Preparation and Applications of Fluorinated Graphenes
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Absence of Stable Atomic Structure in Fluorinated Graphene
Absence of stable atomic structure in fluorinated graphene Danil W. Boukhvalov1,2 1Department of Chemistry, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791, Korea 2Theoretical Physics and Applied Mathematics Department, Ural Federal University, Mira Street 19, 620002 Ekaterinburg, Russia Based on the results of first-principles calculations we demonstrate that significant distortion of graphene sheets caused by adsorption of fluorine atoms leads to the formation of metastable patterns for which the next step of fluorination is considerably less energetically favorable. Existence of these stable patterns oriented along the armchair direction makes possible the synthesis of various CFx structures. The combination of strong distortion of the nonfluorinated graphene sheet with the doping caused by the polar nature of C–F bonds reduces the energy cost of migration and the energy of migration barriers, making possible the migration of fluorine atoms on the graphene surface as well as transformation of the shapes of fluorinated areas. The decreasing energy cost of migration with increasing fluorine content also leads to increasing numbers of single fluorine adatoms, which could be the source of magnetic moments. 1. Introduction Functionalization of graphene is used to tune its electronic, optical, mechanical and chemical properties [1]. The best known kind of functionalized graphene is graphene oxide, which can be obtained by means of exfoliating graphite oxide and was first synthesized more than 150 years ago [2]. Unfortunately, graphene oxide’s complicated method of synthesis and inexact chemical structure make it unsuitable for some prospective applications; structural problems of particular note include the presence of perforations of various sizes and shapes, decreasing size of the graphene flakes and nonuniform distribution of functionalized areas [2]. -
Material Degradation Studies in Molten Halide Salts
MATERIAL DEGRADATION STUDIES IN MOLTEN HALIDE SALTS BRENDAN D’SOUZA Dissertation submitted to the faculty of the Virginia Polytechnic Institute and State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy In Nuclear Engineering Jinsuo Zhang, Chair Mark Pierson Yang Liu Xianming Bai 5th March, 2021 Blacksburg, Virginia Keywords: Molten Salt Purification, Molten Salt Corrosion, Nickel-Based Alloys, Ferrous-Based Alloys, Boriding/Boronizing MATERIAL DEGRADATION STUDIES IN MOLTEN HALIDE SALTS BRENDAN D’SOUZA ABSTRACT This study focused on molten salt purification processes to effectively reduce or eliminate the corrosive contaminants without altering the salt's chemistry and properties. The impurity-driven ® ® corrosion behavior of HAYNES 230 alloy in the molten KCl-MgCl2-NaCl salt was studied at 800 ºC for 100 hours with different salt purity conditions. The H230 alloy exhibited better corrosion resistance in the salt with lower concentration of impurities. Furthermore, it was also found that the contaminants along with salt's own vaporization at high temperatures severely corroded even the non-wetted surface of the alloy. The presence of Mg in its metal form in the salt resulted in an even higher mass-loss possibly due to Mg-Ni interaction. The study also investigated the corrosion characteristics of several nickel and ferrous-based alloys in the molten KCl-MgCl2- NaCl salt. The average mass-loss was in the increasing order of C276 < SS316L < 709-RBB* < IN718 < H230 < 709-RBB < 709-4B2. The corrosion process was driven by the outward diffusion of chromium. However, other factors such as the microstructure of the alloy i.e. -
Cytotoxicity of Fluorographene
