Yiwei Tang, Hui Shao, Yingzhou Lu, Hong Meng, Hongwei Fan and Chunxi Li
{"title":"通过与 AlCl3† 发生机械化学反应,将氟仿转化为 CHCl3 和 AlClxF3-x","authors":"Yiwei Tang, Hui Shao, Yingzhou Lu, Hong Meng, Hongwei Fan and Chunxi Li","doi":"10.1039/D4GC02101K","DOIUrl":null,"url":null,"abstract":"<p >Fluoroform (CHF<small><sub>3</sub></small>) is a byproduct of CHF<small><sub>2</sub></small>Cl with high global warming potential and long atmospheric lifetime, and its efficient utilization is a great challenge. The mechanochemical reaction between CHF<small><sub>3</sub></small> and AlCl<small><sub>3</sub></small> was studied for the first time, and the resultant ACFs (AlCl<small><sub><em>x</em></sub></small>F<small><sub>3−<em>x</em></sub></small>, <em>x</em> ≈ 0.1) were characterized by ion chromatography, X-ray photoelectron spectroscopy and X-ray diffraction. The reaction mechanism is revealed <em>via</em> experiments and DFT calculation. Here, the reactivity of AlCl<small><sub>3</sub></small> is slightly higher than that of AlCl<small><sub>2</sub></small>F and AlClF<small><sub>2</sub></small>, while the reactivity of CHF<small><sub>2</sub></small>Cl and CHFCl<small><sub>2</sub></small> is 2 to 6 orders of magnitude higher than that of CHF<small><sub>3</sub></small>. The reaction is self-accelerated until CHF<small><sub>3</sub></small> is fully converted to CHCl<small><sub>3</sub></small> and ACFs with controllable F-content. The present work provides a viable approach to convert CHF<small><sub>3</sub></small> to CHCl<small><sub>3</sub></small> and ACFs at ambient temperature and pressure, which is superior to the mainstream incineration technique with great energy demand and environmental pollution, and sacrifice of the precious F-resource.</p>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3000,"publicationDate":"2024-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Conversion of fluoroform to CHCl3 and AlClxF3−xvia its mechanochemical reaction with AlCl3†\",\"authors\":\"Yiwei Tang, Hui Shao, Yingzhou Lu, Hong Meng, Hongwei Fan and Chunxi Li\",\"doi\":\"10.1039/D4GC02101K\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Fluoroform (CHF<small><sub>3</sub></small>) is a byproduct of CHF<small><sub>2</sub></small>Cl with high global warming potential and long atmospheric lifetime, and its efficient utilization is a great challenge. The mechanochemical reaction between CHF<small><sub>3</sub></small> and AlCl<small><sub>3</sub></small> was studied for the first time, and the resultant ACFs (AlCl<small><sub><em>x</em></sub></small>F<small><sub>3−<em>x</em></sub></small>, <em>x</em> ≈ 0.1) were characterized by ion chromatography, X-ray photoelectron spectroscopy and X-ray diffraction. The reaction mechanism is revealed <em>via</em> experiments and DFT calculation. Here, the reactivity of AlCl<small><sub>3</sub></small> is slightly higher than that of AlCl<small><sub>2</sub></small>F and AlClF<small><sub>2</sub></small>, while the reactivity of CHF<small><sub>2</sub></small>Cl and CHFCl<small><sub>2</sub></small> is 2 to 6 orders of magnitude higher than that of CHF<small><sub>3</sub></small>. The reaction is self-accelerated until CHF<small><sub>3</sub></small> is fully converted to CHCl<small><sub>3</sub></small> and ACFs with controllable F-content. The present work provides a viable approach to convert CHF<small><sub>3</sub></small> to CHCl<small><sub>3</sub></small> and ACFs at ambient temperature and pressure, which is superior to the mainstream incineration technique with great energy demand and environmental pollution, and sacrifice of the precious F-resource.</p>\",\"PeriodicalId\":78,\"journal\":{\"name\":\"Green Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.3000,\"publicationDate\":\"2024-06-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Green Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/gc/d4gc02101k\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/gc/d4gc02101k","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Conversion of fluoroform to CHCl3 and AlClxF3−xvia its mechanochemical reaction with AlCl3†
Fluoroform (CHF3) is a byproduct of CHF2Cl with high global warming potential and long atmospheric lifetime, and its efficient utilization is a great challenge. The mechanochemical reaction between CHF3 and AlCl3 was studied for the first time, and the resultant ACFs (AlClxF3−x, x ≈ 0.1) were characterized by ion chromatography, X-ray photoelectron spectroscopy and X-ray diffraction. The reaction mechanism is revealed via experiments and DFT calculation. Here, the reactivity of AlCl3 is slightly higher than that of AlCl2F and AlClF2, while the reactivity of CHF2Cl and CHFCl2 is 2 to 6 orders of magnitude higher than that of CHF3. The reaction is self-accelerated until CHF3 is fully converted to CHCl3 and ACFs with controllable F-content. The present work provides a viable approach to convert CHF3 to CHCl3 and ACFs at ambient temperature and pressure, which is superior to the mainstream incineration technique with great energy demand and environmental pollution, and sacrifice of the precious F-resource.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.