. Full article

The efficient depolymerization of lignin has become a key challenge in the preparation of high-value-added chemicals. Graphitic carbon nitride (g-C₃N₄)-based photocatalytic system shows potential due to its mild and green characteristics over other depolymerization methods. However, its inherent defects, such as a wide band gap and rapid carrier recombination, severely limit its catalytic performance. In this paper, a g-C₃N₄ modification strategy of K⁺ doping and surface alkalinization is proposed, which is firstly applied to the photocatalytic depolymerization of the lignin β-O-4 model compound (2-phenoxy-1-phenylethanol). K⁺ doping is achieved by introducing KCl in the precursor thermal polymerization stage to weaken the edge structure strength of g-C₃N₄, and post-treatment with KOH solution is combined to optimize the surface basic groups. The structural/compositional evolution of the materials was analyzed by XRD, FTIR, and XPS. The morphology/element distribution was visualized by SEM-EDS, and the optoelectronic properties were evaluated by UV–vis DRS, PL, EIS, and transient photocurrent (TPC). K⁺ doping and surface alkalinization synergistically regulate the layered structure of the material, significantly increase the specific surface area, introduce nitrogen vacancies and hydroxyl functional groups, effectively narrow the band gap (optimized to 2.35 eV), and inhibit the recombination of photogenerated carriers by forming electron capture centers. Photocatalytic experiments show that the alkalinized g-C₃N₄ can completely depolymerize 2-phenoxy-1-phenylethanol with tunable product selectivity. By adjusting reaction time and catalyst dosage, the dominant product can be shifted from benzaldehyde (up to 77.28% selectivity) to benzoic acid, demonstrating precise control over oxidation degree. Mechanistic analysis shows that the surface alkaline sites synergistically optimize the C_β-O bond breakage path by enhancing substrate adsorption and promoting the generation of active oxygen species (·OH, ·O₂⁻). This study provides a new idea for the efficient photocatalytic depolymerization of lignin and lays an experimental foundation for the interface engineering and band regulation strategies of g-C₃N₄-based catalysts. Full article

Visible-light-driven photocatalytic hydrogen production is one of the ideal green technologies for solar-to-chemical energy conversion. Carbon nitride (C₃N₄, CN) has been attracting extensive attention for its suitable band structure and stability, but the efficiency of photocatalytic hydrogen evolution is low due to insufficient visible-light absorption and rapid charge recombination. Herein, we develop a novel (F, K)-co-doped CN (FKCN) catalyst via a facile thermal polymerization approach using KOH-modified melamine and NH₄F as the dopant precursors. The FKCN catalyst demonstrates broadened light absorption, significantly enhanced charge separation, and excellent cyclic stability. And the optimal F_(0.15)K₍₆₎CN catalyst achieves a hydrogen evolution rate of as high as 3101.5 μmol g⁻¹ h⁻¹ (12-fold that of pristine CN) under visible-light irradiation (λ ≥ 420 nm), which is among the best element-doped CN photocatalysts. This work highlights the effectiveness of a multi-element doping strategy in designing CN-based photocatalysts for efficient hydrogen evolution. Full article

Over the last decade, polymeric carbon nitrides (PCNs) have received exponentially growing attention as metal-free photocatalytic platforms for green energy generation and environmental remediation. Although PCNs can be easily synthesized from abundant precursors in a powdered form, progress in the field of photoelectrochemical applications requires effective methods for the fabrication of PCN films endowed with suitable mechanical stability and modular chemico-physical properties. In this context, as a proof-of-concept, we report herein on a simple and versatile chemical vapor infiltration (CVI) strategy for one-step PCN growth on porous Ni foam substrates, starting from melamine as a precursor compound. Interestingly, tailoring the reaction temperature enabled to control the condensation degree of PCN films from melem/melon hybrids to melon-like materials, whereas the use of different precursor amounts directly affected the mass and morphology of the obtained deposits. Altogether, such features had a remarkable influence on PCN electrochemical performances towards the oxygen evolution reaction (OER), yielding, for the best performing systems, Tafel slopes as low as ≈65 mV/dec and photocurrent density values of ≈1 mA/cm² at 1.6 V vs. the reversible hydrogen electrode (RHE). Full article

