Pub Date : 2025-10-01DOI: 10.1016/j.jfluchem.2025.110483
Viktor G. Makotchenko , Alexander M. Panich , Ekaterina D. Grayfer
Fluorinated graphitic materials are widely studied for various applications including energy storage, lubricants, hydrophobic coatings, neutron reflectors, etc. Here, we investigate the F2 gas fluorination of three starting graphitic materials with different thicknesses: graphite, multi-layer graphene, and “graphene paper”. All synthesized products exhibit similar interplanar spacings, FTIR and XPS spectral characteristics, and similar compositions corresponding to graphite monofluoride CF1.12. However, the thickness of the starting compound affects the temperature required for the fluorination and the decomposition temperatures of the resulting fluorides. Fluorinated graphite CF1.12 prepared from graphite is stable up to 600 °C, while the stability drops dramatically for the fluorinated multi-layer graphene, which starts decomposing already at 100 °C. Besides, few-layer CF1.12 forms stable colloidal dispersions in organic media, unlike its thicker counterpart. The obtained results will facilitate structural engineering of fluorinated nanographite materials to optimize their properties for potential applications.
{"title":"Effect of graphene stack thickness on gaseous fluorination of graphitic materials","authors":"Viktor G. Makotchenko , Alexander M. Panich , Ekaterina D. Grayfer","doi":"10.1016/j.jfluchem.2025.110483","DOIUrl":"10.1016/j.jfluchem.2025.110483","url":null,"abstract":"<div><div>Fluorinated graphitic materials are widely studied for various applications including energy storage, lubricants, hydrophobic coatings, neutron reflectors, etc. Here, we investigate the F<sub>2</sub> gas fluorination of three starting graphitic materials with different thicknesses: graphite, multi-layer graphene, and “graphene paper”. All synthesized products exhibit similar interplanar spacings, FTIR and XPS spectral characteristics, and similar compositions corresponding to graphite monofluoride CF<sub>1.12</sub>. However, the thickness of the starting compound affects the temperature required for the fluorination and the decomposition temperatures of the resulting fluorides. Fluorinated graphite CF<sub>1.12</sub> prepared from graphite is stable up to 600 °C, while the stability drops dramatically for the fluorinated multi-layer graphene, which starts decomposing already at 100 °C. Besides, few-layer CF<sub>1.12</sub> forms stable colloidal dispersions in organic media, unlike its thicker counterpart. The obtained results will facilitate structural engineering of fluorinated nanographite materials to optimize their properties for potential applications.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110483"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262786","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01DOI: 10.1016/j.jfluchem.2025.110484
Olena Voloshyna , Bohdan Moroz , Kostiantyn P. Melnykov , Serhii Holovach , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Andrey A. Filatov , Oleksandr O. Grygorenko
An expedient gram-scale synthesis of stereochemically pure exo- and endo-5,5-difluorooctahydropentalen-2-amines – valuable building blocks for medicinal chemistry – is described. The method commenced from the commercially available Weiss diketone. The compound’s stereochemistry was controlled using diastereoselective NaBH4-mediated reduction and Mitsunobu reaction at the corresponding steps. To install the gem‑difluorinated moiety, classical DAST-mediated deoxofluorination was employed. Physicochemical properties of the synthesized compounds (pKa and LogP) demonstrated their potential for applications in drug discovery as cyclohexane replacements.
