DOCSLIB.ORG

Pressure‐Induced Diels–Alder Reactions in C6H6‐C6F6 Cocrystal

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Pressure‐Induced Diels–Alder Reactions in C6H6‐C6F6 Cocrystal Angewandte Communications Chemie International Edition:DOI:10.1002/anie.201813120 Solid-State Reactions German Edition:DOI:10.1002/ange.201813120 Pressure-Induced Diels–Alder ReactionsinC6H6-C6F6 Cocrystal towards Graphane Structure Yajie Wang,Xiao Dong,Xingyu Tang,Haiyan Zheng,* KuoLi,* Xiaohuan Lin, Leiming Fang, Guangai Sun, Xiping Chen, Lei Xie,Craig L. Bull, Nicholas P. Funnell, Takanori Hattori, Asami Sano-Furukawa, Jihua Chen, Dale K. Hensley,George D. Cody,Yang Ren, Hyun Hwi Lee,and Ho-kwang Mao Abstract: Pressure-induced polymerization (PIP) of aromat- nanothread was reported, which is recognized as an ultra-thin ics is anovel method for constructing sp3-carbon frameworks, sp3-carbon nanowire.[2a,b] Similarly,single-crystal carbon and nanothreads with diamond-like structures were synthe- nitride was synthesized by compressing pyridine slowly.[2c] sized by compressing benzene and its derivatives.Here by Recently,itwas reported that aniline forms diamond-like compressing abenzene-hexafluorobenzene cocrystal (CHCF), polyaniline under external pressure and the hydrogen bond H-F-substituted graphane with alayered structure in the PIP between the NH2 groups is believed to be responsible for product was identified. Based on the crystal structure deter- better crystallinity.[2d] Besides the one-dimensional structure, mined from the in situ neutron diffraction and the intermediate the graphane structure was also obtained by compressing the products identified by gas chromatography-mass spectrum, we aromatics under high-pressure and high-temperature condi- found that at 20 GPaCHCF forms tilted columns with benzene tions.[4] and hexafluorobenzene stackedalternatively,and leads to Thereaction mechanism of these pressure-induced poly- a[4+2] polymer,which then transforms to short-range ordered merizations (PIPs) was explored from various perspectives. H-F-substituted graphane.The reaction process involves [4+2] Various possible connections between benzene molecules Diels–Alder,retro-Diels–Alder,and 1-1’ coupling reactions, were theoretically proposed, and the energies of the formed and the former is the key reaction in the PIP.These studies dimers were examined to evaluate the corresponding reac- confirm the elemental reactions of PIP of CHCF for the first tions.[5,6] Experimentally,apossible reaction route including time,and provide insight into the PIP of aromatics. a[4+2] cycloaddition reaction followed by an intramolecular “zipper” cascade reaction, was proposed according to the p–p Sp3-hybridized carbon-based materials have gained constant stacking of the benzene molecules and the structural model of attention because of their outstanding mechanical and optical the product.[2a] All of these reports suggest the reaction starts properties.[1] However,their types are very limited compared from the bonding between the p–p stacked aromatics. to the diversity of the carbon-based molecules.Applying However,more experimental work is needed to understand extreme pressure to unsaturated molecules,such as aromatics, the elemental reactions in the PIP process and its relation to is proven to be effective in constructing sp3-hybridized carbon the p–p stacking. [2] materials. It is well known that benzene polymerizes into TheC6H6-C6F6 1:1cocrystal (abbreviated as CHCF here- amorphous hydrogenated carbon under high pressure,[3] and after) provides an appropriate p–p stacking model because of with anisotropic stress,awell-ordered single-crystal carbon the strong electrostatic attraction between C6H6 and C6F6. [*] Dr.Y.Wang, Dr.X.Dong, Dr.X.Tang, Dr.H.Zheng, Dr.K.Li, Dr.G.D.Cody,Dr. H.-k. Mao Dr.X.Lin, Dr.H.