Abstract
In this study, we considered changes in the surface chemistry after introducing fluorine into the surface layer of nanoporous activated carbon (BAU) produced from the birch wood. Here, we examined the BAU treated with 1,1,1,2-tetrafluoroethane at the selected temperature in the range of 400–800 °C. Diverse methods, including chemical analysis, nitrogen adsorption–desorption, SEM–EDS, XPS, and 19F solid-state NMR, were used for the characterization of the prepared materials. It was found that one can introduce from 0.17 to 0.42 mmol of F per gram of BAU using fluoroalkylation at 400–500 °C. Increasing the temperature to 600 °C increases the fluorination efficiency, and the relatively high fluorine content of 1.86 mmol of F per gram of BAU can be reached. At least three group types, namely, C–F, CF2, and CF3 groups, were found by XPS and 19F solid-state NMR after such treatment. The content of “semi-ionic” fluorine drastically increases in the surface layer after high-temperature fluoroalkylation at 700 °C and 800 °C. This “semi-ionic” fluorine, in the form of C–F and CF2 groups, is directly conjugated with the π-electron system of the carbon matrix.
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References
Aarva A, Deringer VL, Sainio S, Laurila T, Caro MA (2019) Understanding X-ray spectroscopy of carbonaceous materials by combining experiments, density functional theory, and machine learning. Part II: Quantitative fitting of spectra. Chem Mater 31:9256–9267. https://doi.org/10.1021/acs.chemmater.9b02050
Adamska M, Narkiewicz U (2017) Fluorination of carbon nanotubes—a review. J Fluorine Chem 200:179–189. https://doi.org/10.1016/j.jfluchem.2017.06.018
Akiyama T, Kamihigoshi T, Takagi S, Maeda T (1984) Process for continuous fluorination of carbon. US Patent 4447663
Alemany L, Zhang L, Zeng L, Edwards C, Barron A (2007) Solid-state NMR analysis of fluorinated single-walled carbon nanotubes: assessing the extent of fluorination. Chem Mater 19:735–744. https://doi.org/10.1021/CM0618906
Asanov IP, Paasonen VM, Mazalov LN, Nazarov AS (1998) X-ray photoelectron study of fluorinated graphite intercalation compounds. J Struct Chem 39:928–932. https://doi.org/10.1007/BF02903607
Boltalina OV, Nakajima T (2016) New fluorinated carbons: fundamentals and applications, 1st edn. Elsevier, Amsterdam
Burgess DR, Zachariah MR, Tsang W, Westmoreland PR (1996) Thermochemical and chemical kinetic data for fluorinated hydrocarbons. Prog Energy Combust Sci 21:453–529. https://doi.org/10.1016/0360-1285(95)00009-7
Chen X, Wang X, Fang D (2020) A review on C1s XPS spectra for some kinds of carbon materials. Fuller Nanotub Car N 28:1048–1058. https://doi.org/10.1080/1536383X.2020.1794851
Claves D (2011) Spectroscopic study of fluorinated carbon nanostructures. New J Chem 35:2477–2482. https://doi.org/10.1039/C1NJ20239A
Dai L (2019) Carbon-based metal-free catalysts: design and applications, 2 volumes. Wiley-VCH, Weinheim
Dai Y, Cai S, Wu L, Yang W, Xie J, Wen W, Zheng Y, Zheng J-C, Zhu Y (2014) Surface modified and controlled CFx cathode material for ultrafast discharge and high energy density. J Mater Chem A 2:20896–20901. https://doi.org/10.1039/C4TA05492J
Diyuk VE, Mariychuk RT, Lisnyak VV (2016b) Barothermal preparation and characterization of micro–mesoporous activated carbons: textural studies, thermal destruction and evolved gas analysis with TG-TPD-IR technique. J Thermal Anal Calorim 124:1119–1130. https://doi.org/10.1007/s10973-015-5208-6
Diyuk V, Zaderko A, Grishchenko LM (2016a) Process for producing fluorine-containing carbon material. UA Patent 110585
Dolbier W.R. Jr. (2016) Guide to Fluorine NMR for Organic Chemists, second ed., Wiley, Hoboken NJ, pp. 77, 170, 239–240.
