Abstract
A new method is proposed for the simultaneous introduction of fluorine and chlorine into the surface layer of nanoporous-activated carbon (NAC). The method comprises treatment with dichlorodifluoromethane at 400–800 °C. Elemental analysis, nitrogen adsorption–desorption studies, electron microscopy, X-ray photoelectron (XPS) and solid-state 19F nuclear magnetic resonance (ssNMR) spectroscopies were exploited to analyze the composition, micro-, nanostructure, and functional surface coverage. The NAC modified at 400 °C has the lowest halogen content of 0.21 mmol g–1 of fluorine and 1.11 mmol g–1 of chlorine. Increasing the halogenation temperature to 500–700 °C significantly upsurges the efficiency of both fluorination and chlorination, up to 0.82–0.96 and 2.23–2.87 mmol g–1, respectively. Fluorine and chlorine are randomly but not evenly distributed in the porous structure of NAC. The outer carbon surface is enriched in fluorine, contrasting to the inner surface of the micropores. From XPS and 19F ssNMR measurements, mainly C–F, C–Cl, CClF2, CF2, and CF3 groups were identified as attached forms of halogens. High halogenation temperatures (up to 800 °C) cause a significant increase in the amount of "semi-ionic" fluorine, which is present as C–F and CF2 groups directly bonded to 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
Agopian J, Teraube O, Charlet K, Dubois M (2021) A review about the fluorination and oxyfluorination of carbon fibres. J Fluorine Chem 251:109887. https://doi.org/10.1016/j.jfluchem.2021.109887
Ahmad Y, Disa E, Guérin K, Dubois M, Petit E, Hamwi A, Thomas P, Mansot JL (2014) Structure control at the nanoscale in fluorinated graphitized carbon blacks through the fluorination route. J Fluorine Chem 168:163–172. https://doi.org/10.1016/j.jfluchem.2014.09.021
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
Bezugla TM, Grishchenko LM, Vakaliuk AV, Diyuk VE, Mischanchuk OV, Lisnyak VV (2018) Covalent bonding of sulfogroups to activated carbon fibers: the role of bromine plasma pretreatment. Mol Cryst Liquid Cryst 661:58–67. https://doi.org/10.1080/15421406.2018.1460240
Chen X, Wang X, Fang D (2020) A review on C1s XPS-spectra for some kinds of carbon materials. Fuller Nanotub Carbon Nanostructures 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 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, Zaderko AN, Grishchenko LM et al (2021) Surface chemistry of fluoroalkylated nanoporous activated carbons: XPS and 19F NMR study. Appl Nanosci. https://doi.org/10.1007/s13204-021-01717-7
Dolbier WR Jr (2016) Guide to fluorine NMR for organic chemists, 2nd edn. Wiley, Hoboken NJ, p 77
Emran MY, Shenashen MA, Eid AI, Selim MM, El-Safty SA (2022) Portable sensitive and selective biosensing assay of dopamine in live cells using dual phosphorus and nitrogen doped carbon urchin-like structure. Chem Eng J 430:132818. https://doi.org/10.1016/j.cej.2021.132818
Feng W, Long P, Feng Y, Li Y (2016) Two-dimensional fluorinated graphene: synthesis, structures, properties and applications. Adv Sci (Weinh) 3:1500413. https://doi.org/10.1002/advs.201500413
Gopalakrishnan K, Subrahmanyam KS, Prashant K, Govindaraj A, Rao CNR (2012) Reversible chemical storage of halogens in few-layer graphene. RSC Adv 2:1605–1608. https://doi.org/10.1039/C1RA00403D
Grishchenko LM, Vakaliuk AV, Diyuk VE, Mischanchuk OV, Boldyrieva OYu, Bezugla TM, Lisnyak VV (2018) From destructive CCl4 adsorption to grafting SO3H groups onto activated carbon fibers. Molec Cryst Liquid Cryst 673:1–15. https://doi.org/10.1080/15421406.2019.1578488