Nanomaterials with large specific surface area (SSA) have emerged as pivotal platforms for energy storage and environmental remediation, primarily due to their enhanced active site exposure, improved mass transport capabilities, and superior interfacial reactivity. Among them, polymeric carbon nitride (g-C₃N₄) has garnered significant attention in energy and environmental applications owing to its visible-light-responsive bandgap (~2.7 eV), exceptional thermal/chemical stability, and earth-abundant composition. However, the practical performance of g-C₃N₄ is fundamentally constrained by intrinsic limitations, including its inherently low SSA (<20 m²/g via conventional thermal polymerization), rapid recombination of photogenerated carriers, and inefficient charge transfer kinetics. Notably, the theoretical SSA of g-C₃N₄ reaches 2500 m²/g, yet achieving this value remains challenging due to strong interlayer van der Waals interactions and structural collapse during synthesis. Recent advances demonstrate that state-of-the-art strategies can elevate its SSA to 50–200 m²/g. To break this surface area barrier, advanced strategies achieve SSA enhancement through three primary pathways: pre-treatment (molecular and supramolecular precursor design), in process (templating and controlled polycondensation), and post-processing (chemical exfoliation and defect engineering). This review systematically examines controllable synthesis methodologies for high-SSA g-C₃N₄, analyzing how SSA amplification intrinsically modulates band structures, extends carrier lifetimes, and boosts catalytic efficiencies. Future research should prioritize synergistic multi-stage engineering to approach the theoretical SSA limit (2500 m²/g) while preserving robust optoelectronic properties. Full article

In this research, an emerging, non-metallic photocatalyst was prepared by the thermal polymerization method from three different precursors: urea, melamine, and three mixtures of melamine and cyanuric acid. Graphitic carbon nitride (g-C₃N₄) samples from urea and melamine were synthesized in a muffle furnace at three different temperatures: 450°, 500°, and 550 °C for 2 h, while the samples made of a mixture of melamine and cyanuric acid (with mass ratios of 1:1, 1:2, and 2:1) were synthesized at 550 °C for 2 h. All the samples were characterized in order to determine their chemical and physical properties, such as crystallite size and structure, and phase composition by the following techniques: Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD), and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS). Nitrogen adsorption/desorption isotherms were used to investigate the Brunauer, Emmett, and Teller (BET) specific surface area and Barrett–Joyner–Halenda (BJH) pore size distribution. Band gap values were determined by diffuse reflectance spectroscopy (DRS). Furthermore, adsorption and photocatalytic degradation of the local anesthetic drug procaine were monitored under UV-A, visible, and simulated solar irradiation in a batch reactor. Kinetic parameters, as well as photocatalytic mechanisms using scavengers, were determined and analyzed. The results of the photocatalysis experiments were compared to the benchmark TiO₂ Evonik Aeroxide P25. The results indicated that the g-C₃N₄ sample synthesized from urea at 500 °C for 2 h exhibited the highest degradation rate of procaine under visible light. Full article

Recent research on the use of heptazine-based polymeric carbon nitride materials as potential photocatalysts for hydrogen evolution has made significant progress. However, the impact of the water cluster’s size on the time-dependent photochemical mechanisms during the water splitting process of heptazine–water clusters remains largely unexplored. Here, we present a Landau–Zener trajectory surface hopping dynamics calculation for heptazine–(H₂O)₄ clusters at the ADC(2) level. The electron-driven proton transfer (EDPT) mechanism reaction from water to hydrogen-bonded heptazine–water clusters was confirmed using this method, yielding a heptazinyl radical and an OH biradical as products. The calculated quantum yield of the EDPT for the heptazine–(H₂O)₄ complex was 6.5%, which was slightly lower than that of the heptazine–H₂O complex (9%), suggesting that increasing the water cluster size does not significantly enhance the efficiency of hydrogen transfer. Interestingly, our results show that the de-excitation of the heptazine–water complex from the excited state to the ground state via the EDPT process follows both fast and slow decay modes, which govern population relaxation and facilitate the photochemical water splitting reaction. This newly identified differential decay behavior offers valuable insights that could help deepen our understanding of the EDPT process, potentially improving the efficiency of water splitting under sunlight. Full article

The increasing global demand for clean water is driving the development of advanced wastewater treatment technologies. Graphitic carbon nitride (g-C₃N₄) has emerged as an efficient photocatalyst for degrading organic pollutants, such as synthetic dyes, due to its exceptional thermo-chemical stability. However, its application is limited by an insufficient specific surface area, low photocatalytic efficiency, and an unclear degradation mechanism. In this study, we aimed to enhance g-C₃N₄ by doping it with elemental chlorine, resulting in a series of Cl-C₃N₄ photocatalysts with varying doping ratios, prepared via thermal polymerization. The photocatalytic activity of g-C₃N₄ was assessed by measuring the degradation rate of RhB. A comprehensive characterization of the Cl-C₃N₄ composites was conducted using SEM, XRD, XPS, PL, DRS, BET, EPR, and electrochemical measurements. Our results indicated that the optimized 1:2 Cl-C₃N₄ photocatalyst exhibited exceptional performance, achieving 99.93% RhB removal within 80 min of irradiation. TOC mineralization reached 91.73% after 150 min, and 88.12% removal of antibiotics was maintained after four cycles, demonstrating the excellent stability of the 1:2 Cl-C₃N₄ photocatalyst. Mechanistic investigations revealed that superoxide radicals (·O₂⁻) and singlet oxygen (¹O₂) were the primary reactive oxygen species responsible for the degradation of RhB in the chlorine-doped g-C₃N₄ photocatalytic system. Full article