Feng W, Long P, Feng Y, Li Y (2016) Two-dimensional fluorinated graphene: synthesis, structures. Properties Appl Adv Sci (Weinh) 3:1500413. https://doi.org/10.1002/advs.201500413
Freudenreich R, Mielke I, Rettenbeck K, Schottle T (1994) US Patent 5334783.
Golub MA, Banks BA, Rutledge SK, Kitral MC (2001) Fluoropolymer films deposited by argon ion-beam sputtering of polytetrafluoroethylene, in fluorinated surfaces, coatings, and films, chap. 16. ACS Symp Ser 787:213–221. https://doi.org/10.1021/bk-2001-0787.ch016
Gotzias A, Tylianakis E, Froudakis G, Steriotis T (2013) Effect of surface functionalities on gas adsorption in microporous carbons: a grand canonical Monte Carlo study. Adsorption 19:745–756. https://doi.org/10.1007/s10450-013-9507-6
Groult H, Nakajima T, Perrigaud L, Ohzawa Y, Yashiro H, Komaba S, Kumagai N (2005) Surface–fluorinated graphite anode materials for Li–ion batteries. J Fluorine Chem 126:1111–1116. https://doi.org/10.1016/j.jfluchem.2005.03.014
Guerin K, Dubois M, Houdayer A, Hamwi A (2012) Applicative performances of fluorinated carbons through fluorination routes: a review. J Fluorine Chem 134:11–17. https://doi.org/10.1016/j.jfluchem.2011.06.013
Han W, Li Y, Tang H, Liu H (2012) Treatment of the potent greenhouse gas, CHF3–An overview. J Fluorine Chem 140:7–16. https://doi.org/10.1016/j.jfluchem.2012.04.012
Inagaki M, Kang F (2014) Graphene derivatives: graphane, fluorographene, graphene oxide, graphyne and graphdiyne. J Mater Chem A 2:13193–13206. https://doi.org/10.1039/C4TA01183J
Jung M-J, Kim EJS, Lee SI, Yood J-S, Lee Y-S (2011) Fluorination effect of activated carbon electrodes on the electrochemical performance of electric double layer capacitors. J Fluorine Chem 132:1127–1133. https://doi.org/10.1016/j.jfluchem.2011.06.046
Jung M-J, Jeong E, Lee Y-S (2015) The surface chemical properties of multi-walled carbon nanotubes modified by thermal fluorination for electric double-layer capacitor. Appl Surf Sci 347:250–257. https://doi.org/10.1016/j.apsusc.2015.04.038
Kang JH, Takhar D, Kuznetsov OV, Khabashesku VN, Kelly KF (2012) Fluorination and defluorination of carbon nanotubes: a nanoscale perspective. Chem Phys Lett 534:43–47. https://doi.org/10.1016/j.cplett.2012.03.026
Kemnitz E, Niedersen KU (1995) Isomerization-reactions of 1,1,2,2-tetrafluoroethane - a kinetic and mechanistic study. J Catal 155:283–289. https://doi.org/10.1006/jcat.1995.1210
Kim M-J, Jung M-J, Choi SS, Lee Y-S (2015) Effects of the fluorination of activated carbons on the chromium ion adsorption. Appl Chem Eng 26:92–98. https://doi.org/10.14478/ace.2014.1126
Koseki Y, Aimi K, Ando S (2012) Crystalline structure and molecular mobility of PVDF chains in PVDF/PMMA blend films analyzed by solid-state 19F MAS NMR spectroscopy. Polym J 44:757–763. https://doi.org/10.1038/pj.2012.76
Kundu SK, Kennedy EM, Mackie JC, Holdsworth CI, Molloy TS, Gaikwad VV, Dlugogorski BZ (2014) Nonequilibrium plasma polymerization of HFC-134a in a dielectric barrier discharge reactor: polymer characterization and a proposed mechanism for polymer formation. IEEE Trans Plasma Sci 42(6740081):3095–3100. https://doi.org/10.1109/TPS.2014.2303485
Lee C, Han Y-J, Seo YD, Nakabayashi K et al (2016) C4F8 plasma treatment as an effective route for improving rate performance of natural/synthetic graphite anodes in lithium ion batteries. Carbon 103:28–35. https://doi.org/10.1016/j.carbon.2016.02.060
