Chemical structure of graphyne-1 | |
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Graphyne is an allotrope of carbon. Its structure is one-atom-thick planar sheets of sp and sp2-bonded carbon atoms arranged in crystal lattice. It can be seen as a lattice of benzene rings connected by acetylene bonds. The material is called graphyne-n when benzene rings are connected by n sequential acetylene molecules, and graphdiyne for a particular case of n = 2 (diacetylene links).
Depending on the content of acetylene groups, graphyne can be considered a mixed hybridization, spk, where k can be 1 or 2, [1] [2] and thus differs from the hybridization of graphene (considered pure sp2) and diamond (pure sp3).
First-principles calculations showed that periodic graphyne structures and their boron nitride analogues are stable. The calculations used phonon dispersion curves and ab-initio finite temperature, quantum mechanical molecular dynamics simulations. [3]
Graphyne was first theoretically proposed by Baughman et al. in 1987. [4] In 2010, Li et al. developed the first successful methodology for creating graphdiyne films using the Glaser–Hay cross-coupling reaction with hexaethynylbenzene. [5] The proposed approach makes it possible to synthesize nanometer-scale graphdiyne and graphtetrayne, which lack long-range order. In 2019, Cui and co-workers reported on a mechanochemical technique for obtaining graphyne using benzene and calcium carbide. [6] Although a gram-scale graphyne can be obtained using this approach, graphynes with long-range crystallinity over a large area remain elusive.
Although disputed, researchers used alkyne metathesis, while controlling thermodynamics and kinetics, to synthesize graphyne in 2022. [7] [8] Various analytical methods indicate its excellent chemical and thermal stability. A wide-angle X-ray scattering characterization of the obtained graphyne product suggests a unified crystalline structure. [9]
In 2022, the first scalable synthesis of multi-layered γ‑graphyne was successfully performed through the polymerization of 1,3,5-tribromo-2,4,6-triethynylbenzene under Sonogashira coupling conditions. Near-infrared spectroscopy and cyclic voltammetry of the material determined the bandgap as 0.48 ± 0.05 eV, which agrees with the theoretical prediction for graphyne-based materials. [10] [11]
Through the use of computer models scientists have predicted several properties of the substance on assumed geometries of the lattice. Its proposed structures are derived from inserting acetylene bonds in place of carbon-carbon single bonds in a graphene lattice. [12] Graphyne is theorized to exist in multiple geometries. This variety is due to the multiple arrangements of sp and sp2 hybridized carbon. The proposed geometries include a hexagonal lattice structure and a rectangular lattice structure. [13] Out of the theorized structures the rectangular lattice of 6,6,12-graphyne may hold the most potential for future applications.
Models predict that graphyne has the potential for Dirac cones on its double and triple bonded carbon atoms.[ citation needed ] Due to the Dirac cones, the conduction and valence bands meet in a linear fashion at a single point in the Fermi level. The advantage of this scheme is that electrons behave as if they have no mass, resulting in energies that are proportional to the momentum of the electrons. Like in graphene, hexagonal graphyne has electric properties that are direction independent. However, due to the symmetry of the proposed rectangular 6,6,12-graphyne the electric properties would change along different directions in the plane of the material. [13] This unique feature of its symmetry allows graphyne to self-dope meaning that it has two different Dirac cones lying slightly above and below the Fermi level. [13] The self-doping effect of 6,6,12-graphyne can be effectively tuned by applying in-plane external strain. [14] Graphyne samples synthesized to date have shown a melting point of 250-300 °C, low reactivity in decomposition reactions with oxygen, heat and light. [12]
It has been hypothesized that graphyne is preferable to graphene for specific applications owing to its particular energy structure, namely direction-dependent Dirac cones. [15] [16] The directional dependency of 6,6,12-graphyne could allow for electrical grating on the nanoscale. [17] This could lead to the development of faster transistors and nanoscale electronic devices. [13] [18] [19] Recently it was demonstrated that photoinduced electron transfer from electron-donating partners to γ-graphyne is favorable and occurs on nano to sub-picosecond time scale. [20]
A fullerene is an allotrope of carbon whose molecules consist of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to seven atoms. The molecules may be hollow spheres, ellipsoids, tubes, or other shapes.
A carbon–carbon bond is a covalent bond between two carbon atoms. The most common form is the single bond: a bond composed of two electrons, one from each of the two atoms. The carbon–carbon single bond is a sigma bond and is formed between one hybridized orbital from each of the carbon atoms. In ethane, the orbitals are sp3-hybridized orbitals, but single bonds formed between carbon atoms with other hybridizations do occur. In fact, the carbon atoms in the single bond need not be of the same hybridization. Carbon atoms can also form double bonds in compounds called alkenes or triple bonds in compounds called alkynes. A double bond is formed with an sp2-hybridized orbital and a p-orbital that is not involved in the hybridization. A triple bond is formed with an sp-hybridized orbital and two p-orbitals from each atom. The use of the p-orbitals forms a pi bond.
Carbon is capable of forming many allotropes due to its valency. Well-known forms of carbon include diamond and graphite. In recent decades, many more allotropes have been discovered and researched, including ball shapes such as buckminsterfullerene and sheets such as graphene. Larger-scale structures of carbon include nanotubes, nanobuds and nanoribbons. Other unusual forms of carbon exist at very high temperatures or extreme pressures. Around 500 hypothetical 3‑periodic allotropes of carbon are known at the present time, according to the Samara Carbon Allotrope Database (SACADA).
Coronene is a polycyclic aromatic hydrocarbon (PAH) comprising seven peri-fused benzene rings. Its chemical formula is C
24H
12. It is a yellow material that dissolves in common solvents including benzene, toluene, and dichloromethane. Its solutions emit blue light fluorescence under UV light. It has been used as a solvent probe, similar to pyrene.