RSC Advances Cytotoxicity of fluorographene Journal: RSC Advances Manuscript ID RA-ART-10-2015-022663.R1 Article Type: Paper Date Submitted by the Author: 29-Nov-2015 Complete List of Authors: Teo, Wei Zhe; Nanyang Technological University, Chemistry and Biological Chemistry Sofer, Zdenek; Institute of Chemical Technology, Prague, Department of Inorganic Chemistry Sembera, Filip; Institute of Organic Chemistry and Biochemistry AS CR, v.v.i., Janousek, Zbynek; Institute of Organic Chemistry and Biochemistry, Pumera, Martin; Nanyang Technological University, Chemistry and Biological Chemistry Subject area & keyword: Nanomaterials - Materials < Materials Page 1 of 9 PleaseRSC do not Advances adjust margins Journal Name ARTICLE Cytotoxicity of fluorographene Wei Zhe Teo,a Zdenek Sofer b, Filip Šembera c, Zbyněk Janoušek c and Martin Pumera* a Received 00th January 20xx, Accepted 00th January 20xx Fluorinated graphene (F-G) are gaining popularity in recent years and should they be introduced commercially in the future, these nanomaterials will inevitably be released into the environment through disposal or wearing of the products. DOI: 10.1039/x0xx00000x In view of this, we attempted to investigate the cytotoxicity of three F-G nanomaterials in this study, with the use of two www.rsc.org/ well-establish cell viability assays, to find out their impact on mammalian cells and how their physiochemical properties might affect the extent of their cytotoxicity. Cell viability measurements on A549 cells following 24 h exposure to the F-G revealed that F-G does impart dose-dependent toxicological effects on the cells, and the level of cytotoxicity induced by the nanomaterials differed vastly. It was suggested that the fluorine content, in particular the types of fluorine-containing group present in the nanomaterial played significant roles in affecting its cytotoxicity. -
(12) United States Patent (10) Patent No.: US 9,017,474 B2 Geim Et Al
US00901.7474B2 (12) United States Patent (10) Patent No.: US 9,017,474 B2 Geim et al. (45) Date of Patent: Apr. 28, 2015 (54) FUNCTIONALIZED GRAPHENE AND 2011/0186786 A1* 8, 2011 Scheffer et al. ............... 252/510 METHODS OF MANUFACTURING THE 2011/0186789 A1* 8, 2011 Samulski et al. .. ... 252/514 SAME 2012/0021293 A1 1/2012 Zhamu et al. .............. 429,2315 (75) Inventors: Andre Geim, Manchester (GB); Rahul OTHER PUBLICATIONS Raveendran-Nair, Manchester (GB); Kostya Novoselov, Manchester (GB) http://www.merriam-Webster.com/dictionary/composite; May 23, s 2014. (73) Assignee: The University of Manchester, Blake, P. et al., “Graphene-based liquid crystal device.” Nano Lett. Manchester (GB) 8(6): 1704-1708, (Apr. 30, 2008). Castro Neto, A., et al., “The electronic properties of graphene.” Rev. (*) Notice: Subject to any disclaimer, the term of this Mod. Phys., 81(1): 109-162, (2009). patent is extended or adjusted under 35 Charlier, J., et al., “First-principles study of graphite monofluoride U.S.C. 154(b) by 436 days. (CF).” Phys Rev. B. 47(24): 16162-16168, (1993). Cheng, S., “Reversible fluorination of graphene: towards a two (21) Appl. No.: 13/158,064 dimensional wide bandgap semiconductor. J. Am. Chem. Soc., 101:3832-3841, (1979). (22) Filed: Jun. 10, 2011 Conesa, J. and Font, R., “Poytetrafluoroethylene decomposition in air and nitrogen.” Polym. Eng. Scie., 41(12):2137-2147 (Dec. 2001). (65) Prior Publication Data Eda, C. and Chhowalla, M.. “Chemically derived graphene oxide: US 2011 FO3O3121 A1 Dec. 15, 2011 towards large-area thin-film electronics and optoelectronics.” Adv. • als Mater. -
Arxiv:1109.4050V5 [Cond-Mat.Mtrl-Sci] 24 Jan 2013 Even More Important
First-Principles Investigation of Bilayer Fluorographene J. Sivek,1, ∗ O. Leenaerts,1, y B. Partoens,1, z and F. M. Peeters1, x 1Departement Fysica, Universiteit Antwerpen, Groenenborgerlaan 171, B-2020 Antwerpen, Belgium (Dated: October 7, 2018) Ab initio calculations within the density functional theory formalism are performed to investigate the stability and electronic properties of fluorinated bilayer graphene (bilayer fluorographene). A comparison is made to previously investigated graphane, bilayer graphane, and fluorographene. Bilayer fluorographene is found to be a much more stable material than bilayer graphane. Its electronic band structure is similar to that of monolayer fluorographene, but its electronic band gap is significantly larger (about 1 eV). We also calculate the effective masses around the Γ-point for fluorographene and bilayer fluorographene and find that they are isotropic, in contrast to earlier reports. Furthermore, it is found that bilayer fluorographene is almost as strong as graphene, as its 2D Young's modulus is approximately 300 N m−1. PACS numbers: 61.48.Gh, 68.43.-h, 68.43.Bc, 68.43.Fg, 73.21.Ac, 81.05.Uw I. INTRODUCTION result from the hydrogenation and fluorination of graphene, respectively. They are theoretically predicted Since the first reports on the successful isolation of sta- [19{26] and experimentally observed [14{16, 18, 27, 28] ble two-dimensional crystals consisting of a single atom to form crystalline materials, in contrast to, for example, layer by Novoselov et al. in 2004, [1, 2] researchers graphene oxide. [29, 30] have been looking for ways to employ these new mate- These new two-dimensional crystals are currently the rials in real-world applications. -