-k. Mao GeophysicalLab, Carnegie InstitutionofWashington Center for High Pressure Science and TechnologyAdvanced Research 5251 Broad Branch Road, NW,Washington,DC20015 (USA) Beijing, 100094 (P. R. China) Dr.Y.Ren E-mail:[email protected] Advanced Photon Source, Argonne National Laboratory [email protected] Lemont, IL 60439 (USA) Dr.L.Fang, Dr.G.’a. Sun, Dr.X.Chen, Dr.L.Xie Dr.H.H.Lee Key Laboratory of Neutron Physics and InstituteofNuclear Physics Pohang Accelerator Laboratory,POSTECH and Chemistry, China AcademyofEngineering Physics Pohang 790-784 (Republic of Korea) Mianyang,621999 (P. R. China) Dr.X.Dong Dr.C.L.Bull, Dr.N.P.Funnell Key Laboratory of Weak-Light Nonlinear Photonics,School of ISIS Neutron and Muon Facility,Rutherford Appleton Laboratory, Physics, Nankai University,Tianjin 300071 (China) Chilton, Didcot, Oxon, OX11 0QX (UK) Supportinginformation and the ORCID identification number(s) for Dr.T.Hattori, Dr.A.Sano-Furukawa the author(s) of this article can be found under: J-PARC Center,Japan Atomic Energy Agency https://doi.org/10.1002/anie.201813120. Tokai, Ibaraki 319-1195 (Japan) Dr.J.Chen, Dr.D.K.Hensley Center for Nanophase MaterialsSciences, Oak Ridge National Laboratory,Oak Ridge, TN 37831 (USA) 1468 2019 Wiley-VCH Verlag GmbH &Co. KGaA,Weinheim Angew.Chem. Int. Ed. 2019, 58,1468 –1473 Angewandte Communications Chemie Thealternate stacking of C6H6 and C6F6 can be recognized as Upon further compression of phase VIII using aParis half of the benzene molecules being replaced by hexafluoro- Edinburgh (PE) press,weobtained white solid samples,and benzene,and thus provides atracer during the reaction. their morphology varied with the applied pressure.The Herein we report the PIP of CHCF and its reaction product recovered from 18 GPa (PE18) has an irregular mechanism under applied pressure.The product of PIP morphology (see Figure S4), while that obtained from 20 GPa contains ahydrogenated fluorinated graphane-like structure. (PE20) shows an obviously layered structure under the Diels–Alder,retro-Diels–Alder,and 1–1’ coupling reactions scanning electron microscope (SEM;Figure 2a). When were identified during this process and the former is the key elemental reaction leading to the polymerized material. We describe the PIP route of the aromatic molecules systemati- cally,which provides an alternative method for constructing substituted graphane with atomic-level uniformity. CHCF forms rhombohedral crystals (phase I, R3m) around room temperature and experiences three phase transitions to form phases II (I2/m), III (P1), and IV (P21/a) at low temperature and ambient pressure.[7] In all the phases, [7] C6H6 and C6F6 are alternately stacked. Under high pressure, phases V(P21/c), VI, VII, and VIII were identified and PIP was observed at about 20 GPa after phase VIII.[8] Combining in situ synchrotron X-ray diffraction (XRD;see Figure S1 in the Supporting Information), constant wavelength and time of flight (TOF) neutron diffraction under high pressure (see Figure S2), we determined the structures of phase VI, VII, and VIII ab initio (see Figure S3), including the atomic positions using Rietveld refinement (see Table S1). TheC6H6 and C6F6 molecules are still alternately stacked to form columns in these phases.However,the columns are tilted significantly,and are quite different from those under low temperature.Tounderstand the crystal structure at reaction pressure threshold more precisely,wefurther optimized the Figure 2. a) SEM images, b) 13CCPMAS ssNMR spetra, and c) TEM structure of phase VIII by using density-functional theory image (200 kV) of PE20. d) The corresponding statistical results of d- (DFT) calculations based on the experimental result at spacing in c). e) The total structure factor S(Q) derived from synchro- 20 GPa, as shown in Figure 1. Thestacked aromatic rings tron X-ray and neutron diffraction of PE20. f) Experimental (X-ray) and are progressively tilted away from the previous column axis calculated G(r)ofPE20. g) SAED pattern (120 kV TEM) of the sample PE20. The modelled PDF in Figure 2fis derived from the proposed H- (c-axis), and form closed packed layers on the (102) plane. F-substitutedgraphane model viewed along [001] (h). Every aromatic ring is curved and stacked on the interstitial site of three rings of the neighboring layer, with two of the three rings being of the same type.Along the [001] direction, recovered from 17 GPa, the solid sample (PE17) is too the nearest C···C distance between the C6F6 and C6H6 limited to be analyzed, which means most of the aromatic molecules in the column is about 2.8 ,close to the critical molecules did not react and evaporated upon decompression. reaction distance between the benzene molecules (2.8–3.0 ) Theenergy dispersive spectroscopy (EDS) obtained from at 298 K(Figure 1b).