{"title":"Gram-scale synthesis and physicochemical properties of exo- and endo-5,5-difluorooctahydropentalen-2-amines","authors":"Olena Voloshyna , Bohdan Moroz , Kostiantyn P. Melnykov , Serhii Holovach , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Andrey A. Filatov , Oleksandr O. Grygorenko","doi":"10.1016/j.jfluchem.2025.110484","DOIUrl":"10.1016/j.jfluchem.2025.110484","url":null,"abstract":"<div><div>An expedient gram-scale synthesis of stereochemically pure exo- and endo-5,5-difluorooctahydropentalen-2-amines – valuable building blocks for medicinal chemistry – is described. The method commenced from the commercially available Weiss diketone. The compound’s stereochemistry was controlled using diastereoselective NaBH<sub>4</sub>-mediated reduction and Mitsunobu reaction at the corresponding steps. To install the gem‑difluorinated moiety, classical DAST-mediated deoxofluorination was employed. Physicochemical properties of the synthesized compounds (pK<sub>a</sub> and LogP) demonstrated their potential for applications in drug discovery as cyclohexane replacements.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110484"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01DOI: 10.1016/j.jfluchem.2025.110480
Mohammad Rizehbandi, Behzad Khalili, Khatereh Ghauri
This study used density functional theory (DFT) calculations to investigate the properties of four novel dianionic ionic liquids (DAILs) named as [PMIM]2[TFTP], [PMTA1]2[TFTP], [PMTA2]2[TFTP] and [PMTTA]2[TFTP]. These DAILs consist of a tetrafluoro terephthalate ([TFTP]2-) dianion and various functionalized imidazolium, triazolium and tetrazolium-based cations allowing for an analysis of how cation structure (specifically nitrogen atom number and position) and fluorination affect the DAILs' stability, electronic properties, and electrochemical behavior. The research evaluated energetic, electronic, and thermodynamic parameters, as well as electrostatic potential maps and topological properties, to understand the relationship between DAIL structure and its characteristics. The fluorinated dianion showed a planar preference for interaction with the cation's five-membered rings. Importantly, hydrogen bonding, in conjunction with electrostatic interactions, significantly contributes to the stability of these DAILs and will likely influence their physicochemical properties and suitability for specific applications. The interaction energies for the most stable configurations of the examined DAILs vary between -235.82 and -269.36 kcal mol-1 at M06–2X-GD3/AUG-cc-pVDZ theory level and following a decreasing trend in the order of: [PMIM]2[TFTP] < [PMTA1]2[TFTP] < [PMTA2]2[TFTP] < [PMTTA]2[TFTP]. Additionally, the HOMO–LUMO energy gaps, spanning from 6.49 to 7.38 eV, highlighted notable stability trends in the series. Charge transfer values obtained through NBO analysis were observed between 0.2318 and 0.7307 a.u., reaffirming the contributions of hydrogen bonding.
{"title":"A density functional theory approach for design of fluorine-containing dianionic ionic liquids and investigation of some of their physical and chemical properties","authors":"Mohammad Rizehbandi, Behzad Khalili, Khatereh Ghauri","doi":"10.1016/j.jfluchem.2025.110480","DOIUrl":"10.1016/j.jfluchem.2025.110480","url":null,"abstract":"<div><div>This study used density functional theory (DFT) calculations to investigate the properties of four novel dianionic ionic liquids (DAILs) named as [PMIM]<sub>2</sub>[TFTP], [PMTA1]<sub>2</sub>[TFTP], [PMTA2]<sub>2</sub>[TFTP] and [PMTTA]<sub>2</sub>[TFTP]. These DAILs consist of a tetrafluoro terephthalate ([TFTP]<sup>2-</sup>) dianion and various functionalized imidazolium, triazolium and tetrazolium-based cations allowing for an analysis of how cation structure (specifically nitrogen atom number and position) and fluorination affect the DAILs' stability, electronic properties, and electrochemical behavior. The research evaluated energetic, electronic, and thermodynamic parameters, as well as electrostatic potential maps and topological properties, to understand the relationship between DAIL structure and its characteristics. The fluorinated dianion showed a planar preference for interaction with the cation's five-membered rings. Importantly, hydrogen bonding, in conjunction with electrostatic interactions, significantly contributes to the stability of these DAILs and will likely influence their physicochemical properties and suitability for specific applications. The interaction energies for the most stable configurations of the examined DAILs vary between -235.82 and -269.36 kcal mol<sup>-1</sup> at M06–2X-GD3/AUG-cc-pVDZ theory level and following a decreasing trend in the order of: [PMIM]<sub>2</sub>[TFTP] < [PMTA1]<sub>2</sub>[TFTP] < [PMTA2]<sub>2</sub>[TFTP] < [PMTTA]<sub>2</sub>[TFTP]. Additionally, the HOMO–LUMO energy gaps, spanning from 6.49 to 7.38 eV, highlighted notable stability trends in the series. Charge transfer values obtained through NBO analysis were observed between 0.2318 and 0.7307 a.u., reaffirming the contributions of hydrogen bonding.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110480"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145216482","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01DOI: 10.1016/j.jfluchem.2025.110487
Craig Sommer, Dakota L. Leenstra, Ryan Fjordbotten, Douglas Turnbull, Stacey D. Wetmore, Michael Gerken
Lewis acid-base adducts of MOF4 (M = Mo or W) with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) were synthesized from their parent CH3CN adducts and the bases as insoluble off-white or yellow (MoOF4(bipy)) powders. Additionally, the adduct between WOF4 and 4,4′-di‑tert‑butyl‑2,2′-bipyridine (dtbipy) was synthesized in the same manner. The adducts were characterized by Raman and infrared spectroscopy and the vibrational assignment was aided by DFT calculations. DFT geometry optimizations of the adducts predict pentagonal bipyramidal structures with the bidentate bases coordinating in the equatorial plane. NBO analyses of the adducts were done to better understand the bonding as well as the stability of the heptacoordinated adducts.
