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Graphitic carbon nitride

Graphitic carbon nitride (g-C₃N₄) is a metal-free, two-dimensional layered polymeric semiconductor material primarily composed of carbon and nitrogen atoms in a tri-s-triazine (heptazine) network, with a stoichiometric C/N ratio of approximately 0.75 and minor hydrogen impurities.^[1] This structure resembles graphite but incorporates nitrogen-rich motifs that confer unique electronic properties, including a moderate bandgap of ~2.7 eV that enables efficient absorption of visible light up to ~460 nm.^[1] Known for its high thermal stability up to 600°C and chemical inertness in acidic or basic environments, g-C₃N₄ has emerged as a sustainable, earth-abundant alternative to traditional metal-based photocatalysts.^[1] First synthesized in bulk form through thermal polycondensation of nitrogen-rich precursors like melamine, urea, or dicyandiamide at temperatures around 500–550°C, g-C₃N₄ can also be prepared via advanced methods such as chemical vapor deposition, solvothermal processes, or microwave-assisted synthesis to achieve tailored morphologies like nanosheets or nanotubes.^[1] Although carbon nitrides were theorized as early as the 19th century and Liebig reported melon (a precursor) in 1834, the material gained prominence in 2009 when Wang et al. demonstrated its photocatalytic activity for visible-light-driven water splitting without metals, marking a breakthrough in sustainable energy conversion.^[2]^[3] Key properties of g-C₃N₄ include a high specific surface area (typically 10–100 m²/g, tunable up to 250 m²/g in mesoporous forms), low density (~2.0–2.5 g/cm³), and favorable charge carrier dynamics, though it suffers from modest quantum efficiency due to rapid electron-hole recombination.^[4]^[1] Modifications such as non-metal doping (e.g., phosphorus or sulfur), metal co-catalysts (e.g., Pt), or heterojunction formation with oxides like TiO₂ enhance its performance by narrowing the bandgap, improving charge separation, and increasing active sites.^[1] In applications, g-C₃N₄ excels in photocatalysis for hydrogen evolution from water (rates up to several hundred μmol h⁻¹ g⁻¹ under visible light), CO₂ reduction to fuels like methane or methanol, and degradation of organic pollutants such as dyes (e.g., >90% removal of rhodamine B in under 2 hours).^[2]^[1] Beyond energy and environment, it serves in sensing (e.g., for heavy metals or explosives), antibacterial disinfection, and energy storage as supercapacitor electrodes, with ongoing research focusing on nanostructuring and composites to overcome limitations like low conductivity.^[4]^[1]

Introduction

Definition and composition

Graphitic carbon nitride, often denoted as g-C₃N₄, is a metal-free polymeric semiconductor featuring a layered structure analogous to graphite. It serves as a visible-light-responsive photocatalyst and is distinguished by its thermal and chemical stability. The material is predominantly composed of carbon and nitrogen atoms in a stoichiometric ratio of 3:4, yielding the empirical formula C₃N₄, though trace amounts of hydrogen may be present due to incomplete polymerization.^[2]^[5] The fundamental building block of g-C₃N₄ is the tri-s-triazine (heptazine) unit, represented as C₆N₇, where these planar rings are interconnected via tertiary nitrogen bridges to form an extended two-dimensional covalent network. This arrangement results in stacked layers held together by van der Waals forces, mimicking the interlayer interactions in graphite. The polymeric nature of g-C₃N₄ sets it apart from other carbon nitride allotropes, such as β-C₃N₄, which possesses a denser, three-dimensional crystalline structure predicted to exhibit superhard properties.^[2]^[6]^[5] Compositional variations in g-C₃N₄ arise from synthesis-induced defects, such as nitrogen vacancies or amino groups, which can deviate the actual C/N ratio from the ideal 0.75 and affect electronic properties. Doping with heteroatoms like phosphorus, sulfur, or oxygen further modifies the stoichiometry, introducing tunable bandgaps and enhanced charge carrier dynamics without altering the core polymeric framework.^[6]^[5]

History and discovery

The discovery of graphitic carbon nitride can be traced to the early 19th century, when chemists began exploring nitrogen-rich carbon compounds. In 1834, Justus von Liebig, inspired by Jöns Jacob Berzelius, synthesized the first polymeric form of carbon nitride, termed "melon," through the thermal decomposition of mercury(II) thiocyanate.^[7] This yellow, insoluble material was recognized as a linear polymer primarily composed of heptazine units linked by hydrogen bonds, marking the initial identification of a stable, albeit amorphous, carbon nitride structure.^[8] Subsequent investigations in the early 20th century built on this foundation, with researchers like Edgar C. Franklin analyzing melon's composition in 1922 and confirming its approximate formula as (C₃N₃H)ₓ through elemental analysis. Efforts to synthesize crystalline, non-graphitic carbon nitride polymorphs during this period, however, were hampered by their inherent instability under ambient conditions, limiting progress to polymeric variants like melon.^[9] A resurgence of interest occurred in the 1990s, driven by theoretical predictions of exceptional mechanical properties for dense carbon nitride phases. In 1990, A.Y. Liu and M.L. Cohen used first-principles calculations to propose that the β-C₃N₄ polymorph, analogous to β-Si₃N₄, could exhibit a bulk modulus and hardness surpassing that of diamond due to its high atomic density and strong covalent bonding. This work sparked extensive experimental attempts to realize such superhard materials, though stable synthesis remained elusive. The modern era of graphitic carbon nitride began with its rediscovery in 2006 by Markus Antonietti, Frédéric Goettmann, and coworkers, who prepared a stable, layered graphitic form (g-C₃N₄) via thermal polycondensation of cyanamide at moderate temperatures, yielding a semiconductor with potential catalytic applications.^[10] This breakthrough was followed in 2009 by confirmation of g-C₃N₄'s photocatalytic activity, as demonstrated by Xinchen Wang and colleagues, who showed its ability to evolve hydrogen from water under visible light without metal cocatalysts, highlighting its promise as a metal-free photocatalyst.