Grishchenko LM, Diyuk VE, Mariychuk RT et al (2020) Surface reactivity of nanoporous carbons: preparation and physicochemical characterization of sulfonated activated carbon fibers. Appl Nanosci 10:2923–2939. https://doi.org/10.1007/s13204-019-01069-3
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
Huang L, Luo Z, Luo M, Zhang Q, Zhu H, Shi K, Zhu S (2021) One-step synthesis of nitrogen−fluorine dual-doped porous carbon for supercapacitors. J Energy Storage 38:102509. https://doi.org/10.1016/j.est.2021.102509
Ischenko EV, Matzui LY, Gayday SV, Vovchenko LL, Kartashova TV, Lisnyak VV (2010) Thermo-exfoliated graphite containing CuO/Cu2(OH)3NO3:(Co2+/Fe3+) composites: preparation, characterization and catalytic performance in CO conversion. Materials 3:572. https://doi.org/10.3390/ma3010572
Jo H, Kim KH, Jung M, Park JH, Lee Y (2017) Fluorination effect of activated carbons on performance of asymmetric capacitive deionization. Appl Surf Sci 409:117–123. https://doi.org/10.1016/j.apsusc.2017.02.234
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
Kim MH, Yang JH, Kang YM, Park SM, Han JT, Kim KB, Roh KC (2014) Fluorinated activated carbon with superb kinetics for the supercapacitor application in nonaqueous electrolyte. Colloids Surf a: Phys Eng Asp 443:535–539. https://doi.org/10.1016/j.colsurfa.2013.12.020
Khavryuchenko VD, Khavryuchenko OV, Tarasenko YA, Lisnyak VV (2008) Computer simulation of N-doped polyaromatic hydrocarbons clusters. Chem Phys 352:231–234. https://doi.org/10.1016/j.chemphys.2008.06.019
Khavryuchenko VD, Khavryuchenko OV, Shkilnyy AI et al (2009) by SEM, TEM and quantum-chemical simulations of the spherical carbon with nitrogen (SCN) active carbon produced by thermal decomposition of poly(vinylpyridine-divinylbenzene) copolymer. Materials 2:1239–1251. https://doi.org/10.3390/ma2031239
Khavryuchenko VD, Khavryuchenko OV, Lisnyak VV (2010a) High multiplicity states in disordered carbon systems: ab initio and semiempirical study. Chem Phys 368:83–86. https://doi.org/10.1016/j.chemphys.2009.12.022
Khavryuchenko VD, Tarasenko YA, Khavryuchenko OV et al (2010b) Nanostructurization in the SKS active carbon, by SEM, TEM, EDX and quantum-chemical simulations. Int J Modern Phys B 24:1449–1462. https://doi.org/10.1142/S0217979210055627
Khavryuchenko OV, Khavryuchenko VD, Lisnyak VV, Peslherbe GH (2011) A density-functional theory investigation of the electronic structure of the active carbon graphite-like and amorphous domains. Chem Phys Lett 513:261–266. https://doi.org/10.1016/j.cplett.2011.08.009
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
Kumaran SS, Lim KP, Michael JV, Wagner AF (1995) Thermal Decomposition of CF2Cl2. J Phys Chem 99:8673–8680. https://doi.org/10.1021/j100021a036
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
Liang C, Xie X, Shi Q, Feng J, Zhang D, Huang X (2022) Nitrogen/sulfur-doped dual-emission carbon dots with tunable fluorescence for ratiometric sensing of ferric ions and cell membrane imaging. Appl Surf Sci 572:151447. https://doi.org/10.1016/j.apsusc.2021.151447
Li B, Zhou L, Wu D, Peng H, Yan K, Zhou Y, Liu Z (2011) Photochemical chlorination of graphene. ACS Nano 5:5957–5961. https://doi.org/10.1021/nn201731t
Li Q, Wei H, Li H, Zhang Y, Hu Y (2019) Facile preparation and properties of porous carbon from chlorinated polymer with high chlorine content. Colloids Surf A Physicochem Eng Asp 579:123628. https://doi.org/10.1016/j.colsurfa.2019.123628