Li D, Liao M (2017) Dehydrofluorination mechanism, structure and thermal stability of pure fluoroelastomer (poly(VDF-ter-HFP-ter-TFE) terpolymer) in alkaline environment. J Fluorine Chem 201:55–67. https://doi.org/10.1016/j.jfluchem.2017.08.002
Li D, Liao M (2018) Study on the dehydrofluorination of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) copolymer. Polym Degrad Stab 152:116–125. https://doi.org/10.1016/j.polymdegradstab.2018.04.008
Liu Y, Vander Wal RL, Khabashesku VN (2007) Functionalization of carbon nano-onions by direct fluorination. Chem Mater 19:778–786. https://doi.org/10.1021/cm062177j
Malkov GS, Martin IT, Schwisow WB, Chandler JP, Wickes BT, Gamble LJ, Castner DG, Fisher ER (2008) Pulsed-plasma-induced micropatterning with alternating hydrophilic and hydrophobic surface chemistries. Plasma Processes Polym 5:129–145. https://doi.org/10.1002/ppap.200700118
Matthews ES, Duan X, Powell RL (2010) Fluorinated carbon nanostructures of CFx where 0.05<x<0.30. US Patent 7700192 B2
Meng LY, Park S-J (2014) Superhydrophobic carbon-based materials: a review of synthesis, structure, and applications. Carbon Lett 15:89–104. https://doi.org/10.5714/CL.2014.15.2.089
Murakami M, Matsumoto K, Hagiwara R, Matsuo Y (2018) 13C/19F high-resolution solid-state NMR studies on layered carbon-fluorine compounds. Carbon 138:179–187. https://doi.org/10.1016/j.carbon.2018.06.004
Nakajima T (2007) Surface modification of carbon anodes for secondary lithium battery by fluorination. J Fluorine Chem 128:277–284. https://doi.org/10.1016/B978-0-12-800679-5.00009-9
Nansé G, Papirer E, Fioux P, Moguet F, Tressaud A (1997) Fluorination of carbon blacks: an X-ray photoelectron spectroscopy study: I. A literature review of XPS studies of fluorinated carbons. XPS investigation of some reference compounds. Carbon 35:175–194. https://doi.org/10.1016/s0008-6223(96)00095-4
Neira-Carrillo A, Verdejo R, López-Manchado MA (2018) Synthesis of fluorinated graphene oxide by using an easy one-pot deoxyfluorination reaction. J Colloid Interface Sci 524:219–222. https://doi.org/10.1016/j.jcis.2018.04.030
Panich AM (1999) Nuclear magnetic resonance study of fluorine-graphite intercalation compounds and graphite fluorides. Synth Met 100:169–185. https://doi.org/10.1016/S0379-6779(98)01512-4
Plötze M, Niemz P (2011) Porosity and pore size distribution of different wood types as determined by mercury intrusion porosimetry. Eur J Wood Prod 69:649–657. https://doi.org/10.1007/s00107-010-0504-0
Sato Y, Itoh K, Hagiwara R, Fukunaga T, Ito Y (2004) On the socalled ‘semi-ionic’ C-F bond character in fluorine–GIC. Carbon 42:3243–3249. https://doi.org/10.1016/j.carbon.2004.08.012
Saunders C, Khaled MB, Weaver JD, Tantillo DJ (2018) Prediction of 19F NMR chemical shifts for fluorinated aromatic compounds. J Org Chem 83:3220–3225. https://doi.org/10.1021/acs.joc.8b00104
Struzzi C, Scardamaglia M, Reckinger N, Sezen H et al (2017) Probing plasma fluorinated graphene via spectromicroscopy. Phys Chem Chem Phys 19:31418–31428. https://doi.org/10.1039/C7CP05305C
Struzzi C, Scardamaglia M, Colomer JF, Verdini A et al (2017) Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization. Beilstein J Nanotechnol 8:1723–1733. https://doi.org/10.3762/bjnano.8.173
Touhara H, Okino F (2000) Property control of carbon materials by fluorination. Carbon 38:241–267. https://doi.org/10.1016/S0008-6223(99)00140-2
