Graphitic carbon nitride (g-C₃N₄) is a family of

carbon nitride In organic chemistry, carbon nitrides are compounds consisting only of carbon and nitrogen atoms. Covalent network compounds * Beta carbon nitride - a solid with a formula β-, which is predicted to be harder than diamond. * Graphitic carbon ...

compounds with a general formula near to C₃N₄ (albeit typically with non-zero amounts of hydrogen) and two major substructures based on

heptazine Heptazine, or tri-''s''-triazine or cyamelurine, is a chemical compound with formula , that consist of a planar triangular core group or three fused triazine rings, with three hydrogen atoms at the corners. It is a yellow, weakly fluorescent soli ...

and poly(triazine imide) units which, depending on reaction conditions, exhibit different degrees of

condensation Condensation is the change of the state of matter from the gas phase into the liquid phase, and is the reverse of vaporization. The word most often refers to the water cycle. It can also be defined as the change in the state of water vapor to ...

, properties and reactivities.

Preparation

Graphitic carbon nitride can be made by

polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer, monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are ...

cyanamide Cyanamide is an organic compound with the chemical formula, formula carbon, Cnitrogen, N2hydrogen, H2. This white solid is widely used in agriculture and the production of pharmaceuticals and other organic compounds. It is also used as an alcoho ...

dicyandiamide 2-Cyanoguanidine is a nitrile derived from guanidine. It is a dimer of cyanamide, from which it can be prepared. 2-Cyanoguanidine is a colourless solid that is soluble in water, acetone, and alcohol, but not nonpolar organic solvents. Production ...

melamine Melamine is an organic compound with the formula C3H6N6. This white solid is a trimer of cyanamide, with a 1,3,5-triazine skeleton. Like cyanamide, it contains 67% nitrogen by mass, and its derivatives have fire retardant properties due t ...

. The firstly formed polymeric C₃N₄ structure,

melon A melon is any of various plants of the family Cucurbitaceae with sweet, edible, and fleshy fruit. The word "melon" can refer to either the plant or specifically to the fruit. Botanically, a melon is a kind of berry, specifically a "pepo". The ...

, with pendant

amino group In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent such a ...

s, is a highly ordered

polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...

. Further reaction leads to more condensed and less defective C₃N₄ species, based on tri-s-triazine (C₆N₇) units as elementary building blocks. Graphitic carbon nitride can also be prepared by electrodeposition on Si(100) substrate from a saturated

acetone Acetone (2-propanone or dimethyl ketone), is an organic compound with the formula . It is the simplest and smallest ketone (). It is a colorless, highly volatile and flammable liquid with a characteristic pungent odour. Acetone is miscib ...

solution of

cyanuric trichloride Cyanuric chloride is an organic compound with the formula (NCCl)3. This white solid is the chlorinated derivative of 1,3,5-triazine. It is the trimer of cyanogen chloride. Cyanuric chloride is the main precursor to the popular but controvers ...

and melamine (ratio =1: 1.5) at room temperature. Well-crystallized graphitic carbon nitride nanocrystallites also can be have prepared via benzene-thermal reaction between C₃N₃Cl₃ and NaNH₂ at 180–220 °C for 8–12 h. Recently, a new method of syntheses of graphitic carbon nitrides by heating at 400-600 °C of a mixture of melamine and

uric acid Uric acid is a heterocyclic compound of carbon, nitrogen, oxygen, and hydrogen with the formula C5H4N4O3. It forms ions and salts known as urates and acid urates, such as ammonium acid urate. Uric acid is a product of the metabolic breakdown of ...

in the presence of alumina has been reported. Alumina favored the deposition of the graphitic carbon nitrides layers on the exposed surface. This method can be assimilated to an in situ

chemical vapor deposition Chemical vapor deposition (CVD) is a vacuum deposition method used to produce high quality, and high-performance, solid materials. The process is often used in the semiconductor industry to produce thin films. In typical CVD, the wafer (substra ...

(CVD).