Synthesis

Thermal polymerization methods

Thermal polymerization represents the primary and most straightforward method for synthesizing graphitic carbon nitride (g-C3N4), relying on the thermal condensation of nitrogen-rich organic precursors to form the polymeric network. Common precursors include urea (CO(NH2)2), melamine (C3H6N6), dicyandiamide (C2H4N4), and cyanamide (CN2H2), which are selected for their high nitrogen content and ability to undergo polycondensation. These materials are heated in a furnace at temperatures ranging from 500 to 600°C for 2 to 4 hours, typically in air or an inert atmosphere such as nitrogen to control oxidation and ensure complete reaction.^[11] The synthesis proceeds through a stepwise mechanism. Initially, at lower temperatures around 400°C, the precursor decomposes and oligomerizes to form melon, an intermediate composed of tri-s-triazine (heptazine) units connected by imino (-NH-) bridges. Further heating to 520–550°C induces graphitization, where melon chains align and stack into layered, two-dimensional sheets with a graphite-like structure, driven by the elimination of ammonia and other volatile byproducts. This process yields yellow to pale yellow g-C3N4 powder with a composition approximating C3N4.^[11] Yield and material quality are optimized by controlling reaction parameters, particularly temperature, to avoid excessive carbonization that leads to structural defects or reduced porosity. For example, calcination of dicyandiamide at 520°C typically produces g-C3N4 with a surface area of 10–70 m²/g, while higher temperatures can lead to sintering and reduced porosity below 10 m²/g. Precursor choice also influences outcomes; melamine typically yields more crystalline material, while urea promotes higher porosity but requires careful handling to manage gas evolution.^[11] The thermal polymerization route excels in scalability for bulk production, utilizing readily available, low-cost precursors and standard laboratory or industrial furnaces without specialized equipment. This economic viability has made it the dominant method since its refinement in early works on polymeric carbon nitrides. The dehydrative coupling builds the C-N framework through progressive condensation.

Advanced fabrication techniques

Template-assisted synthesis represents an advanced approach to fabricate porous graphitic carbon nitride (g-C₃N₄) structures, enabling controlled porosity and enhanced surface area compared to bulk materials derived from basic thermal polymerization. In hard-templating methods, ammonium chloride (NH₄Cl) serves as a sacrificial template, where melamine or urea precursors are mixed with NH₄Cl and heated at approximately 550°C, followed by template removal via acid washing to yield yolk-shell or porous morphologies. This technique produces g-C₃N₄ with hierarchical pores, improving mass transport in applications.^[12] Solvothermal and hydrothermal routes offer low-temperature alternatives for synthesizing nanostructured g-C₃N₄, typically employing organic solvents or water to facilitate precursor assembly under pressure. For instance, melamine dissolved in acetonitrile undergoes solvothermal treatment at 150–200°C for 12–24 hours in a sealed autoclave, resulting in spherical or nanosheet-like particles with improved crystallinity and reduced defects. These conditions promote in situ polymerization while suppressing aggregation, yielding materials with tunable morphologies. Hydrothermal variants using aqueous urea solutions at similar temperatures produce analogous ultrathin sheets, leveraging water's polarity for better dispersion.^[13] Chemical vapor deposition (CVD) variants enable the precise growth of thin g-C₃N₄ films on substrates, suitable for device integration. Thermal CVD involves vaporizing melamine at 400–600°C in a carrier gas flow over heated substrates like silicon or metals, depositing uniform films as thin as 10 nm with high conformity. This method allows scalable production of 2D g-C₃N₄ layers directly on conductive surfaces. Complementarily, electrodeposition, particularly cathodic methods, deposits g-C₃N₄ films from electrolyte solutions containing melamine and cyanuric chloride in organic solvents like acetone or acetonitrile, applying a negative potential (e.g., -1.5 V) to drive precursor reduction and polymerization on electrodes. These films exhibit thicknesses of 50–200 nm and adhere well to metals or semiconductors.^[14]^[15] Exfoliation techniques transform bulk g-C₃N₄ into few-layer nanosheets, increasing the specific surface area and exposing more active edges. Ultrasonication of bulk material in water for several hours shears interlayer van der Waals forces, producing dispersions of 2–5 layer nanosheets with lateral sizes of 100–500 nm. Acid-assisted variants, such as protonation with phosphoric acid followed by ultrasonication, intercalate H⁺ ions to swell the structure, yielding porous nanosheets approximately 3 nm thick after neutralization and washing. These methods are simple, scalable, and preserve the tri-s-triazine framework while achieving yields up to 20–30% of ultrathin products.^[16]^[17]

