View source for Graphyne

{{short description|Allotrope of carbon}}
{{distinguish|Graphene|Grapheme|Graphane}}
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[[File:Graphynes.png|thumb|upright=1.2|Graphyne-''n'' varieties, where ''n'' indicates the number of carbon–carbon triple bonds in a link between two adjacent hexagons. Graphyne is graphyne-1; graphdiyne is graphyne-2.]]
'''Graphyne''' is an [[allotrope]] of [[carbon]]. Although it has been studied in theoretical models, it is very difficult to synthesize and only small amounts of uncertain purity have been created. Its structure is one-atom-thick [[Planar crystallographic group|planar]] sheets of sp and [[Sp2 bond|sp<sup>2</sup>-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, sp<sup>''k''</sup>, where k can be 1 or 2,<ref>{{cite journal | first1 = R.B. | last1 = Heimann | first2 = S.E. | last2 = Evsvukov | first3 = Y. | last3 = Koga | year = 1997 | title = Carbon allotropes: a suggested classification scheme based on valence orbital hybridization | journal = [[Carbon (journal)|Carbon]] | volume = 35 | issue = 10–11 | pages = 1654–1658 | doi = 10.1016/S0008-6223(97)82794-7 }}</ref><ref>{{cite journal | first1 = Andrey N. | last1 = Enyashin | first2 = Alexander L. | last2 = Ivanovskii | year = 2011 | title = Graphene Allotropes | journal = [[Physica Status Solidi B]] | volume = 248 | issue = 8 | pages = 1879–1883 | doi = 10.1002/pssb.201046583 | bibcode = 2011PSSBR.248.1879E | s2cid = 125591804 | doi-access = free }}</ref> and thus differs from the hybridization of [[graphene]] (considered pure sp<sup>2</sup>) and [[diamond]] (pure sp<sup>3</sup>).
First-principles calculations showed that periodic graphyne structures and their [[boron nitride]] analogues are stable. The calculations used [[Phonon scattering|phonon dispersion curves]] and [[Ab initio|ab-initio]] finite temperature, quantum mechanical molecular dynamics simulations.<ref>{{cite journal|last=Özçelik|first=V. Ongun|author2=Ciraci, S. |title=Size Dependence in the Stabilities and Electronic Properties of α-Graphyne and Its Boron Nitride Analogue|journal=The Journal of Physical Chemistry C|date=January 10, 2013|doi=10.1021/jp3111869|volume=117|issue=5|pages=2175–2182|arxiv=1301.2593|s2cid=44136901}}</ref>
== History ==
Graphyne was first theoretically proposed by Baughman et al. in 1987.<ref>{{cite journal|doi=10.1063/1.453405|title=Structure‐property predictions for new planar forms of carbon: Layered phases containing sp2 and sp atoms |year=1987 |last1=Baughman |first1=R. H. |last2=Eckhardt |first2=H. |last3=Kertesz |first3=M. |journal=The Journal of Chemical Physics |volume=87 |issue=11 |pages=6687–6699 |bibcode=1987JChPh..87.6687B }}</ref> In 2010, Li et al. developed the first successful methodology for creating graphdiyne films using the Glaser–Hay cross-coupling reaction with hexaethynylbenzene.<ref>{{cite journal|last1=Li|first1=G. |last2=Li|first2=Y. |last3=Lui|first3=H.|last4=Guo|first4=Y.|last5=Li|first5=Y.|last6=Zhu|first6=D.|title=Architecture of graphdiyne nanoscale films|journal=Chemical Communications|date=2010|doi=10.1039/B922733D|volume=46|issue=19|pages=3256–3258|pmid=20442882 }}</ref> 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]].<ref>{{cite journal|last1=Li|first1=Q. |last2=Yang|first2=C. |last3=Wu|first3=L.|last4=Wang|first4=H.|last5=Cui|first5=X.|title=Converting benzene into γ-graphyne and its enhanced electrochemical oxygen evolution performance|journal=Journal of Materials Chemistry A|date=2019|doi=10.1039/C8TA10317H|volume=7|issue=11|pages=5981–5990|s2cid=104431102 }}</ref> Although a gram-scale graphyne can be obtained using this approach, graphynes with long-range crystallinity over a large area remain elusive.