Characterization

Characterization of crystalline g-C₃N₄ can be carried out by identifying the

triazine Triazines are a class of nitrogen-containing heterocycles. The parent molecules' molecular formula is . They exist in three isomeric forms, 1,3,5-triazines being common. Structure The triazines have planar six-membered benzene-like ring but ...

ring existing in the products by

X-ray photoelectron spectroscopy X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic technique based on the photoelectric effect that can identify the elements that exist within a material (elemental composition) or are covering its surface, ...

(XPS) measurements,

photoluminescence Photoluminescence (abbreviated as PL) is light emission from any form of matter after the absorption of photons (electromagnetic radiation). It is one of many forms of luminescence (light emission) and is initiated by photoexcitation (i.e. photon ...

spectra and

Fourier transform infrared spectroscopy Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectr ...

(FTIR) spectrum (peaks at 800 cm⁻¹, 1310 cm⁻¹ and 1610 cm⁻¹).

Properties

Due to the special

semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...

properties of carbon nitrides, they show unexpected

catalytic Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

activity for a variety of reactions, such as for the activation of

benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...

trimerization In chemistry, a trimer (; ) is a molecule or polyatomic anion formed by combination or association of three molecules or ions of the same substance. In technical jargon, a trimer is a kind of oligomer derived from three identical precursors ofte ...

reactions, and also the activation of

carbon dioxide Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...

(

artificial photosynthesis Artificial photosynthesis is a chemical process that biomimics the natural process of photosynthesis to convert sunlight, water, and carbon dioxide into carbohydrates and oxygen. The term artificial photosynthesis is commonly used to refer to ...

Uses

A commercial graphitic carbon nitride is available under the brand name Nicanite. In its micron-sized graphitic form, it can be used for

tribological Tribology is the science and engineering of interacting surfaces in relative motion. It includes the study and application of the principles of friction, lubrication and wear. Tribology is highly interdisciplinary, drawing on many academic field ...

coatings, biocompatible medical coatings, chemically inert coatings, insulators and for

energy storage Energy storage is the capture of energy produced at one time for use at a later time to reduce imbalances between energy demand and energy production. A device that stores energy is generally called an accumulator or battery. Energy comes in ...

solutions. Graphitic carbon nitride is reported as one of the best hydrogen storage materials. It can also be used as a support for catalytic

nanoparticle A nanoparticle or ultrafine particle is usually defined as a particle of matter that is between 1 and 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 1 ...

Areas of interest

Due to their properties (primarily large, tuneable band gaps and efficient intercalation of salts) graphitic carbon nitrides are under research for a variety of applications: * Photocatalysts ** Decomposition of water to H₂ and O₂ ** Degradation of pollutants * Large band gap

Heterogeneous catalyst In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Ph ...

and support ** The significant resilience of carbon nitrides combined with surface and intralayer reactivities make them potentially useful catalysts relying on their labile protons and Lewis base functionalities. Modifications such as doping, protonation and molecular functionalisation can be exploited to improve selectivity and performance. ** Nanoparticle catalysts supported on gCN are under development for both

proton exchange membrane fuel cell A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...

s and water electrolyzers. ** Despite graphitic carbon nitride having some advantages, such as mild band gap (2.7 eV), absorption of visible light and flexibility, it still has limitations for practical applications due to low efficiency of visible light utilization, high recombination rate of the photo generated charge carriers, low electrical conductivity and small specific surface area (<10 m²g⁻¹). To modify these shortages, one of the most attractive approaches is doping graphitic carbon nitride with carbon nanomaterials, such as carbon nanotubes. First, carbon nanotubes have large specific surface area, so they can provide more sites to separate the charge carriers, then decrease the recombination rate of the charge carriers and further increase the activity of reduction reaction. Second, carbon nanotubes show high electron conducting ability, which means they can improve graphitic carbon nitride with visible light response, efficient charge carrier separation and transfer, thereby improving its electronic properties. Third, carbon nanotubes can be regarded as a kind of narrow band semiconductor material, also known as a photosensitizer, which can extend the range of the light absorption of semiconductor photocatalytic material, thereby enhancing its utilization of visible light. * Energy Storage materials ** Due to the intercalation of Li being able to occur to more sites than for graphite due to intra layer voids in addition to intercalation between layers, gCN can store a large amount of Li making them potentially useful for rechargeable batteries.

References