{"title":"Syntheses, characterization, and computational study of heptacoordinate adducts of WOF4 and MoOF4","authors":"Craig Sommer, Dakota L. Leenstra, Ryan Fjordbotten, Douglas Turnbull, Stacey D. Wetmore, Michael Gerken","doi":"10.1016/j.jfluchem.2025.110487","DOIUrl":"10.1016/j.jfluchem.2025.110487","url":null,"abstract":"<div><div>Lewis acid-base adducts of MOF<sub>4</sub> (M = Mo or W) with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) were synthesized from their parent CH<sub>3</sub>CN adducts and the bases as insoluble off-white or yellow (MoOF<sub>4</sub>(bipy)) powders. Additionally, the adduct between WOF<sub>4</sub> and 4,4′-di‑tert‑butyl‑2,2′-bipyridine (dtbipy) was synthesized in the same manner. The adducts were characterized by Raman and infrared spectroscopy and the vibrational assignment was aided by DFT calculations. DFT geometry optimizations of the adducts predict pentagonal bipyramidal structures with the bidentate bases coordinating in the equatorial plane. NBO analyses of the adducts were done to better understand the bonding as well as the stability of the heptacoordinated adducts.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110487"},"PeriodicalIF":1.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145332617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-18DOI: 10.1016/j.jfluchem.2025.110477
Mannab Yu. Tashmetov , Normamat B. Ismatov , Shermakhmat M. Makhkamov , Sadulla.R. Allayarov , Matthew P. Confer , David A. Dixon
The effect of γ-irradiation on the post-irradiation thermoluminescent and photoluminescent properties of an industrial ethylene-tetrafluoroethylene (ETFE) copolymer was investigated. The radiothermoluminescence (RTL) curve in the temperature range of 77 to 400 K exhibits three maxima: the most intense peak occurs at 116 K, while two additional maxima appear as shoulders at 168 K and 210 K. These maxima result from the formation and subsequent quenching of electronically excited states caused by the recombination of charge carriers accumulated during γ-irradiation of the copolymer at 77 K. Photoluminescence arises from the radiative recombination of excitons formed in the copolymer upon photoexcitation with a xenon lamp at 300 K. The photoluminescence maximum occurs at 340 nm, and its intensity decreases as the γ-irradiation dose increases. Structural defects and macromolecular cross-linking induced by γ-irradiation act as centers of nonradiative exciton recombination, thereby reducing the intensity of the post-irradiation luminescence of the copolymer. Electronic structure predictions of the degradation thermodynamics indicate that polymer backbone degradation through either loss of small unsaturated molecules or carbenes is unfavorable at room temperature but is possible under γ-irradiation conditions.