In 2022, 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.<ref name=LiHan2023Review/>{{rp|4}}<ref>{{cite journal|title=Scalable Synthesis and Characterization of Multilayer γ‑Graphyne, New Carbon Crystals with a Small Direct Band Gap|year=2022 |doi=10.1021/jacs.2c06583|pmid=36130080 |last1=Desyatkin |first1=V. G. |last2=Martin |first2=W. B. |last3=Aliev |first3=A. E. |last4=Chapman |first4=N. E. |last5=Fonseca |first5=A. F. |last6=Galvão |first6=D. S. |last7=Miller |first7=E. R. |last8=Stone |first8=K. H. |last9=Wang |first9=Z. |last10=Zakhidov |first10=D. |last11=Limpoco |first11=F. T. |last12=Almahdali |first12=S. R. |last13=Parker |first13=S. M. |last14=Baughman |first14=R. H. |last15=Rodionov |first15=V. O. |journal=Journal of the American Chemical Society |volume=144 |issue=39 |pages=17999–18008 |arxiv=2301.05291 |s2cid=252438218 }}</ref>
==Synthesis==
Despite numerous efforts by different approaches, no synthesis method has been discovered to create quality graphyne. The small impure amounts created to date do not allow characterization sufficient to verify theoretical properties.<ref name=LiHan2023Review>{{Cite journal |last=Li |first=Jiaqiang |last2=Han |first2=Yu |date=2023-03-01 |title=Artificial carbon allotrope γ-graphyne: Synthesis, properties, and applications |url=https://linkinghub.elsevier.com/retrieve/pii/S2666542523000024 |journal=Giant |volume=13 |pages=100140 |doi=10.1016/j.giant.2023.100140 |issn=2666-5425|doi-access=free }}</ref>{{rp|12|q=synthesis of γ -GY with high crystallinity,
controllable layer number, and large crystal size has not been
achieved}}
==Structure==
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 bond|carbon-carbon single bond]]s in a graphene lattice.<ref name="arxiv">{{cite journal | last1 = Kim | first1 = Bog G. | last2 = Choi | first2 = Hyoung Joon | year = 2012 | title = Graphyne: Hexagonal network of carbon with versatile Dirac cones | journal = [[Physical Review B]] | volume = 86 | issue = 11 | page = 115435 | doi = 10.1103/PhysRevB.86.115435 | arxiv = 1112.2932 |bibcode = 2012PhRvB..86k5435K | s2cid = 119288235 }}</ref> Graphyne is theorized to exist in multiple geometries. This variety is due to the multiple arrangements of sp and sp<sup>2</sup> hybridized carbon. The proposed geometries include a [[Hexagonal crystal system|hexagonal lattice structure]] and a [[Cubic crystal system|rectangular lattice structure]].<ref name="physicsworld">{{cite journal | journal = [[Physics World]] | last1 = Dumé | first1 = Belle |date=1 March 2012 |title = Could graphynes be better than graphene? | url = http://physicsworld.com/cws/article/news/2012/mar/01/could-graphynes-be-better-than-graphene | publisher = [[Institute of Physics]] }}</ref> Out of the theorized structures the rectangular lattice of 6,6,12-graphyne may hold the most potential for future applications.