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
Miao S, Xu J, Tang D, Zhang W et al (2021) N, S dual doped mesoporous carbon supported Co9S8 nanoparticles as efficient hydrogen evolving electrocatalysts in a wide pH range. ChemistrySelect 6:9513–9516. https://doi.org/10.1002/slct.202102920
Mirhosseyni MS, Nemati F (2022) Metal-free aerobic oxidation of benzyl alcohols over the selective N, P dual-doped hollow carbon sphere as the efficient and sustainable heterogeneous catalyst under mild reaction condition. Micropor Mesopor Mater 329:111514. https://doi.org/10.1016/j.micromeso.2021.111514
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
Nagaraja SS, Sahu AB, Panigrahy S, Curran HJ (2021) A fundamental study on the pyrolysis of hydrocarbons. Combust Flame 233:111579. https://doi.org/10.1016/C2016-0-05137-9
Nakajima T, Groult H (2015) Advanced fluoride-based materials for energy conversion. Elsevier, Amsterdam. https://doi.org/10.1016/C2013-0-18650-3
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
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
Parmentier J, Schlienger S, Dubois M, Disa E, Masin F, Centeno TA (2012) Structural/textural properties and water reactivity of fluorinated activated carbons. Carbon 50:5135–5147. https://doi.org/10.1016/j.carbon.2012.06.054
Pełech I, Narkiewicz U, Moszyński D, Pełech R (2012) Simultaneous purification and functionalization of carbon nanotubes using chlorination. J Mater Res 27:2368–2374. https://doi.org/10.1557/jmr.2012.243
Pérez-Cadenas AF, Maldonado-Hódar FJ, Moreno-Castilla C (2003) On the nature of surface acid sites of chlorinated activated carbons. Carbon 41:473–478. https://doi.org/10.1016/S0008-6223(02)00353-6
Sakintuna B, Yürüm Y, Çetinkaya S (2004) Evolution of carbon microstructures during the pyrolysis of Turkish Elbistan Lignite in the temperature range 700–1000 °C. Energy Fuels 18:883–888. https://doi.org/10.1021/ef0301809
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
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
Shi J, Fang M, Qiao J, Liu Y (2014) Nitrogen and chlorine dual-doped mesoporous carbon as efficient non-precious electrocatalyst for oxygen reduction reaction both in alkaline and acidic electrolytes. Chem Lett 43:1484–1486. https://doi.org/10.1246/cl.140589
Sosa JE, Malheiro C, Ribeiro RP, Castro PJ, Piñeiro MM, Araújo JM, Plantier F, Mota JP, Pereiro AB (2020) Adsorption of fluorinated greenhouse gases on activated carbons: evaluation of their potential for gas separation. J Chem Technol Biotechnol 95:1892–1905. https://doi.org/10.1002/jctb.6371
Struzzi C, Scardamaglia M, Colomer JF, Verdini A et al (2017a) 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
Struzzi C, Scardamaglia M, Reckinger N, Sezen H et al (2017b) Probing plasma fluorinated graphene via spectromicroscopy. Phys Chem Chem Phys 19:31418–31428. https://doi.org/10.1039/C7CP05305C
Sugiyamaa H, Hattori Y (2020) Selective and enhanced CO2 adsorption on fluorinated activated carbon fibers. Chem Phys Lett 758:137909. https://doi.org/10.1016/j.cplett.2020.137909
Tiwari B, Joshi A, Munjal M, Kaur G et al (2022) Synergistic combination of N/P dual-doped activated carbon with redox-active electrolyte for high performance supercapacitors. J Phys Chem Solids 161:110449. https://doi.org/10.1016/j.jpcs.2021.110449
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