{"title":"Post-Irradiation photoluminescence and thermoluminescence of the ethylene-tetrafluoroethylene copolymer","authors":"Mannab Yu. Tashmetov , Normamat B. Ismatov , Shermakhmat M. Makhkamov , Sadulla.R. Allayarov , Matthew P. Confer , David A. Dixon","doi":"10.1016/j.jfluchem.2025.110477","DOIUrl":"10.1016/j.jfluchem.2025.110477","url":null,"abstract":"<div><div>The effect of γ-irradiation on the post-irradiation thermoluminescent and photoluminescent properties of an industrial ethylene-tetrafluoroethylene (ETFE) copolymer was investigated. The radiothermoluminescence (RTL) curve in the temperature range of 77 to 400 K exhibits three maxima: the most intense peak occurs at 116 K, while two additional maxima appear as shoulders at 168 K and 210 K. These maxima result from the formation and subsequent quenching of electronically excited states caused by the recombination of charge carriers accumulated during γ-irradiation of the copolymer at 77 K. Photoluminescence arises from the radiative recombination of excitons formed in the copolymer upon photoexcitation with a xenon lamp at 300 K. The photoluminescence maximum occurs at 340 nm, and its intensity decreases as the γ-irradiation dose increases. Structural defects and macromolecular cross-linking induced by γ-irradiation act as centers of nonradiative exciton recombination, thereby reducing the intensity of the post-irradiation luminescence of the copolymer. Electronic structure predictions of the degradation thermodynamics indicate that polymer backbone degradation through either loss of small unsaturated molecules or carbenes is unfavorable at room temperature but is possible under γ-irradiation conditions.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110477"},"PeriodicalIF":1.9,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-18DOI: 10.1016/j.jfluchem.2025.110479
Olga A. Zhupikova, Vyacheslav I. Krasnov, Olga I. Yarovaya, Andrey A. Nefedov, Vadim V. Bardin, Yuri V. Gatilov, Artem D. Rogachev, Nariman F. Salakhutdinov, Mikhail V. Khvostov
In this work, the Selectfluor-mediated transformation of cedrol and cedrene under the Ritter reaction conditions is presented for the first time. The possibility of the formation of acetamides, including fluorine-containing compounds, is shown. In the absence of Selectfluor, no amides are formed from cedrol under the conditions of the classical Ritter reaction and the only reaction product is cedrene.
{"title":"Selectfluor-mediated transformation of cedrol and cedrene under the Ritter reaction conditions","authors":"Olga A. Zhupikova, Vyacheslav I. Krasnov, Olga I. Yarovaya, Andrey A. Nefedov, Vadim V. Bardin, Yuri V. Gatilov, Artem D. Rogachev, Nariman F. Salakhutdinov, Mikhail V. Khvostov","doi":"10.1016/j.jfluchem.2025.110479","DOIUrl":"10.1016/j.jfluchem.2025.110479","url":null,"abstract":"<div><div>In this work, the Selectfluor-mediated transformation of cedrol and cedrene under the Ritter reaction conditions is presented for the first time. The possibility of the formation of acetamides, including fluorine-containing compounds, is shown. In the absence of Selectfluor, no amides are formed from cedrol under the conditions of the classical Ritter reaction and the only reaction product is cedrene.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110479"},"PeriodicalIF":1.9,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Trans-1,2-difluoroethylene (R-1132(E)) is expected as a next-generation refrigerant component because of its ultra-low global warming potential (GWP) compared to previous refrigerants. However, R-1132(E) is unstable and self-decomposed in the presence of an ignition source similar to tetrafluoroethylene (TFE) and trifluoroethylene (HFO-1123). In this reseach, the self-decomposition of R-1132(E) and its mixture was investigated by spark generator to elucidate the self-decomposition limit conditions in terms of initial gas pressure (p0) and spark discharge energy (Ed). It was found that the Ed for self-decomposition of R-1132(E) and its mixture depends on the p0 and there is the relationship of Ed ∝ 1/p02. The self-decomposition boundary (SDB) in Ed was increased with increasing discharge duration. The study of SDB in p0 for R-1132(E) mixed with 2,3,3,3-tetrafluoropropene (R-1234yf) indicated the relationship of R-1132(E) density ∝ R-1234yf density. From the above two relationships it was possible to predict SDB in p0 for any Ed.