[9] This indicates ahigh possibility of the SEM shows PE20 maintains most of the fluorine atoms (see addition reaction between the C6F6 and C6H6 in the CHCF Table S2). Using solid-state nuclear magnetic resonance columns. (ssNMR;Figure 2b), we found three types of carbon species, C(sp2)(d = 131 ppm) and C(sp3)connected to fluorine (F- CR3 ; d = 94 ppm) and nonfluorine atoms (H-CR3 ; d = 38 ppm). Theratio of the peak area of the C(sp2)and C(sp3) is 1:4, which indicates C(sp3)isthe dominant species.These data are consistent with the 1H-ssNMR result (see Figure S5), which is well fitted using three peaks at d = 1.3, 2.5, and 3 3 6.3 ppm, and recognized as HonC(sp )(H-C-R3), C(sp ) 2 connected to afluorine atom (H-CFR2)and C(sp )(H-CR= CR2), respectively.Hence,the ssNMR data prove that the 3 Figure 1. The crystal structure of C6D6-C6F6 before reaction (20 GPa). sample is mainly an H-F bonded sp -C material. Viewed perpendicular to (102) (a) and approximately along [010] (b). When we measured EDS using atransmission electron The black, pink, and green atoms are carbon, hydrogen (deuterium), microscope (TEM) of 200 kV,PE20 lost most of fluorine (see and fluorine, respectively.This crystal structure is optimized by DFT calculations based on the structure obtained from the Rietveld refine- Table S2), and the corresponding image shows acurved ment result of the neutron data collected at BL11 PLANET,J-PARC[10] layered structure with the interlayer d-spacing of 3.7 at 20 GPa.[8] (Figure 2c and d), consistent with that in graphite.[11] These Angew.Chem.
Load more

Recommended publications
  • Covalent Functionalization of Two-Dimensional Group 14 Graphane Analogues
    Chemical Society Reviews Covalent Functionalization of Two-Dimensional Group 14 Graphane Analogues Journal: Chemical Society Reviews Manuscript ID CS-REV-04-2018-000291.R1 Article Type: Review Article Date Submitted by the Author: 29-May-2018 Complete List of Authors: Huey, Warren; The Ohio State University, Chemistry and Biochemistry Goldberger, Joshua; The Ohio State University, Chemistry and Biochemistry Page 1 of 25 PleaseChemical do not Society adjust Reviews margins Chem Soc Rev Review Article Covalent Functionalization of Two-Dimensional Group 14 Graphane Analogues a a Received 00thJanuary 20xx, Warren L. B. Huey and Joshua E. Goldberger* Accepted 00th January 20xx The sp3-hybridized group 14 graphane analogues are a unique family of 2D materials in which every atom requires a DOI: 10.1039/x0xx00000x terminal ligand for stability. Consequently, the optical, electronic, and thermal properties of these materials can be www.rsc.org/ manipulated via covalent chemistry. Herein, we review the methodologies for preparing these materials, and compare their functionalization densities to Si/Ge(111) surfaces and other covalently terminated 2D materials. We discuss how the electronic structure, optical properties, and thermal stability of the 2D framework can be broadly tuned with the ligand identity and framework element. We highlight their recent application in electronics, optoelectronics, photocatalysis, and batteries. Overall, these materials are an intriguing regime in materials design in which both surface functionalization and solid-state chemistry can be uniquely exploited to systematically design properties and phenomena. electronic structure. In addition, the local dielectric constant, A. Introduction the hydrophobicity, and the thermal stability can be controlled by grafting different ligands.