Structure and characterization

Molecular and crystal structure

Graphitic carbon nitride (g-C₃N₄), often referred to as melon in its polymeric form, exhibits a two-dimensional layered architecture characterized by heptazine (tri-s-triazine) units linked by bridging nitrogen atoms to form extended planar sheets. These heptazine cores, with the formula C₆N₇, are connected via -NH- bridges, creating a conjugated polymeric network that mimics the graphene-like arrangement in graphite but with alternating carbon and nitrogen atoms. The in-plane connectivity relies on strong covalent bonds, while the layers stack through weak van der Waals forces, enabling facile exfoliation and interlayer sliding. This structural motif was elucidated through a combination of electron diffraction, solid-state NMR, and theoretical modeling, confirming the presence of heptazine rings as the fundamental building blocks rather than triazine units.^[8] The crystal structure of g-C₃N₄ is hexagonal, featuring a unit cell with lattice parameter a ≈ 0.325 nm, corresponding to the in-plane repeat distance between adjacent structural motifs, and an interlayer spacing of approximately 0.326 nm as determined from X-ray diffraction peaks at around 27.5° (002 reflection). Within the layers, the polymeric nature is defined by covalent C-N bonds with lengths varying between 1.33 Å and 1.47 Å, reflecting partial double-bond character due to π-conjugation across the heptazine units and bridges; shorter bonds (≈1.33 Å) occur in the aromatic rings, while longer ones (≈1.47 Å) appear at the bridging sites. This bonding arrangement imparts a high degree of planarity to the sheets, with minimal buckling, as supported by density functional theory calculations that optimize the geometry for delocalized electron systems. The overall stoichiometry approaches C₃N₄, though residual hydrogen from incomplete condensation introduces slight deviations.^[18]^[19]^[20] Defects are inherent to g-C₃N₄ due to its condensation-based formation, with common imperfections including nitrogen vacancies that disrupt the ideal heptazine lattice and create localized charge imbalances. These vacancies, often at bridge or peripheral sites, can alter the electronic structure by introducing mid-gap states, as observed in samples prepared via thermal polymerization. Additionally, incomplete polymerization leads to amorphous regions comprising oligomeric fragments or uncondensed amino groups, reducing long-range order and contributing to the typically observed broadening in diffraction patterns. Such defects, while prevalent in bulk materials, can be minimized through controlled synthesis to enhance crystallinity.^[21]^[22]

Spectroscopic and analytical techniques

Fourier-transform infrared (FTIR) spectroscopy is widely employed to identify the functional groups and confirm the chemical bonding in graphitic carbon nitride (g-C3N4). Characteristic absorption peaks typically appear around 800 cm⁻¹, attributed to the breathing mode of the triazine or heptazine ring, while broad bands in the 1200–1600 cm⁻¹ range correspond to stretching vibrations of C-N and C=N bonds in the polymeric network.^[5] Additionally, a broad peak between 3000 and 3500 cm⁻¹ indicates N-H stretching from uncondensed amine groups at the edges of the layers.^[23] These spectral features verify the presence of the heptazine-based framework, distinguishing g-C3N4 from other carbon nitrides.^[24] X-ray diffraction (XRD) provides insights into the crystalline structure and interlayer arrangement of g-C3N4. The diffraction pattern commonly exhibits two distinct peaks: one at approximately 13° (2θ), corresponding to the (100) plane that reflects the in-plane structural packing of the tri-s-triazine units, and a stronger peak at around 27.5° (2θ), associated with the (002) plane indicating interlayer stacking along the c-axis.^[5] These peaks confirm the graphitic-like layered morphology, with the interlayer distance calculated from the (002) peak typically around 0.32 nm, similar to graphite.^[23] Variations in peak intensity or position can indicate changes in crystallinity or exfoliation degree in modified samples. X-ray photoelectron spectroscopy (XPS) is essential for elemental composition analysis and probing the chemical states of carbon and nitrogen atoms on the surface of g-C3N4. The C 1s spectrum usually shows a main peak at about 288 eV, assigned to the sp²-hybridized carbon in the N-C=N configuration within the triazine rings, with minor contributions from adventitious carbon at lower binding energies around 284–285 eV.^[25] For the N 1s spectrum, the dominant peak at approximately 398.5 eV is characteristic of pyridinic nitrogen (C-N=C) in the aromatic structure, while peaks near 400–401 eV may arise from tertiary amines or hydrogen-bonded nitrogen.^[5] The atomic ratio of N/C close to 1.33:1 (or C/N ≈ 0.75) from XPS indicates stoichiometric purity, though surface contamination can slightly alter these values.^[26] Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) are crucial for visualizing the morphology and nanoscale architecture of g-C3N4. SEM images often reveal a layered, sheet-like or porous structure with irregular stacking, highlighting the bulk or exfoliated nature depending on synthesis conditions.^[25] TEM further resolves the ultrathin nanosheets or nanorods, typically 2–10 nm thick, and selected area electron diffraction (SAED) patterns display diffuse rings or spots that confirm the semi-crystalline, turbostratic arrangement of the layers.^[27] These techniques collectively assess purity by identifying any impurities or defects in the morphology.^[28]

Properties

Physical and mechanical properties

Graphitic carbon nitride (g-C₃N₄) in its bulk form exhibits a theoretical density ranging from 1.9 to 2.16 g/cm³, depending on the crystal structure and space group, while porous or powdered variants can have lower densities around 1.3–1.4 g/cm³.^[29]^[30] This density reflects its polymeric, layered architecture, which contributes to its lightweight nature compared to denser carbon-based materials like graphite (2.26 g/cm³). The material demonstrates high thermal stability, remaining intact up to approximately 600°C in air, with decomposition occurring above 600–700°C, primarily releasing isocyanic acid (HNCO), ammonia (NH₃), carbon dioxide (CO₂), and water (H₂O).^[31]^[32]^[33]^[1] This stability arises from strong in-plane C-N bonds within its heptazine units, enabling applications requiring heat resistance, though prolonged exposure beyond 600°C leads to oxidative breakdown. Surface area varies significantly with morphology: bulk g-C₃N₄ typically shows low values below 10 m²/g due to its compact layered stacking, whereas exfoliated or nanosheet forms can achieve up to 300 m²/g or higher through processes like thermal or liquid exfoliation, enhancing accessibility for interactions.^[34]^[35]^[36] Mechanically, g-C₃N₄ nanosheets exhibit a Young's modulus of approximately 200–210 GPa, indicating high stiffness comparable to graphene, with tensile strength around 30 GPa at rupture strains of about 15%.^[37]^[38] Hardness for thin films is measured at 1.0–1.5 GPa via nanoindentation, inferior to diamond (~100 GPa) but sufficient for protective coatings; commercial variants like Nicanite leverage this for tribological uses in low-friction, wear-resistant applications.^[39]^[40]