{"title":"Evaluation of self-decomposition of trans-1,2-difluoroethylene by spark ignition","authors":"Takashi Usui , Tomoyuki Goto , Takashi Yoshimura , Yasufu Yamada , Kaito Santa , Yasuhiro Oshime , Kenji Takizawa , Takaaki Mizutani","doi":"10.1016/j.jfluchem.2025.110463","DOIUrl":"10.1016/j.jfluchem.2025.110463","url":null,"abstract":"<div><div>Trans-1,2-difluoroethylene (R-1132(E)) is expected as a next-generation refrigerant component because of its ultra-low global warming potential (GWP) compared to previous refrigerants. However, R-1132(E) is unstable and self-decomposed in the presence of an ignition source similar to tetrafluoroethylene (TFE) and trifluoroethylene (HFO-1123). In this reseach, the self-decomposition of R-1132(E) and its mixture was investigated by spark generator to elucidate the self-decomposition limit conditions in terms of initial gas pressure (<em>p</em><sub>0</sub>) and spark discharge energy (<em>E</em><sub>d</sub>). It was found that the <em>E</em><sub>d</sub> for self-decomposition of R-1132(E) and its mixture depends on the <em>p</em><sub>0</sub> and there is the relationship of <em>E</em><sub>d</sub> ∝ 1/<em>p</em><sub>0</sub><sup>2</sup>. The self-decomposition boundary (SDB) in <em>E</em><sub>d</sub> was increased with increasing discharge duration. The study of SDB in <em>p</em><sub>0</sub> for R-1132(E) mixed with 2,3,3,3-tetrafluoropropene (R-1234yf) indicated the relationship of R-1132(E) density ∝ R-1234yf density. From the above two relationships it was possible to predict SDB in <em>p</em><sub>0</sub> for any <em>E</em><sub>d</sub>.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110463"},"PeriodicalIF":1.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145027549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-10DOI: 10.1016/j.jfluchem.2025.110478
J.H. Kim, C.H. Cho, I.J. Kang, J.K. Yang, H. Choi
Nitrogen trifluoride (NF3), with a global warming potential (GWP) of 16,100, is increasingly being used in the manufacturing of flat-panel displays, photovoltaics, light-emitting diodes (LEDs), and other microelectronics and semiconductors, and efficient processes for its removal using less energy to increase productivity are being developed. In this study, an optimal process was developed by comparing the processes of injecting oxygen and steam as the oxidising agents to increase the decomposition rate of NF3 using a microwave plasma torch. Using a microwave plasma torch, 1000 J/L of energy was saved compared to the previous method of applying the gas treatment flow rate of a commercially available scrubber (nitrogen: 250 L/min, NF3:5000 ppm). In the optimal process, steam (6 and 10 g/min) was used as the oxidising agent, 1000 J/L of energy was consumed, and at least 5 kW of plasma power was used. Under these conditions, destruction and removal efficiencies (DREs) of > 99 % were achieved. For theoretical verification, chemical reaction rates of NF3 with oxygen and steam were calculated and compared with the experimental results. The comparison showed that the chemical reaction rate of steam was higher than that of oxygen, and the experiment confirmed that when steam was used as an oxidising agent, NF3 could be decomposed using less energy than that of oxygen.
{"title":"Experimental and theoretical studies for optimization of NF3 removal from semiconductor processes using microwave plasma torch","authors":"J.H. Kim, C.H. Cho, I.J. Kang, J.K. Yang, H. Choi","doi":"10.1016/j.jfluchem.2025.110478","DOIUrl":"10.1016/j.jfluchem.2025.110478","url":null,"abstract":"<div><div>Nitrogen trifluoride (NF<sub>3</sub>), with a global warming potential (GWP) of 16,100, is increasingly being used in the manufacturing of flat-panel displays, photovoltaics, light-emitting diodes (LEDs), and other microelectronics and semiconductors, and efficient processes for its removal using less energy to increase productivity are being developed. In this study, an optimal process was developed by comparing the processes of injecting oxygen and steam as the oxidising agents to increase the decomposition rate of NF<sub>3</sub> using a microwave plasma torch. Using a microwave plasma torch, 1000 J/L of energy was saved compared to the previous method of applying the gas treatment flow rate of a commercially available scrubber (nitrogen: 250 L/min, NF<sub>3</sub>:5000 ppm). In the optimal process, steam (6 and 10 g/min) was used as the oxidising agent, 1000 J/L of energy was consumed, and at least 5 kW of plasma power was used. Under these conditions, destruction and removal efficiencies (DREs) of > 99 % were achieved. For theoretical verification, chemical reaction rates of NF<sub>3</sub> with oxygen and steam were calculated and compared with the experimental results. The comparison showed that the chemical reaction rate of steam was higher than that of oxygen, and the experiment confirmed that when steam was used as an oxidising agent, NF<sub>3</sub> could be decomposed using less energy than that of oxygen.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110478"},"PeriodicalIF":1.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-04DOI: 10.1016/j.jfluchem.2025.110476