    [Show full text]
  • WO 2016/074683 Al 19 May 2016 (19.05.2016) W P O P C T
    (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2016/074683 Al 19 May 2016 (19.05.2016) W P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C12N 15/10 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/DK20 15/050343 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 11 November 2015 ( 11. 1 1.2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: PA 2014 00655 11 November 2014 ( 11. 1 1.2014) DK (84) Designated States (unless otherwise indicated, for every 62/077,933 11 November 2014 ( 11. 11.2014) US kind of regional protection available): ARIPO (BW, GH, 62/202,3 18 7 August 2015 (07.08.2015) US GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, (71) Applicant: LUNDORF PEDERSEN MATERIALS APS TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, [DK/DK]; Nordvej 16 B, Himmelev, DK-4000 Roskilde DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (DK).
    [Show full text]
  • Effective Mechanical Properties of Multilayer Nano-Heterostructures," Scientific Reports, Vol
    Missouri University of Science and Technology Scholars' Mine Materials Science and Engineering Faculty Research & Creative Works Materials Science and Engineering 17 Nov 2017 Effective Mechanical Properties of Multilayer Nano- Heterostructures T Mukhopadhyay A Mahata S Adhikari Mohsen Asle Zaeem Missouri University of Science and Technology, [email protected] Follow this and additional works at: https://scholarsmine.mst.edu/matsci_eng_facwork Part of the Materials Science and Engineering Commons Recommended Citation T. Mukhopadhyay et al., "Effective Mechanical Properties of Multilayer Nano-Heterostructures," Scientific Reports, vol. 7, no. 1, pp. 15818-15818, Nature Publishing Group, Nov 2017. This Article - Journal is brought to you for free and open access by Scholars' Mine. It has been accepted for inclusion in Materials Science and Engineering Faculty Research & Creative Works by an authorized administrator of Scholars' Mine. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. www.nature.com/scientificreports OPEN Efective mechanical properties of multilayer nano-heterostructures T. Mukhopadhyay1, A. Mahata2, S. Adhikari 3 & M. Asle Zaeem 2 Two-dimensional and quasi-two-dimensional materials are important nanostructures because of Received: 6 June 2017 their exciting electronic, optical, thermal, chemical and mechanical properties. However, a single- Accepted: 27 October 2017 layer nanomaterial may not possess a particular property adequately, or multiple desired properties Published: xx xx xxxx simultaneously. Recently a new trend has emerged to develop nano-heterostructures by assembling multiple monolayers of diferent nanostructures to achieve various tunable desired properties simultaneously. For example, transition metal dichalcogenides such as MoS2 show promising electronic and piezoelectric properties, but their low mechanical strength is a constraint for practical applications.