Tsapyuk GG, Diyuk VE, Mariychuk R et al (2020) Effect of ultrasonic treatment on the thermal oxidation of detonation nanodiamonds. Appl Nanosci 10:4991–5001. https://doi.org/10.1007/s13204-020-01277-2
Tsubouchi N, Mochizuki Y, Shinohara Y, Kawashima A, Ohtsuka Y (2019) Formation of surface chlorine species by low temperature reaction of HCl with metal-doped carbon. Fuel 246:51–59. https://doi.org/10.1016/j.fuel.2019.02.084
Uklein AV, Diyuk VE, Grischenko LM, Kozhanov VO, Boldyrieva OYu, Lisnyak VV, Multian VV, Gayvoronsky VYa (2016) Characterization of oxidized carbon materials with photoinduced absorption response. Appl Phys B 122:287. https://doi.org/10.1007/s00340-016-6561-2
Velasco LF, Kim KH, Lee Y-S, Lodewyckx P (2021) Influence of fluorine doping of activated carbon fibers on their water vapor adsorption characteristics. Front Chem 8:593756. https://doi.org/10.3389/fchem.2020.593756
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
Wan H, Shen X, Jiang H, Zhang C et al (2021) Biomass-derived N/S dual-doped porous hard-carbon as high-capacity anodes for lithium/sodium ions batteries. Energy 231:121102. https://doi.org/10.1016/j.energy.2021.121102
Wang T, Zang X, Wang X, Gu X, Shao Q, Cao N (2020) Recent advances in fluorine-doped/fluorinated carbon-based materials for supercapacitors. Energy Storage Mater 30:367–384. https://doi.org/10.1016/j.ensm.2020.05.003
Watanabe N, Nakajima T, Touhara H (2013) Graphite fluorides. Elsevier, Amsterdam
Yuan D, Huang L, Ding Y, Zhang L, Qian L, Zheng G (2020) Chlorine-doped carbon for electrocatalytic nitrogen reduction. Mol Catal 492:111029. https://doi.org/10.1016/j.mcat.2020.111029
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 (2018) Method for carbon materials surface modification by the fluorocarbons and derivatives. US Patent 10,000,382, June 19, 2018
Zaderko AN, Shvets RYa, Grygorchak II et al (2019) Fluoroalkylated nanoporous carbons: testing as a supercapacitor electrode. Appl Surf Sci 470:882–892. 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
Zhang X, Schiros T, Nordlund D, Shin YC, Kong J, Dresselhaus M, Palacios T (2015) X-ray spectroscopic investigation of chlorinated graphene: surface structure and electronic effects. Adv Funct Mater 25:4163–4169. https://doi.org/10.1002/adfm.201500541
Zhang X, Hsu A, Wang H, Song Y, Kong J, Dresselhaus MS, Palacios T (2013) Impact of chlorine functionalization on high-mobility chemical vapor deposition grown graphene. ACS Nano 7:7262–7270. https://doi.org/10.1021/nn4026756
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
Acknowledgements
This work has been supported by the Ministry of Education and Science of Ukraine: Grant of the Ministry of Education and Science of Ukraine for perspective development of a scientific direction "Mathematical sciences and natural sciences" at the Taras Shevchenko National University of Kyiv. S.A. acknowledges support by the Helmholtz Association (Program NACIP) and by the German Research Foundation (DFG) (Instrument Grant INST 121384/58-1).
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Diyuk, V.E., Zaderko, A.N., Grishchenko, L.M. et al. Preparation, texture and surface chemistry characterization of nanoporous-activated carbons co-doped with fluorine and chlorine. Appl Nanosci 12, 2103–2116 (2022). https://doi.org/10.1007/s13204-022-02459-w
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DOI: https://doi.org/10.1007/s13204-022-02459-w