Jingjing Liu , Runlong Yang , Yang Li , Benli Liu , Ming Yang , Shuangshuang Tian
Perfluorohexanone (C6F12O) has been widely used in fire suppression systems for energy storage battery. However, toxic gases such as CO, CO2, HF, and COF2 produced during extinguishing process pose significant risks to human health and equipment safety, making it essential to monitor them. Recent studies show that metal-doped Transition Metal Dichalcogenides (TMDs) exhibit excellent gas adsorption properties, demonstrating great potential in gas sensing applications. To further explore this potential, Pd doped MoTe2 is selected in this paper, for which the doping process is simulated and the adsorption properties are systematically investigated. These configurations are analyzed using the Electron Localization Function (ELF), the Independent Gradient Model based on Hirshfeld partition (IGMH), and the Density of States (DOS). Finally, the gas sensing capabilities of Pd-MoTe2 are comprehensively evaluated to investigate its viability as a sensing material. The results reveal that Pd-MoTe2 exhibits strong adsorption for CO and COF2, with adsorption energies of -1.866 eV and -0.935 eV, respectively. Furthermore, the IGMH and ELF analyses confirm the existence of chemical bonding between the CO, COF2, and the Pd atoms. The DOS study further verifies the phenomenon of orbital hybridization. Additionally, the recovery time of Pd-MoTe2 requires high temperatures to release CO, but it is ideal for COF2, making it suitable for the adsorption of CO and the detection of COF₂. The results of this research can provide a theoretical foundation and data support for the application of Pd-MoTe2.
{"title":"First-principles study of the adsorption performance of Pd-MoTe2 on decomposition products of perfluorohexanone fire extinguishing agents","authors":"Jingjing Liu , Runlong Yang , Yang Li , Benli Liu , Ming Yang , Shuangshuang Tian","doi":"10.1016/j.jfluchem.2025.110476","DOIUrl":"10.1016/j.jfluchem.2025.110476","url":null,"abstract":"<div><div>Perfluorohexanone (C<sub>6</sub>F<sub>12</sub>O) has been widely used in fire suppression systems for energy storage battery. However, toxic gases such as CO, CO<sub>2</sub>, HF, and COF<sub>2</sub> produced during extinguishing process pose significant risks to human health and equipment safety, making it essential to monitor them. Recent studies show that metal-doped Transition Metal Dichalcogenides (TMDs) exhibit excellent gas adsorption properties, demonstrating great potential in gas sensing applications. To further explore this potential, Pd doped MoTe<sub>2</sub> is selected in this paper, for which the doping process is simulated and the adsorption properties are systematically investigated. These configurations are analyzed using the Electron Localization Function (ELF), the Independent Gradient Model based on Hirshfeld partition (IGMH), and the Density of States (DOS). Finally, the gas sensing capabilities of Pd-MoTe<sub>2</sub> are comprehensively evaluated to investigate its viability as a sensing material. The results reveal that Pd-MoTe<sub>2</sub> exhibits strong adsorption for CO and COF<sub>2</sub>, with adsorption energies of -1.866 eV and -0.935 eV, respectively. Furthermore, the IGMH and ELF analyses confirm the existence of chemical bonding between the CO, COF<sub>2</sub>, and the Pd atoms. The DOS study further verifies the phenomenon of orbital hybridization. Additionally, the recovery time of Pd-MoTe<sub>2</sub> requires high temperatures to release CO, but it is ideal for COF<sub>2</sub>, making it suitable for the adsorption of CO and the detection of COF₂. The results of this research can provide a theoretical foundation and data support for the application of Pd-MoTe<sub>2</sub>.</div></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"287 ","pages":"Article 110476"},"PeriodicalIF":1.9,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145010586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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