    [Show full text]
  • Benzene-Derived Diamondoid Carbon Nanothreads J
    3,0 Tube Polymer 1 Crespi et.al. H Phys Rev Le* Hoffman et.al. JACS 87 (2001) 133, 9023 (2011) C Benzene-Derived Diamondoid Carbon Nanothreads J. V. Badding, T. Fitzgibbons, V. Crespi, E. Xu, N. Alem Pennsylvania State University G. Cody Carnegie Institution of Washington S. K. Davidowski Arizona State University R. Hoffmann, B. Chen Funding: EFRee DOE Energy Cornell University Frontier Research Center M. Guthrie European Spallation Source Carbon Nanomaterial Dimensionality and Hybridization 0-d 1-d 2-d sp2 C60 nanotubes Graphene sp3 ? diamondoids Graphane sp3 Carbon Nanotube Theory Predictions 3,0 Tube Polymer I Hydrogen First evidence that very small sp3 sp3 tube predicted to form during a carbon nanotubes are high pressure reaction of benzene thermodynamically stable. Stojkovic, D. et.al. PRL 87, (2001) Wen, X-D. et.al. JACS 133, 9023 (2011) Benzene Rapid Decompression: Amorphous Product Liquid Benzene Yellow/white solid Diamond 25 GPa anvil cell Diamond gasket aer Anvil cell decompression Decompression rate ≈12-20 GPa/hr Broad spectral features Powder X-Ray Diffraction UV Raman Spectrum 257 nm excitaon Slow Decompression in Larger Volumes SNAP/ORNL Paris- Edinburgh cell allows for large sample volumes 43 cm (mg to tens of mg scale). Decompression rate ≈ 2-7 GPa/hr PCD WC Steel C13 Solid State NMR Reveals sp3 Bonding sp2 sp3 ~80 % sp3/ tetrahedral bonding 20% 80% TEM of Slowly Decompressed Benzene: Nanothreads! 10 nm After Sonication Fitzgibbons et.al., Benzene-derived carbon nanothreads. Nat. Mater. 14, 43-47 (2015) Crystalline order
    [Show full text]
  • Hybrid Structures and Strain-Tunable Electronic Properties of Carbon Nanothreads
    Hybrid Structures and Strain-Tunable Electronic Properties of Carbon Nanothreads Weikang Wu,y Bo Tai,y Shan Guan,∗,z,y Shengyuan A. Yang,∗,y and Gang Zhang∗,{ yResearch Laboratory for Quantum Materials, Singapore University of Technology and Design, Singapore 487372, Singapore zBeijing Key Laboratory of Nanophotonics and Ultrafine Optoelectronic Systems, School of Physics, Beijing Institute of Technology, Beijing 100081, China. {Institute of High Performance Computing, Agency for Science, Technology and Research, 1 Fusionopolis Way, Singapore 138632, Singapore. E-mail: [email protected]; [email protected]; [email protected] arXiv:1803.04694v1 [cond-mat.mtrl-sci] 13 Mar 2018 1 Abstract The newly synthesized ultrathin carbon nanothreads have drawn great attention from the carbon community. Here, based on first-principles calculations, we investigate the electronic properties of carbon nanothreads under the influence of two important factors: the Stone-Wales (SW) type defect and the lattice strain. The SW defect is intrinsic to the polymer-I structure of the nanothreads and is a building block for the general hybrid structures. We find that the bandgap of the nanothreads can be tuned by the concentration of SW defects in a wide range of 3:92 ∼ 4:82 eV, interpolating between the bandgaps of sp3-(3,0) structure and the polymer-I structure. Under strain, the bandgaps of all the structures, including the hybrid ones, show a nonmonotonic variation: the bandgap first increases with strain, then drops at large strain above 10%. The gap size can be effectively tuned by strain in a wide range (> 0:5 eV). Interestingly, for sp3-(3,0) structure, a switch of band ordering occurs under strain at the valence band maximum, and for the polymer-I structure, an indirect-to-direct-bandgap transition occurs at about 8% strain.