Graphene is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure. The name is derived from "graphite" and the suffix -ene, reflecting the fact that the graphite allotrope of carbon contains numerous double bonds.
In nanotechnology, a carbon nanobud is a material that combines carbon nanotubes and spheroidal fullerenes, both allotropes of carbon, forming "buds" attached to the tubes. Carbon nanobuds were discovered and synthesized in 2006.
Elemental phosphorus can exist in several allotropes, the most common of which are white and red solids. Solid violet and black allotropes are also known. Gaseous phosphorus exists as diphosphorus and atomic phosphorus.
Linear acetylenic carbon (LAC), also known as carbyne or Linear Carbon Chain (LCC), is an allotrope of carbon that has the chemical structure (−C≡C−)n as a repeat unit, with alternating single and triple bonds. It would thus be the ultimate member of the polyyne family.
Graphane is a two-dimensional polymer of carbon and hydrogen with the formula unit (CH)n where n is large. fully hydrogenation results in hydrogenated graphene, which was reported by Elias et al. in 2009 by a TEM study to be "direct evidence for a new graphene-based derivative". The authors viewed the panorama as "a whole range of new two-dimensional crystals with designed electronic and other properties".
Rodney S. "Rod" Ruoff is an American physical chemist and nanoscience researcher. He is one of the world experts on carbon materials including carbon nanostructures such as fullerenes, nanotubes, graphene, diamond, and has had pioneering discoveries on such materials and others. Ruoff received his B.S. in chemistry from the University of Texas at Austin (1981) and his Ph.D. in chemical physics at the University of Illinois-Urbana (1988). After a Fulbright Fellowship at the MPI fuer Stroemungsforschung in Goettingen, Germany (1989) and postdoctoral work at the IBM T. J. Watson Research Center (1990–91), Ruoff became a staff scientist in the Molecular Physics Laboratory at SRI International (1991–1996). He is currently UNIST Distinguished Professor at the Ulsan National Institute of Science and Technology (UNIST), and the director of the Center for Multidimensional Carbon Materials, an Institute for Basic Science Center located at UNIST.
Silicene is a two-dimensional allotrope of silicon, with a hexagonal honeycomb structure similar to that of graphene. Contrary to graphene, silicene is not flat, but has a periodically buckled topology; the coupling between layers in silicene is much stronger than in multilayered graphene; and the oxidized form of silicene, 2D silica, has a very different chemical structure from graphene oxide.
Silicynes are allotropes of silicon.
Borophene is a crystalline atomic monolayer of boron, i.e., it is a two-dimensional allotrope of boron and also known as boron sheet. First predicted by theory in the mid-1990s, different borophene structures were experimentally confirmed in 2015.
In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials derived from single elements generally carry the -ene suffix in their names, e.g. graphene. Single-layer materials that are compounds of two or more elements have -ane or -ide suffixes. 2D materials can generally be categorized as either 2D allotropes of various elements or as compounds.
Germanene is a material made up of a single layer of germanium atoms. The material is created in a process similar to that of silicene and graphene, in which high vacuum and high temperature are used to deposit a layer of germanium atoms on a substrate. High-quality thin films of germanene have revealed unusual two-dimensional structures with novel electronic properties suitable for semiconductor device applications and materials science research.
A carbon nanothread is a sp3-bonded, one-dimensional carbon crystalline nanomaterial. The tetrahedral sp3-bonding of its carbon is similar to that of diamond. Nanothreads are only a few atoms across, more than 300,000 times thinner than a human hair. They consist of a stiff, strong carbon core surrounded by hydrogen atoms. Carbon nanotubes, although also one-dimensional nanomaterials, in contrast have sp2-carbon bonding as is found in graphite. The smallest carbon nanothread has a diameter of only 0.2 nanometers, much smaller than the diameter of a single-wall carbon nanotube.
Penta-graphene is a hypothetical carbon allotrope composed entirely of carbon pentagons and resembling the Cairo pentagonal tiling. Penta-graphene was proposed in 2014 on the basis of analyses and simulations. Further calculations predicted that it is unstable in its pure form, but can be stabilized by hydrogenation. Due to its atomic configuration, penta-graphene has an unusually negative Poisson’s ratio and very high ideal strength believed to exceed that of a similar material, graphene.
A rapidly increasing list of graphene production techniques have been developed to enable graphene's use in commercial applications.
Graphene is a semimetal whose conduction and valence bands meet at the Dirac points, which are six locations in momentum space, the vertices of its hexagonal Brillouin zone, divided into two non-equivalent sets of three points. The two sets are labeled K and K'. The sets give graphene a valley degeneracy of gv = 2. By contrast, for traditional semiconductors the primary point of interest is generally Γ, where momentum is zero. Four electronic properties separate it from other condensed matter systems.
The term Dirac matter refers to a class of condensed matter systems which can be effectively described by the Dirac equation. Even though the Dirac equation itself was formulated for fermions, the quasi-particles present within Dirac matter can be of any statistics. As a consequence, Dirac matter can be distinguished in fermionic, bosonic or anyonic Dirac matter. Prominent examples of Dirac matter are graphene and other Dirac semimetals, topological insulators, Weyl semimetals, various high-temperature superconductors with -wave pairing and liquid helium-3. The effective theory of such systems is classified by a specific choice of the Dirac mass, the Dirac velocity, the gamma matrices and the space-time curvature. The universal treatment of the class of Dirac matter in terms of an effective theory leads to a common features with respect to the density of states, the heat capacity and impurity scattering.