Electronic and optical properties

Graphitic carbon nitride (g-C₃N₄) is a direct bandgap semiconductor with a bulk optical bandgap of 2.7 eV, enabling absorption of visible light up to approximately 460 nm. This bandgap value arises from the π-π* transitions within its conjugated tri-s-triazine framework. Through exfoliation into few-layer nanosheets or doping with elements such as oxygen or metals, the bandgap can be tuned over the range of 1.8–2.7 eV, which modulates the material's visible-light response and extends its potential for optoelectronic applications.^[41]^[42] The conduction band minimum of g-C₃N₄ is located at approximately -1.1 V versus the normal hydrogen electrode (NHE, at pH 7), while the valence band maximum is at +1.6 V vs. NHE. These band edge positions provide a sufficient driving force for the reduction of protons to hydrogen (at 0 V vs. NHE) and the oxidation of water to oxygen (at +1.23 V vs. NHE), positioning g-C₃N₄ as a viable material for photocatalytic redox processes.^[41]^[43] Due to pronounced excitonic effects stemming from its low dielectric constant and reduced dimensionality, g-C₃N₄ displays a relatively high photoluminescence quantum yield of up to 23%, reflecting efficient radiative recombination of excitons. The electron-hole recombination dynamics occur on a fast timescale of about 200 ps, dominated by non-radiative pathways in the bulk material, which limits charge separation but underscores the strong electron-hole binding.^[44] As an intrinsically p-type semiconductor owing to its nitrogen-rich composition, g-C₃N₄ exhibits very low electrical conductivity on the order of 10⁻¹¹ S/cm, primarily due to limited charge carrier mobility within its layered structure. Doping with acceptors or structural modifications, such as introducing defects or copolymerization, can enhance conductivity by several orders of magnitude, facilitating better charge transport for device integration.^[45]^[46]

Applications

Photocatalytic applications

Graphitic carbon nitride (g-C₃N₄) has emerged as a promising metal-free photocatalyst for visible-light-driven processes due to its suitable bandgap and stability in aqueous environments.^[41] One of its primary applications is in hydrogen evolution through water splitting, where photoexcited electrons in g-C₃N₄ reduce protons to H₂ in the presence of sacrificial electron donors like triethanolamine.^[41] In optimized systems, such as those incorporating platinum (Pt) nanoparticles as co-catalysts, apparent quantum efficiencies of up to 10% at 420 nm have been achieved, highlighting the material's potential for sustainable hydrogen production. Beyond energy generation, g-C₃N₄ excels in the photocatalytic degradation of organic pollutants, including dyes like Reactive Black 5 and antibiotics such as tetracycline, under visible light irradiation.^[47] This process involves the generation of reactive oxygen species (ROS), primarily hydroxyl radicals (•OH) and superoxide radicals (O₂⁻•), which oxidize and mineralize contaminants into harmless byproducts like CO₂ and H₂O.^[48] The efficiency stems from the material's ability to absorb visible light and separate photogenerated charge carriers effectively, often enhanced by modifications like halogen doping (e.g., chlorine) to boost ROS production.^[47] In the realm of carbon dioxide (CO₂) reduction, g-C₃N₄ facilitates the conversion of CO₂ into valuable fuels such as methane (CH₄) or carbon monoxide (CO) using visible light and water or sacrificial agents.^[49] Representative systems demonstrate turnover numbers exceeding 30,000 for formic acid production, with selectivity toward HCOOH often exceeding 87% when paired with co-catalysts like ruthenium complexes.^[50] These applications underscore g-C₃N₄'s role in addressing environmental challenges by mitigating greenhouse gases through solar-driven valorization. The underlying mechanism of these photocatalytic processes begins with photoexcitation of g-C₃N₄ under visible light, promoting electrons from the valence band to the conduction band and leaving holes behind.^[41] The conduction band electrons transfer rapidly to co-catalysts such as Pt, which lowers the overpotential for reduction reactions like H⁺ to H₂ or CO₂ to CO/CH₄, while holes oxidize water or donors to prevent recombination. This charge separation is crucial for sustaining activity, with ultrafast electron transfer dynamics observed at the g-C₃N₄/Pt interface.^[44]

Energy storage and other uses

Graphitic carbon nitride (g-C₃N₄) has emerged as a promising material for electrochemical energy storage due to its layered structure, high nitrogen content, and tunable porosity, which facilitate ion transport and storage mechanisms distinct from its photocatalytic roles.^[51] In supercapacitors, g-C₃N₄ electrodes leverage their porous architecture and nitrogen heteroatoms for pseudocapacitive contributions, achieving specific capacitances of up to 235 F g⁻¹ in protonated nanosheet forms at optimized conditions.^[52] This performance stems from enhanced electrolyte accessibility and reversible redox reactions at nitrogen sites, enabling energy densities suitable for high-power applications.^[51] Its surface area, often exceeding 100 m² g⁻¹, further supports double-layer capacitance alongside pseudocapacitive effects.^[52] As an anode material in lithium-ion batteries, g-C₃N₄ accommodates Li⁺ ions through intercalation between its graphitic layers, delivering reversible capacities of approximately 1525 mAh g⁻¹ in covalently coupled hybrids with reduced graphene oxide.^[53] This mechanism exploits the material's two-dimensional interlayer spacing for reversible ion insertion, offering higher theoretical capacities than traditional graphite anodes while maintaining structural stability over cycles.^[53] In tribological applications, g-C₃N₄-based coatings, commercially known as Nicanite, provide low-friction surfaces with coefficients as low as 0.022 when used as nanoadditives in lubricants for steel contacts.^[54] These coatings form protective tribofilms via amino group interactions, reducing wear and enabling use in biocompatible implants, where amorphous carbon nitride variants exhibit excellent corrosion resistance and hemocompatibility in vitro and in vivo.^[54]^[55] For gas storage, g-C₃N₄ supports hydrogen adsorption through physisorption on its nitrogen-rich surfaces, attaining capacities up to 1.11 wt% at 77 K in scandium-decorated variants, highlighting its potential for low-temperature storage systems.^[56] Beyond energy storage, g-C₃N₄ finds applications in sensing for detecting heavy metals or explosives and in antibacterial disinfection due to its photocatalytic generation of ROS that inactivate bacteria.^[4]^[1]