    [Show full text]
  • Stability and Exfoliation of Germanane: a Germanium Graphane Analogue
    Stability and Exfoliation of Germanane: A Germanium Graphane Analogue Undergraduate Thesis Presented in Partial Fulfillment of the Requirements for the Degree of Bachelor of Science in Chemistry with Research Distinction in Chemistry in the College of Arts and Sciences of The Ohio State University By Elisabeth Bianco The Ohio State University May 2013 Thesis Committee: Joshua Goldberger, Advisor Patrick Woodward Abstract Graphene's success has shown that it is not only possible to create stable, single-atom thick sheets from a crystalline solid, but that these materials have fundamentally different properties than the parent material. We have synthesized for the first time, mm-scale crystals of a hydrogen-terminated germanium multilayered graphane analogue (germanane, GeH) from the topochemical deintercalation of CaGe2. This layered van der Waals solid is analogous to multilayered graphane (CH). The surface layer of GeH only slowly oxidizes in air over the span of 5 months, while the underlying layers are resilient to oxidation based on X-ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR) measurements. The GeH is thermally stable up to 75 oC, however, above this temperature amorphization and dehydrogenation begin to occur. These sheets can be mechanically exfoliated as single and few layers onto SiO2/Si surfaces. This material represents a new class of covalently terminated graphane analogues and has great potential for a wide range of optoelectronic and sensing applications, especially since theory predicts a direct band gap of 1.53 eV and an electron mobility ~five times higher than that of bulk Ge. ii Acknowledgements This work was supported in part by an allocation of computing time from the Ohio Supercomputing Center, as well as the Analytical Surface Facility at OSU chemistry, supported by National Science Foundation under the grant number (CHE- 0639163).
    [Show full text]
  • Effects of Biaxial Strain on Performance of Graphyne TFET/MOSFET
    제8회 EDISON SW 활용 경진대회 Effects of biaxial strain on Performance of Graphyne TFET/MOSFET Jihoon Byun and Hyeongu Lee because band gap of channel material significantly affects the device performance. In this project, the Introduction strain effects on electronic properties were reproduced The alltrope of carbon has been steadily studied and biaxially strained graphyne TFETs and nMOSFETs because it shows unique physical properties. Since are investigated by quantum transport simulations. fullerens were observed for the first time in 1985 [1], Computational Method carbon system has attracted attention in the field of nanoelectronics in that the remarkable properties Graphyne ( ) has a hexagonal lattice structure could open many opportunities beyond Moore’s law. with 12 atoms in a primitive unitcell as shown in Fig. 1 Among the allropes, graphene, which consists of sp2- (a). First-principles calculations are performed with the hybridized carbon network system with a linear energy use of density functional theory (DFT) in the basis of a dispersion relation, has been the most intensely linear combination of atomic orbitals (LCAO) using studied because of its high electrical, thermal SIESTA code. The exchange-correlation interacionts are mobilities. However, the applications to treated by the genralized gradient approximation (GGA) nanoelectronics are hindered because pristine with Perdew-Burke-Ernzerhof (PBE) functional. The graphene has zero band gap which limits achievable Brillouin zone is sampled using 15 x 15 x 1 Monkhorst- on-off current ratios.[2] As an alternative materials, Pack grid. The k grid points are tested to converge total other alltropes with non-zero band gap, such as energy as shown in Fig.
    [Show full text]
  • Trends Analysis of Graphene Research and Development
    Research Paper Trends Analysis of Graphene Research and Development Lixue Zou1,2†, Li Wang1,2, Yingqi Wu3, Caroline Ma3, Sunny Yu3, Xiwen Liu1,2 1 Citation: Lixue Zou, National Science Library, Chinese Academy of Sciences, Beijing 100190, China Li Wang, Yingqi Wu, 2University of Chinese Academy of Sciences, No.19(A) Yuquan Road, Shijingshan District, Caroline Ma, Sunny Yu, Beijing 100049, China & Xiwen Liu (2018). 3Chemical Abstracts Service, 2540 Olentangy River Road Columbus, OH 43202, USA Trends Analytsis of Graphene Research and Development. Abstract Vol. 3 No. 1, 2018 pp 82–100 Purpose: This study aims to reveal the landscape and trends of graphene research in the world DOI: 10.2478/jdis-2018-0005 by using data from Chemical Abstracts Service (CAS). Received: Jan. 15, 2018 Revised: Feb. 8, 2018 Design/methodology/approach: Index data from CAS have been retrieved on 78,756 papers Accepted: Feb. 9, 2018 and 23,057 patents on graphene from 1985 to March 2016, and scientometric methods were used to analyze the growth and distribution of R&D output, topic distribution and evolution, and distribution and evolution of substance properties and roles. Findings: In recent years R&D in graphene keeps in rapid growth, while China, South Korea and United States are the largest producers in research but China is relatively weak in patent applications in other countries. Research topics in graphene are continuously expanding from mechanical, material, and electrical properties to a diverse range of application areas such as batteries, capacitors, semiconductors, and sensors devices. The roles of emerging substances are increasing in Preparation and Biological Study.