Tressaud A, Moguet F, Flandroiss S, Chambon M et al (1996) On the nature of CF bonds in various fluorinated carbon materials: XPS and TEM investigations. J Phys Chem Solids 57:745–751. https://doi.org/10.1016/0022-3697(96)00343-5
Vyalikh A, Bulusheva LG, Chekhova GN, Pinakov DV, Okotrub AV, Scheler U (2013) Fluorine patterning in room-temperature fluorinated graphite determined by solid-state NMR and DFT. J Phys Chem C 117:7940–7948. https://doi.org/10.1021/jp4028029
Watanabe N, Nakajima T, Touhara H (2013) Graphite fluorides. Elsevier, Amsterdam
Weigert FJ (1990) Fluorine NMR parameters of two-carbon chlorofluorohydrocarbons. J Fluorine Chem 46:375–384. https://doi.org/10.1016/S0022-1139(00)82923-1
Yi JW, Lee YH, Farouk B (2000) Low dielectric fluorinated amorphous carbon thin films grown from C6F6 and Ar plasma. Thin Solid Films 374:103–108. https://doi.org/10.1016/S0040-6090(00)01021-X
Zaderko A, Prusov V, Diyuk V (2016) Method for carbon materials surface modification by the fluorocarbons and derivatives. WO2016072959 Patent.
Zaderko AN, Shvets RYa, Grygorchak II et al. (2019) Fluoroalkylated nanoporous carbons: testing as a supercapacitor electrode. Appl Surf Sci 470:882–892. DOI: https://doi.org/10.1016/j.apsusc.2018.11.141
Zaderko AN, Grishchenko LM, Pontiroli D, Scaravonati S, Ricco M, Diyuk VE, Skryshevsky VA, Lisnyak VV (2021) Enhancing the performance of carbon electrodes in supercapacitors through medium-temperature fluoroalkylation. Appl Nanosci. https://doi.org/10.1007/s13204-020-01651-0
Zhong G, Chen H, Huang X, Yue H, Lu C (2018) High-power-density, high-energy-density fluorinated graphene for primary lithium batteries. Front Chem 6:50. https://doi.org/10.3389/fchem.2018.00050
Zhou S, Sherpa SD, Hess DW, Bongiorno A (2014) Chemical bonding of partially fluorinated graphene. J Phys Chem C 118:26402–26408. https://doi.org/10.1021/jp508965q
Acknowledgments
This research was supported by the Ministry of Education and Science of Ukraine under the State budget programs, Grants Nos. 0118U001125, 0116U002558, 0119U100167, 0119U100326, and 0120U102178. A.N. Zaderko acknowledges the support of the National Scholarship Programme of the Slovak Republic, SAIA, n.o., by the grant ID 32492 in 2021. S. Afonin acknowledges the support by the Helmholtz Association (Program BIFTM) and of the solid-state NMR facility at KIT by the Instrument Grant INST 121384/58-1 from Deutsche Forschungsgemeinschaft.
Funding
This study was funded by the Ministry of Education and Science of Ukraine, Grants Nos. 0118U001125, 0116U002558, 0119U100167, 0119U100326, and 0120U102178. A.N. Zaderko was supported by grant ID 32492 from the National Scholarship Programme of the Slovak Republic, SAIA, in 2021. S. Afonin was supported by the Helmholtz Association (Program BIFTM) and by the Instrument Grant INST 121384/58-1 from Deutsche Forschungsgemeinschaft.
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V.E. Diyuk and A.N. Zaderko are the inventors of the patent WO/2016/072959. A.N. Zaderko is the owner of the trademark Fluocar®. All other authors declare that they have no conflict of interest with this study.
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Diyuk, V.E., Zaderko, A.N., Grishchenko, L.M. et al. Surface chemistry of fluoroalkylated nanoporous activated carbons: XPS and 19F NMR study. Appl Nanosci 12, 637–650 (2022). https://doi.org/10.1007/s13204-021-01717-7
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DOI: https://doi.org/10.1007/s13204-021-01717-7