Electronic and Optical Properties of Fluorographene
Electronic Structure and Optical Absorption of Fluorographene Yufeng Liang and Li Yang Department of Physics, Washington University in St. Louis, One Brookings Drive, St. Louis, MO 63130, USA ABSTRACT A first-principles study on the quasiparticles energy and optical absorption spectrum of fluorographene is presented by employing the GW + Bethe-Salpeter Equation (BSE) method with many-electron effects included. The calculated band gap is increased from 3.0 eV to 7.3 eV by the GW approximation. Moreover, the optical absorption spectrum of fluorographene is dominated by enhanced excitonic effects. The prominent absorption peak is dictated by bright resonant excitons around 9.0 eV that exhibit a strong charge transfer character, shedding light on the exciton condensation and relevant optoelectronic applications. At the same time, the lowest-lying exciton at 3.8 eV with a binding energy of 3.5 eV is identified, which gives rise to explanation of the recent ultraviolet photoluminescence experiment. INTRODUCTION Graphene [1] has attracted intensive attention recently because of its extraordinary physical properties and broad applications. The linear dispersion relation near the Dirac point results in the relativistic nature of electrons [2] and leads to an ultrahigh mobility of charge carriers, rendering graphene a promising candidate for future high speed nano-electronic devices [3]. However, one known obstacle of putting graphene into realistic applications is the absence of a finite band gap that is essential for semiconductor devices, such as building bipolar junction structures. As a result, many efforts have been performed to generate a finite band gap in graphene or its derivatives. Among them, the chemical modification [4-7] has been regarded as a promising candidate because of its low cost and capability for large-scale productions. -
Synergistically Chemical and Thermal Coupling Between Graphene Oxide and Graphene Fluoride for Enhancing Aluminum Combustion
Synergistically Chemical and Thermal Coupling between Graphene Oxide and Graphene Fluoride for Enhancing Aluminum Combustion The MIT Faculty has made this article openly available. Please share how this access benefits you. Your story matters. Citation Jiang, Yue et al. "Synergistically Chemical and Thermal Coupling between Graphene Oxide and Graphene Fluoride for Enhancing Aluminum Combustion." ACS Applied Materials and Interfaces 12, 6 (January 2020): 7451–7458 © 2020 American Chemical Society As Published http://dx.doi.org/10.1021/acsami.9b20397 Publisher American Chemical Society (ACS) Version Author's final manuscript Citable link https://hdl.handle.net/1721.1/127994 Terms of Use Creative Commons Attribution-Noncommercial-Share Alike Detailed Terms http://creativecommons.org/licenses/by-nc-sa/4.0/ * Unknown *|ACSJCA | JCA11.2.5208/W Library-x64 | manuscript.3f (R5.0.i2:5002 | 2.1) 2020/01/15 13:43:00 | PROD-WS-118 | rq_1369240 | 1/24/2020 09:25:19 | 8 | JCA-DEFAULT www.acsami.org Research Article 1 Synergistically Chemical and Thermal Coupling between Graphene 2 Oxide and Graphene Fluoride for Enhancing Aluminum Combustion # # # 3 Yue Jiang, Sili Deng, Sungwook Hong, Subodh Tiwari, Haihan Chen, Ken-ichi Nomura, 4 Rajiv K. Kalia, Aiichiro Nakano, Priya Vashishta, Michael R. Zachariah, and Xiaolin Zheng* Cite This: https://dx.doi.org/10.1021/acsami.9b20397 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information 5 ABSTRACT: Metal combustion reaction is highly exothermic and is used in energetic 6 applications, such as propulsion, pyrotechnics, powering micro- and nano-devices, and 7 nanomaterials synthesis. Aluminum (Al) is attracting great interest in those applications 8 because of its high energy density, earth abundance, and low toxicity. -
Organic Adsorbates Have Higher Affinities to Fluorographene Than To