==Properties==
Models predict that graphyne has the potential for [[Dirac cone]]s on its double and triple bonded carbon atoms.{{citation needed|date=January 2022}} Due to the Dirac cones, the [[Conduction band|conduction]] and [[valence band]]s 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.<ref name="physicsworld" /> This unique feature of its symmetry allows graphyne to [[Doping (semiconductor)|self-dope]] meaning that it has two different Dirac cones lying slightly above and below the Fermi level.<ref name="physicsworld" /> The self-doping effect of 6,6,12-graphyne can be effectively tuned by applying in-plane external strain.<ref>{{cite journal|title=Strain engineering of Dirac cones in graphyne |journal=Applied Physics Letters | volume = 104 | issue = 21 | pages = 213107 |date=May 26, 2014|doi=10.1063/1.4880635|last1=Wang |first1=Gaoxue |last2=Si |first2=Mingsu |last3=Kumar |first3=Ashok |last4=Pandey |first4=Ravindra |bibcode=2014ApPhL.104u3107W }}</ref>
Graphyne samples synthesized to date have shown a melting point of 250-300&nbsp;°C, low reactivity in decomposition reactions with oxygen, heat and light.<ref name="arxiv" />
==Potential applications==
It has been hypothesized that graphyne is preferable to graphene for specific applications owing to its particular energy structure, namely direction-dependent Dirac cones.<ref>{{cite journal |last1=Malko |first1=Daniel |last2=Neiss |first2=Christian |last3=Viñes |first3=Francesc |last4=Görling |first4=Andreas |date=24 February 2012 |title=Competition for Graphene: Graphynes with Direction-Dependent Dirac Cones |url=http://diposit.ub.edu/dspace/bitstream/2445/65316/1/619276.pdf |journal=[[Phys. Rev. Lett.]] |volume=108 |issue=8 |page=086804 |bibcode=2012PhRvL.108h6804M |doi=10.1103/PhysRevLett.108.086804 |pmid=22463556 |hdl-access=free |hdl=2445/65316}}</ref><ref>{{cite journal |last=Schirber |first=Michael |date=24 February 2012 |title=Focus: Graphyne May Be Better than Graphene |url=http://physics.aps.org/articles/v5/24 |journal=[[Physics (American Physical Society journal)|Physics]] |volume=5 |issue=24 |pages=24 |bibcode=2012PhyOJ...5...24S |doi=10.1103/Physics.5.24}}</ref> The directional dependency of 6,6,12-graphyne could allow for electrical [[Diffraction grating|grating]] on the nanoscale.<ref>{{cite web | last1 = Bardhan | first1 = Debjyoti |date=2 March 2012 |title = Novel new material graphyne can be a serious competitor to graphene | url = http://techie-buzz.com/science/graphyne.html|work=techie-buzz.com }}</ref> This could lead to the development of faster transistors and nanoscale electronic devices.<ref name="physicsworld" /><ref>{{cite web | last1 = Cartwright | first1 = J. | date = 1 March 2012 | title = Graphyne could be better than graphene | url = http://news.sciencemag.org/sciencenow/2012/03/graphyne-could-be-better-than-gr.html | work = news.sciencemag.org | url-status = dead| archiveurl = https://web.archive.org/web/20121002073046/http://news.sciencemag.org/sciencenow/2012/03/graphyne-could-be-better-than-gr.html | archivedate = 2 October 2012 }}</ref><ref>{{cite web|title=Graphyne Better Than Graphene?|date=5 March 2012| url=http://www.materialstoday.com/carbon/news/graphyne-better-than-graphene/|work=Materials Today}}</ref> 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.<ref>{{cite journal|last1=Stasyuk|first1=O.A. |last2=Stasyuk|first2=A.J. |last3=Solà|first3=M.|last4=Voityuk|first4=A.A.|title=γ-graphyne: a promising electron acceptor for organic photovoltaics|journal=Materials & Design|date=2022|volume=225 |doi=10.1016/j.matdes.2022.111526|pages=111526|s2cid=254961210 |hdl=10256/22532|hdl-access=free}}</ref>
==References==
{{reflist|30em}}
==External links==
{{commons category|Graphyne}}
*{{cite web |last=Rawat |first=Sachin |title=Graphene is a Nobel Prize-winning "wonder material." Graphyne might replace it |website=Big Think |date=2022-08-05 |url=https://bigthink.com/the-future/graphyne/ |access-date=2022-08-07 |ref=none}}
*{{cite journal |last1=Wang |first1=Xiluan |last2=Shi |first2=Gaoquan |title=An introduction to the chemistry of graphene |journal=Physical Chemistry Chemical Physics |publisher=Royal Society of Chemistry (RSC) |volume=17 |issue=43 |year=2015 |doi=10.1039/c5cp05212b |pages=28484–28504 |pmid=26465215 |bibcode=2015PCCP...1728484W |ref=none}}
[[Category:Allotropes of carbon]]
[[Category:Alkyne derivatives]]
[[Category:Two-dimensional nanomaterials]]