Recent developments

Material modifications and composites

Non-metal doping with elements such as oxygen and sulfur has been employed to modify the electronic structure of graphitic carbon nitride (g-C₃N₄), narrowing its bandgap and mitigating charge carrier recombination. Oxygen doping, achieved through methods like hydrothermal treatment with hydrogen peroxide or peroxymonosulfate oxidation, reduces the bandgap to 1.80–2.85 eV, enhancing visible-light absorption and charge separation as evidenced by decreased photoluminescence intensity. For instance, oxygen-doped g-C₃N₄ synthesized via thermal polymerization of melamine in ethanol yielded a hydrogen evolution rate of 64.30 μmol·h⁻¹, compared to 3.60 μmol·h⁻¹ for pristine g-C₃N₄ under visible light with triethanolamine as a sacrificial agent and Pt co-catalyst, representing an enhancement of over 17-fold. Similarly, sulfur doping via copolymerization with thioacetamide precursors narrows the bandgap to 1.85–2.56 eV, suppressing recombination and boosting photocatalytic activity; sulfur-doped nanosheets achieved a hydrogen production rate of 127.4 μmol·h⁻¹ versus 0.51 μmol·h⁻¹ for undoped counterparts.^[57]^[57]^[57] Metal co-catalysts, particularly platinum (Pt) and palladium (Pd), are loaded onto g-C₃N₄ at concentrations of 1–3 wt% to facilitate charge separation by acting as electron traps and reaction sites. Single-atom Pd dispersed on g-C₃N₄ at 0.1 wt% loading promotes efficient electron transfer from the photocatalyst, achieving a hydrogen evolution rate of 728 μmol·g⁻¹·h⁻¹ under visible light, significantly higher than higher loadings where Pd aggregates into nanoparticles. Likewise, Pt and Pd single atoms at ~3 wt% enhance proton adsorption and reduce overpotential for hydrogen evolution, with Pd single-atom/g-C₃N₄ exhibiting 8.6 times greater activity per atom than Pd nanoparticles due to superior charge dynamics confirmed by transient absorption spectroscopy. These modifications address g-C₃N₄'s inherent recombination challenges, improving overall photocatalytic efficiency.^[58]^[59]^[59] Composites of g-C₃N₄ with conductive materials like graphene further enhance electron mobility and conductivity, often by 2–5 times compared to pristine g-C₃N₄, by providing pathways for rapid charge transport and reducing recombination. Reduced graphene oxide/g-C₃N₄ hybrids, prepared via thermal copolymerization, exhibit improved electrical conductivity and a narrowed bandgap of 2.40 eV, enabling stable photoreduction of CO₂ to methanol at 114 μmol·g⁻¹·h⁻¹ without scavengers. Homojunctions within g-C₃N₄, such as 0D carbon nitride quantum dots anchored on 2D nanosheets, form type-I band alignments, driving spatial charge separation in layered structures and boosting hydrogen peroxide production to 115 μmol·L⁻¹·h⁻¹—8.6 times higher than bulk g-C₃N₄. These configurations leverage internal band offsets for efficient carrier migration.^[60]^[61]^[61] Defect engineering through vacancy creation, such as nitrogen vacancies induced by KOH-assisted thermal treatment of urea-derived precursors, increases active sites and narrows the bandgap to 2.36 eV, extending visible-light absorption to 525 nm. This approach generates abundant -C≡N groups that stabilize defect structures, enhancing photocarrier separation and yielding a hydrogen evolution rate of 6.9 mmol·g⁻¹·h⁻¹. KOH treatment promotes etching to form ultrathin nanosheets with dual carbon-nitrogen vacancies, further amplifying surface reactivity for solar-driven applications.^[62]^[62]^[63]

Emerging research challenges

Despite significant progress, graphitic carbon nitride (g-C₃N₄) faces persistent challenges in achieving high performance for photocatalytic applications, particularly low quantum efficiency in solar-to-hydrogen (STH) conversion, typically below 5% due to rapid recombination of photogenerated charge carriers.^[64] Poor charge carrier mobility further exacerbates this issue, limiting the separation and transport of electrons and holes to reactive sites.^[65] Additionally, scalability remains a major hurdle for industrial adoption, as current synthesis methods, such as thermal polycondensation, involve complex, energy-intensive processes and specialized equipment that hinder large-scale production.^[66] Recent advances from 2020 to 2025 have targeted these limitations through innovative material engineering. Z-scheme heterojunctions, such as Al–SrTiO₃/g-C₃N₄ with co-catalysts, have demonstrated enhanced charge separation, achieving external quantum efficiencies up to 14% at 365 nm by facilitating direct electron transfer and reducing recombination losses. Meanwhile, AI-optimized doping strategies, leveraging machine learning models like genetic algorithm-supported vector regression, enable precise bandgap tuning (e.g., reducing from 2.7 eV to ~2.0 eV), improving visible-light absorption and photocatalytic rates for hydrogen evolution.^[67]^[68] Stability in operational environments remains a challenge, necessitating greener synthesis routes and enhancements for sustainable deployment.^[66] Looking ahead, promising prospects include integrating g-C₃N₄ as an electron transport layer in perovskite solar cells, where it has boosted power conversion efficiencies to over 22% by passivating defects and improving charge extraction.^[69] In CO₂ capture photocatalysis, g-C₃N₄-based systems show potential for selective reduction to value-added products like CO or CH₄, though challenges in product selectivity and reaction kinetics must be addressed through advanced heterostructures. Recent 2025 developments emphasize intrinsic defect modulation, such as tailored vacancies, and adaptive synthetic approaches to further enhance photocatalytic efficiency and scalability.^[70]^[71]^[72]