Applied Materials Today 5 (2016) 142–149 Contents lists available at ScienceDirect Applied Materials Today j ournal homepage: www.elsevier.com/locate/apmt Organic adsorbates have higher affinities to fluorographene than to graphene ∗ Eva Otyepková, Petr Lazar, Klára Cépe,ˇ Ondrejˇ Tomanec, Michal Otyepka Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky´ University Olomouc, tr.ˇ 17. Listopadu 12, 771 46 Olomouc, Czech Republic a r t i c l e i n f o a b s t r a c t Article history: The large surfaces of two-dimensional carbon-based materials, such as graphene and fluorographene, Received 1 September 2016 are exposed to analytes, impurities and other guest molecules, so an understanding of the strength and Received in revised form nature of the molecule–surface interaction is essential for their practical applications. Using inverse gas 24 September 2016 chromatography, we determined the isosteric adsorption enthalpies and entropies of six volatile organic Accepted 24 September 2016 molecules (benzene, toluene, cyclohexane, n-hexane, 1,4-dioxane, and nitromethane) to graphene and graphite fluoride powders. The adsorption entropies of the molecules ranged from −17 to −34 cal/mol K Keywords: and the maximum adsorption-induced entropy loss occurred for nitromethane at the high-energy sites. Enthalpy Entropy The enthalpies of bulkier adsorbates were almost coverage-independent on both surfaces and ranged − − IGC from 11 to 14 kcal/mol. Despite the fact that fluorographene has lower surface energy than graphene Graphene and graphene represents an ideal surface for the – stacking, the adsorbates had lower adsorption Fluorographene enthalpies to fluorographene than to graphene by ∼9%. -
A Brief Review for Fluorinated Carbon: Synthesis, Properties and Applications
Nanotechnol Rev 2019; 8:573–586 Review Article Yifan Liu, Lingyan Jiang, Haonan Wang, Hong Wang, Wei Jiao*, Guozhang Chen*, Pinliang Zhang, David Hui, and Xian Jian A brief review for fluorinated carbon: synthesis, properties and applications https://doi.org/10.1515/ntrev-2019-0051 Received Nov 30, 2019; accepted Dec 18, 2019 1 Introduction Abstract: Fluorinated carbon (CFx), a thriving member of Fluorinated carbon (CFx) is a promising member of the car- the carbonaceous derivative, possesses various excellent bon derivative family since graphite fluoride was synthe- properties of chemically stable, tunable bandgap, good sized by Ruff et al. in 1934 firstly [1]. Due to its extraordi- thermal conductivity and stability, and super-hydrophobic nary properties, such as good chemical stability, tunable due to its unique structures and polar C-F bonding. Herein, bandgap, good thermal conductivity and stability, and we present a brief review of the recent development of fluo- super-hydrophobicity [2–6], fluorinated carbon materials rinated carbon materials in terms of structures, properties attracts more and more attention. So, fluorinated carbon is and preparation techniques. Meanwhile, the applications a potential material in wide application fields such as self- in energy conversions and storage devices, biomedicines, cleaning, lubricants, super-hydrophobic coating and en- gas sensors, electronic devices, and microwave absorption ergy storage [7–11]. The synthesis methods of fluorinated devices are also presented. The fluorinated carbon con- carbon can be mainly classified into direct gas fluorination, tains various types of C-F bonds including ionic, semi- indirect fluorination and plasma-assisted fluorination [12– ionic and covalent C-F, C-F2, C-F3 bonds with tunable F/C 14]. -
Carbon – Element of Many Faces 1
1 1 Carbon – Element of Many Faces The sixth in the periodic table of elements is, at the same time, among the most important ones. With about 180 ppm, carbon is only 17th on the list of terrestrial elements ’ frequency, situated even after barium or sulfur – for comparison, the second - most frequent element, silicon, is about 1300 times as abundant as carbon. Still the latter is essential for the assembly of all organic matter. It is predestined for this central role especially due to its mid position in the periodic system and its associated ability to form stable substances with more electropositive and more electronegative reaction partners. Yet in the present text the organic chemistry resulting from these various bonding possibilities will