    [Show full text]
  • Conceptual DFT Reactivity Descriptors Computational Study Of
    Article J. Mex. Chem. Soc. 2020, 64(3) Regular Issue ©2020, Sociedad Química de México ISSN-e 2594-0317 Conceptual DFT Reactivity Descriptors Computational Study of Graphene and Derivatives Flakes: Doped Graphene, Graphane, Fluorographene, Graphene Oxide, Graphyne, and Graphdiyne Brenda Manzanilla, Juvencio Robles* Departamento de Farmacia, DCNE, Universidad de Guanajuato, Noria Alta S/N. Col. Noria Alta, C. P. 36050, Guanajuato, Gto., México. *Corresponding author: Juvencio Robles, email: [email protected] Received March 11th, 2020; Accepted June 24th , 2020. DOI: http://dx.doi.org/10.29356/jmcs.v64i3.1167 Abstract. Allotropes of carbon such as graphene, graphane, fluorographene, doped graphene with N, B or P, graphene oxide, graphyne, and graphdiyne were studied through conceptual DFT reactivity descriptor indexes. To understand their chemical behavior and how they interact with different types of molecules, for instance, drugs (due to their potential use in drug carrier applications). This work shows the results of the changes in the global and local reactivity descriptor indexes and geometrical characteristics within the different graphene derivatives and rationalizes how they can interact with small molecules. Molecular hardness, the ionization energy, the electron affinity, electrodonating power index, and electroaccepting power indexes are the computed global reactivity descriptors. While, fukui functions, local softness, and molecular electrostatic potential are the local reactivity descriptors. The results suggest that the hybridization of carbons in the derivatives is kept close to sp3, while for graphene is sp2, the symmetry changes have as consequence changes in their chemical behavior. We found that doping with B or P (one or two atoms doped) and functionalizing with -OH or -COOH groups (as in graphene oxide), decreases the ionization energy in water solvent calculations, allowing for easier electron donation.
    [Show full text]
  • Boron Content and the Superconducting Critical Temperature of Carbon-Based Materials (November 26, 2020)
    1 Boron Content and the Superconducting Critical Temperature of Carbon-Based Materials (November 26, 2020) Nadina Gheorghiu, Charles R. Ebbing, and Timothy J. Haugan Abstract—In this paper, we present results on magnetization properties of boron nitride-carbon (BN-C) and boron carbide- carbon (B4C-C) granular mixtures. The temperature-dependent magnetization for field-cooled during cooling and field- cooled during warming shows a kind of thermal hysteresis that is always seen around a metamagnetic phase transition from an antiferromagnetic martensite to a ferromagnetic austenite phase. The low-temperature magnetization has an upward turn that can be attributed to superparamagnetism, diamagnetic shielding, and trapped flux characteristic to high-temperature superconducting materials. After subtracting the diamagnetic background, the field-dependent magnetization loops M(B) are ferromagnetic-like, more significant for the BN-C than for the B4C-C mixture. In addition, the magnetization loops show the kink feature characteristic to granular superconductivity. The irreversibility temperature for a B4C-C mixture having 37.5 wt% B is Tc 76 K. Combining our data with previous results on B-doped diamond and Q-carbon, we find that Tc increases linearly with the B concentration. Index Terms—boron-doped carbon, boron carbide, boron nitride, metamagnetic phase transition, granular superconductors I. INTRODUCTION Power systems, including for aerospace applications, need to optimally combine advanced functions with low-cost production. Currently, most of the high-temperature superconducting materials (HTS) materials are rare-earth based. The more available, thus cost-effective carbon (C) allotropes and C-based materials are ultra-high-strength yet much lighter than copper or steel.