References

[1]
A Comprehensive Review of Graphitic Carbon Nitride (g-C 3 N 4 )
This review covers recent advances, including applications in water splitting, CO 2 reduction, and photodegradation of organic pollutants, sensors, bacterial ...
[2]
A metal-free polymeric photocatalyst for hydrogen production from water under visible light - Nature Materials
### Summary of Graphitic Carbon Nitride as a Photocatalyst
[3]
From Triazine to Heptazine: Origin of Graphitic Carbon Nitride as a ...
May 18, 2020 · Graphitic carbon nitride (g-C3N4) has, since 2009, attracted great attention for its activity as a visible-light-active photocatalyst for ...
[4]
Graphitic carbon nitride (g-C3N4) as an emerging photocatalyst for ...
This review article provides a comprehensive examination of g-C3N4, spanning its synthesis methods, structural properties, photocatalytic mechanisms, and ...
[5]
A Comprehensive Review of Graphitic Carbon Nitride (g-C3N4) - NIH
Graphitic carbon nitride (g-C3N4) is a polymeric, visible-light-active photocatalyst with a bandgap of ~2.7 eV (~460 nm), that was introduced since 2006 [1].Missing: history | Show results with:history
[6]
Thermodynamic Equilibria in Carbon Nitride Photocatalyst Materials ...
Apr 28, 2017 · A review; graphitic carbon nitride, g-C3N4, is a polymeric material consisting of C, N, and some impurity H, connected via tris-triazine-based ...
[7]
Polymeric Graphitic Carbon Nitride for Heterogeneous Photocatalysis
Polymeric graphitic carbon nitride (for simplicity, g-C3N4) is a layered material similar to graphene, being composed of only C, N, and some impurity H.Missing: seminal | Show results with:seminal
[8]
Unmasking Melon by a Complementary Approach Employing ...
May 22, 2007 · The structure of Liebig's melon [C6N9H3]n has been unravelled by means of electron diffraction after decades; it represents the missing link ...
[9]
Synthesis and applications of carbon nitride (CN x ) family with ...
However, this material is relatively unstable at room temperature and ambient pressure. The researchers once again turned their attention toward the more ...Missing: instability | Show results with:instability
[10]
Chemical Synthesis of Mesoporous Carbon Nitrides Using Hard ...
Jun 28, 2006 · A material first synthesized in 1834, carbon nitride (C 3 N 4 ), was synthesized in a graphitic mesoporous form by using silica nanoparticles as templates.
[11]
https://doi.org/10.3390/nano12020294
[12]
One-pot synthesis of porous gC 3 N 4 nanomaterials with different ...
Graphitic carbon nitride (gC 3 N 4 ), liking a yolk-shell cake, was successfully prepared via a gas-bubble template method with the assistance of NH 4 Cl.Missing: NH4Cl | Show results with:NH4Cl
[13]
Influence of solvothermal synthesis on the photocatalytic ...
Aug 10, 2017 · This study reports the solvothermal synthesis of carbon nitride (C3N4) photocatalysts by using acetonitrile as a solvent and solvothermal ...
[14]
Controlled Growth of Ultrathin Graphitic Carbon Nitride Films by ...
Feb 6, 2025 · In this work, a thermal chemical vapor deposition (CVD) method was developed for the synthesis of homogeneous g-C3N4 films on various substrates ...Missing: seminal thin
[15]
Graphitic carbon nitride thin films deposited by electrodeposition
Electrodeposition method was used to deposit the graphitic carbon nitride thin film on Si (100) substrate from a saturated acetonitrile solution.Missing: cathodic | Show results with:cathodic
[16]
Simultaneous layer exfoliation and defect activation in g-C3N4 ...
Conventional methods for layer exfoliation are ultrasonication, chemical, thermal oxidation, etc. A thermal oxidation method of bulk g-C3N4 results in ...
[17]
Drastic Enhancement of Photocatalytic Activities over Phosphoric ...
Jul 13, 2016 · A facile approach is developed to fabricate protonated porous g-C3N4 nanosheets by protonation–exfoliation of bulk g-C3N4 with phosphoric ...
[18]
Graphitic carbon nitride materials: variation of structure and ...
Jul 10, 2008 · Graphitic carbon nitride, g-C3N4, can be made by polymerization of cyanamide, dicyandiamide or melamine. Depending on reaction conditions, ...
[19]
Using Dynamics to Determine the Ground-State Properties of g-C3N4
Aug 12, 2025 · The lattice parameters calculated using different DFT functionals are listed in Table 1. Table 1. Lattice Parameters for All Three Structures ...
[20]
mp-567885: C3N4 (Hexagonal, P-6m2, 187) - Materials Project
C₃N₄ crystallizes in the hexagonal P̅6m2 space group. The structure is two-dimensional and consists of two C₃N₄ sheets oriented in the (0, 0, 1) direction.
[21]
Investigating the Role of Tunable Nitrogen Vacancies in Graphitic ...
Jul 5, 2017 · The nitrogen vacancies could cause the excitation of electrons into midgap states so as to absorb photons with longer wavelengths, trap ...
[22]
A Tour‐Guide through Carbon Nitride‐Land: Structure
Jul 11, 2021 · This article reviews the current understanding of the structure–property–function relationship of the graphitic carbon nitride family of ...Historical Development and... · Characterization... · Reactivity of Graphitic Carbon...
[23]
Graphitic Carbon Nitride (g-C3N4) in Photocatalytic Hydrogen ...
Graphitic carbon nitride (gC 3 N 4 ) is one of the most utilized graphitic materials in hydrogen (H 2 ) production via photocatalytic water splitting.Missing: seminal | Show results with:seminal
[24]
Green synthesis of a magnetite/graphitic carbon nitride 2D ...