only be mentioned if it is employed to modify carbon materials or, to put it in other words, the element itself as a material will be in the focus. Another feature that gave reason to write this book was the occurrence of various allotrope modifi cations with in parts completely opposite properties. For the time being, this renders carbon one of the most interesting topics in materials science and research. Be it fullerenes, nanotubes or nanocrystalline diamond phases – they all are subject to intensive investigation and promise a multitude of applications, for example, in electronics, medicine, and nanotechnology. Nevertheless, it is hardly possible to assess the development within the last two decades and to perceive its impact on the multitalented carbon ’ s perspectives in chemistry, material science, and physics, without an understanding of its long - known modifi cations, mainly graphite and diamond. -
Ultrastrong Adhesion of Fluorinated Graphene on a Substrate
Carbon 169 (2020) 248e257 Contents lists available at ScienceDirect Carbon journal homepage: www.elsevier.com/locate/carbon Ultrastrong adhesion of fluorinated graphene on a substrate: In situ electrochemical conversion to ionic-covalent bonding at the interface Yu-Yu Sin a, Cheng-Chun Huang a, Cin-Nan Lin b, Jui-Kung Chih b, Yu-Ling Hsieh b, * I-Yu Tsao c,JuLid, Ching-Yuan Su a, b, a Graduate Institute of Energy Engineering, National Central University, Tao-Yuan, 32001, Taiwan b Department of Mechanical Engineering, National Central University, Tao-Yuan, 32001, Taiwan c Institute of Materials Science and Engineering, National Central University, Tao-Yuan, 32001, Taiwan d Department of Nuclear Science and Engineering and Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA article info abstract Article history: Graphene shows unique properties such as high mechanical strength and high thermal and chemical Received 20 May 2020 stability, making it promising for versatile applications. However, the lack of either interlayer or interface Received in revised form covalent bonds causes this type of 2D materials assembled via van der Waals forces to suffer from weak 10 July 2020 adhesion with the underlying substrates, thus hindering their application. In this study, a novel method Accepted 28 July 2020 based on a hydrothermal reaction was proposed to synthesize fluorinated graphene (FG) through a facile, Available online 1 August 2020 scalable, and highly safe process, where a mixture of poly(perfluorosulfonic acid) (C7HF13O5S$C2F4, PFSA) and graphene oxide (GO) as the precursor was employed. The FG sheets prepared by the electrophoretic Keywords: Fluorination-graphene deposition (EPD) method exhibit superior conformity layered structure on a metal foil. -
(12) Patent Application Publication (10) Pub. No.: US 2015/0207145 A1 Palazzo Et Al
US 20150207145A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0207145 A1 Palazzo et al. (43) Pub. Date: Jul. 23, 2015 (54) HIGH CAPACITY CATHODE MATERIAL HIM I/0568 (2006.01) WITH IMPROVED RATE CAPABILITY HIM I/0563 (2006.01) PERFORMANCE HOLM 4/485 (2006.01) HOLM 4/62 (2006.01) (71) Applicant: Greatbatch Ltd., Clarence, NY (US) (52) U.S. Cl. CPC .............. H01 M 4/521 (2013.01); H0IM 4/485 (72) Inventors: Marcus J. Palazzo, Wheatfield, NY (2013.01); H01 M 4/622 (2013.01); H0IM (US); Ashish Shah, East Amherst, NY 4/625 (2013.01); H01 M 4/523 (2013.01); (US) H0IM 10/0568 (2013.01); H0IM 10/0563 (21) Appl. No.: 14/599,915 ( 2013.01);) H0IM(2013.01); 4/62 E.(2013.01); 2): H01 (2013.01) M 4/049 (22) Filed: Jan. 19, 2015 (57) ABSTRACT Related U.S. Application Data (60) Provisional application No. 61/928,768, filed on Jan. The present invention related to an electrochemical cell com 17, 2014. prising an anode of a Group IA metal and a cathode of a s composite material prepared from an aqueous mixture of iron Publication Classification sulfate, cobalt sulfate and sulfur. The cathode material of the present invention provides an increased rate pulse perfor (51) Int. Cl. mance compared to iron disulfide cathode material. This HOLM 4/52 (2006.01) makes the cathode material of the present invention particu HOLM 4/04 (2006.01) larly useful for implantable medical applications. Patent Application Publication Jul. 23, 2015 Sheet 1 of 6 US 2015/02071.45 A1 xx CD t -- & Patent Application Publication Jul.