    [Show full text]
  • The New Skinny in Two-Dimensional Nanomaterials Kristie J
    PERSPECTIVE The New Skinny in Two-Dimensional Nanomaterials Kristie J. Koski† and Yi Cui†,‡,* †Department of Materials Science & Engineering, Stanford University, Stanford, California 94305, United States, and ‡Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States ABSTRACT While the advent of graphene has focused attention on the extraordinary properties of two-dimensional (2D) materials, graphene's lack of an intrinsic band gap and limited amenability to chemical modification has sparked increasing interest in its close relatives and in other 2D layered nanomaterials. In this issue of ACS Nano, Bianco et al. report on the production and characterization of one of these related materials: germanane, a one-atom-thick sheet of hydrogenated puckered germanium atoms structurally similar to graphane. It is a 2D nanomaterial generated via mechanical exfoliation from GeH. Germanane has been predicted to have technologically relevant properties such as a direct band gap and high electron mobility. Monolayer 2D materials like germanane, in general, have attracted enormous interest for their potential technological applications. We offer a perspective on the field of 2D layered nanomaterials and the exciting growth areas and discuss where the new development of germanane fits in, now and in the foreseeable future. gnited by immense technological pro- 2D electron gas physics, superconductivity, mise, the field of two-dimensional (2D) spontaneous magnetization, and anisotropic layered nanomaterials has grown ex- transport properties. Layered 2D materials I 1,2 tensively over the past decade. Two- find current applications in a wide array of dimensional nanomaterials are typically capacities such as batteries, electrochromics, generated from bulk layered crystalline cosmetics, catalysts, and solid lubricants.3 solids (Figure 1) such as graphite or di- With successive thinning of the layers to chalcogenides.
    [Show full text]
  • Superconductivity in Hydrogenated Carbon Nanostructures?
    Eur. Phys. J. B (2018) 91: 177 https://doi.org/10.1140/epjb/e2018-90168-7 THE EUROPEAN PHYSICAL JOURNAL B Regular Article Superconductivity in hydrogenated carbon nanostructures? Antonio Sanna1, a, Arkadiy Davydov2, John Kay Dewhurst1, Sangeeta Sharma1, and Jos´eA. Flores-Livas3 1 Max-Planck Institute f¨urMikrostrukturPhysik, Weinberg 2, 06120 Hale, Germany 2 Department of Physics, Kings College London, London WC2R 2LS, UK 3 Department of Physics, Universit¨atBasel, Klingelbergstr. 82, 4056 Basel, Switzerland Received 13 March 2018 / Received in final form 29 May 2018 Published online 6 August 2018 c The Author(s) 2018. This article is published with open access at Springerlink.com Abstract. We present an application of density functional theory for superconductors to superconductivity in hydrogenated carbon nanotubes and fullerane (hydrogenated fullerene). We show that these systems are chemically similar to graphane (hydrogenated graphene) and like graphane, upon hole doping, develop a strong electron phonon coupling. This could lead to superconducting states with critical temperatures approaching 100 K, however this possibility depends crucially on if and how metallization is achieved. 1 Introduction gating or by a chemical substitution. So far the doped configuration of graphane has not been synthesized and The development of accurate ab-initio many body meth- the prediction is not yet confirmed. Still this material ods for superconductivity, such as Eliashberg´ theory [1,2] is of great importance for several reasons: first graphane and
    [Show full text]