Jul 1, 2023 · This study presents an effective thermal-sonication technique for producing unique de novo tris-s-triazine carbon nitride nanosheets decorated with magnetite ...
[25]
Room-temperature synthesis of nanoporous 1D microrods ... - Nature
Aug 8, 2016 · In this report, we synthesized nanoporous 1D microrods of graphitic carbon nitride (gC 3 N 4 ) via a facile and template-free chemical approach at room ...<|control11|><|separator|>
[26]
Morphology Control and Photocatalysis Enhancement by the One ...
Jan 2, 2014 · TEM and SEM morphologies indicate that the product is mainly composed of graphitic carbon nitride. ... Graphitic Carbon Nitride (g-C3N4)-Based ...
[27]
Synthesis and characterization of graphitic carbon nitride sub ...
A facile microwave irradiation synthetic method to synthesize carbon nitride sub-microspheres, has been compared with the traditional solvothermal method.
[28]
What is the density of g-C3N4? - ResearchGate
Jan 15, 2019 · The reported density for this compound is at range of 1.9 to 2.16 depending to the space groups and crystal structure.Missing: cm³ | Show results with:cm³
[29]
Graphitic Carbon Nitride (g-C3N4) Micron Powder 1-10 μm
In stockDensity: Approximately 1.3-1.4 g/cm³; Melting Point: Decomposes around 500°C (932°F); Boiling Point: Sublimes at higher temperatures (decomposition point ...
[30]
Rapid high-temperature treatment on graphitic carbon nitride for ...
Oct 5, 2018 · Due to good thermal stability of graphitic carbon nitride up to 600 °C in air atmosphere [30,31], it is necessary to ensure the treated ...
[31]
Insights into chemical reactions of graphitic carbon nitride with alkali ...
Dec 15, 2022 · ... isocyanic acid, HNCO, which is a product of thermal decomposition of cyameluric acid derivatives [26]. Thus, OH. − probably produces sodium ...
[32]
Synthesis of High-Quality Crystalline Carbon Nitride Oxide by ...
Aug 22, 2017 · (34) In the pyrolysis of urea, biuret further reacts with isocyanic acid (formed by urea decomposition) to give cyanuric acid and ammelide ...
[33]
From Synthesis to Applications: Graphitic Carbon Nitride in ...
Oct 11, 2025 · Template-assisted synthesis involves using a scaffold (template) to impose porosity, shape, or hierarchical structure on g-C₃N₄ during or before ...Missing: NH4Cl | Show results with:NH4Cl
[34]
Graphitic carbon nitride nanosheets obtained by liquid stripping as ...
Jul 26, 2017 · The speci c surface area of g-C3N4. (100) was measured to be 41.1 m2 g 1, which was much higher than that of bulk g-C3N4 (15.2 m2 g 1). The high ...
[35]
[PDF] Efficient Advanced Oxidation Process (AOP) for Photocatalytic ...
May 23, 2021 · The surface area of exfoliated g-C3N4 was significantly higher than that of bulk g-C3N4 (170 and 11 m2/g, respectively), and the pore size ...
[36]
[PDF] Mechanical properties and thermal conductivity of graphitic carbon ...
Our MD results suggest that TgCN films can yield elastic modulus 210±5 GPa and tensile strength of around 30 GPa at rupture strain of around 0.15 indpendent ...
[37]
[PDF] Mechanical and electronic properties of graphitic carbon nitride (g ...
Mar 31, 2020 · The lattice constant for g-C3N4 without strain is a ¼ b ¼ 7.15 Å, which is the same with previous theoretical results [29,30]. It shows that ...
[38]
Structural, mechanical and optical properties of thin films deposited ...
Jun 1, 2016 · Surprisingly, nano-indentation experiments showed a lower mechanical hardness (~ 1.0 to 1.5 GPa) and reduced Young's modulus (24 to 27 GPa) for ...
[39]
Carbodeon | OEM Off-Highway
Similarly, the company's Nicanite graphitic carbon nitride can be converted to carbon nitride thin-film coatings with unique properties. Products & Press ...
[40]
Photocatalytic Activities of Graphitic Carbon Nitride Powder for ...
Mar 5, 2009 · Graphitic carbon nitride (g-C3N4) with a band gap of 2.7 eV is studied as a nonmetallic photocatalyst for H2 or O2 evolution from water ...
[41]
Visible-Light-Responsive Graphitic Carbon Nitride: Rational Design ...
Recently, graphitic carbon nitride (g-C3N4) has emerged as an innovative photocatalyst with tunable band gaps of 1.8–2.7 eV that allow the harvesting of visible ...<|control11|><|separator|>
[42]
Energy band engineering of graphitic carbon nitride for ...
Jul 9, 2024 · This review systematically elaborates the inherent relationship between band structure tuning strategies and resulting energy band ...Abstract · INTRODUCTION · ENERGY BAND... · PERSPECTIVES AND...
[43]
Time-Resolved Spectroscopic Investigation of Charge Trapping in ...
Mar 20, 2017 · We have investigated the photophysics of a series of carbon nitrides on time scales ranging from femtoseconds to seconds.
[44]
Dielectric constant of thin film graphitic carbon nitride (g-C3N4) and ...
Mar 8, 2021 · The reported conductivity of g-C3N4 is very low (10–11 S/cm)14 and, hence, has not been well studied for semiconductor device applications.
[45]
Element-doped graphitic carbon nitride - RSC Publishing
Jun 17, 2021 · The bandgap of g-CN is ∼2.7 eV with the conduction band (CB) minimum at ∼−1.1 eV and the valence band (VB) maximum at ∼+1.6 eV vs.
[46]
Chlorine-Doped Graphitic Carbon Nitride for Enhanced ...
Aug 27, 2025 · The photocatalytic degradation mechanism is carried out by the production of reactive oxygen species, such as hydroxyl radicals (•OH) and ...
[47]
Graphitic carbon nitride photocatalysis: the hydroperoxyl radical role ...
The photocatalytic degradation mechanism using GCN is attributed to a series of reactions with reactive oxygen species and photogenerated holes.
[48]
Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial ...
May 20, 2016 · This critical review summarizes a panorama of the latest progress related to the design and construction of pristine gC 3 N 4 and gC 3 N 4 -based ...<|control11|><|separator|>
[49]
Nature-Inspired, Highly Durable CO2 Reduction System Consisting ...
Apr 20, 2016 · Modification of C3N4 with Ag nanoparticles resulted in a RuRu'/Ag/C3N4 photocatalyst that exhibited a very high turnover number (>33000 with ...
[50]
Emerging role of graphitic carbon nitride in advanced supercapacitors
Among the seven carbon nitride phases, graphitic carbon nitride (g-C3N4) stands unique for its lowest band gap energy (∼2.6 eV). Its structural framework is ...
[51]
Protonated C 3 N 4 Nanosheets for Enhanced Energy Storage in ...
Graphitic carbon nitride (g-C3N4) has emerged as one of the most promising photocatalysts due to its metal-free nature, abundance of raw material, and thermal ...
[52]
Covalently coupled hybrid of graphitic carbon nitride with reduced ...
Covalently coupled hybrid of graphitic carbon nitride with reduced graphene oxide as a superior performance lithium-ion battery anode† ... capacity of 1525 ...
[53]
https://pubs.rsc.org/en/content/articlelanding/2014/nr/c4nr03145h
[54]
Improved corrosion resistance and biocompatibility of ...
Jan 5, 2019 · The biocompatibility and hemolysis rate of graphitic carbon nitride films were studied via in vitro cellular experiments and in vivo animal ...
[55]
Hydrogen storage in scandium decorated triazine based g-C3N4
... hydrogen storage investigated at 298 K and 77 K showing gravimetric adsorption capacity for hydrogen of 0.12–0.14% and 0.21–1.11% respectively for different ...
[56]
Doping of Graphitic Carbon Nitride with Non-Metal Elements and Its ...
The doping of more oxygen groups in O-g-C3N4 caused a decrease of the optical band gap from 2.82 to 2.79 eV. The doping of oxygen improved the separation of ...
[57]
Atomic palladium on graphitic carbon nitride as a hydrogen ... - Nature
Feb 15, 2019 · Using noble metals as co-catalysts is an effective strategy to enhance photocatalytic efficiency of semiconductors, for which noble metals not ...
[58]
Metal Single‐Atom Cocatalyst on Carbon Nitride for the ...
May 8, 2023 · The role of the cocatalysts is to i) promote charge separation of electrons and holes generated by photoexcitation, as well as ii) work as the ...
[59]
Bandgap engineered g-C3N4 and its graphene composites for ...
Jun 15, 2022 · To further improve the charge separation and conductivity, g-C3N4 and reduced graphene oxide (rGO) based composites were synthesized. The ...
[60]
Band alignment of homojunction by anchoring CN quantum dots on ...
We developed a simple method to anchor CN quantum dots (QDs) onto gC 3 N 4 nanosheets to form a homojunction structure (HJ-C 3 N 4 ), which could improve ...Band Alignment Of... · 3. Results And Discussion · 3.4. Catalytic Performance...
[61]
Decade Milestone Advancement of Defect-Engineered g-C3N4 for ...
Jan 4, 2024 · In general, the defect engineering on g-C3N4 should obey three important principles, namely the basic creation of abundant active sites, ...
[62]
Construction of carbon and nitride double vacancy defects on ...
This work provides a mild approach for engineering carbon and nitride double vacancy defects on gC 3 N 4 nanosheets, accompanied by tuning carbon/nitride ratio.
[63]
Tailoring Graphitic Carbon Nitride (g-C 3 N 4 ) for Multifunctional ...
Sep 2, 2025 · Thermal polymerization is a widely used method for synthesizing g-C3N4 due to its simplicity and cost-effectiveness.
[64]
Current Strategies to Improve the Properties of Graphitic Carbon ...
... Justus von Liebig, in 1834, who ended up calling it 'melon'. Its empirical composition was detailed by Franklin in 1922, who determined that it varied ...
[65]
Graphitic carbon nitride (gC 3 N 4 ) as an emerging photocatalyst for ...
Dec 4, 2023 · Finally, scaling up g-C3N4 production from laboratory-scale to practical, large-scale applications presents logistical challenges, requiring ...2. Synthesis Methods · 4. Photocatalytic Mechanism · 5.6 Solar Fuel Cells
[66]
Development of Z-scheme Al–SrTiO 3 /gC 3 N 4 heterojunctions with ...
May 1, 2025 · The optimized Al–SrTiO3/g-C3N4 showed significant improvement in hydrogen evolution up to 15.9 mmolg−1h−1, and the maximum value of EQE reached ...
[67]
Prediction of Band Gap Energy of Doped Graphitic Carbon Nitride ...
This work for modeling the associated band gap using hybrid genetic algorithm-based support vector regression (GSVR) and extreme learning machine (ELM).
[68]
Unveiling Versatile Applications and Toxicity Considerations of ...
In this review, we first describe the fundamental methods of synthesis of both bulk and exfoliated g-C3N4 nanomaterials. Subsequently, we aim to provide a brief ...
[69]
Recent Advances in g-C 3 N 4 for the Application of Perovskite Solar ...
Currently, the power conversion efficiency of PSCs based on modified g-C3N4 has been increased up to 22.13%, and its unique two-dimensional (2D) package ...
[70]
Recent advancements in g-C3N4-based photocatalysts for ...
Aug 11, 2020 · This review summarizes the advancements that have been made in the synthesis and photocatalytic applications of gC 3 N 4 -based catalysts for CO 2 reduction in ...