Sandro Dattilo , Chiara Zagni , Tommaso Mecca , Vincenzo Patamia , Giuseppe Floresta , Pietro Nicotra , Sabrina C. Carroccio , Antonio Rescifina
{"title":"通过可持续大孔催化剂实现碳酸盐中二氧化碳的无溶剂转化","authors":"Sandro Dattilo , Chiara Zagni , Tommaso Mecca , Vincenzo Patamia , Giuseppe Floresta , Pietro Nicotra , Sabrina C. Carroccio , Antonio Rescifina","doi":"10.1016/j.giant.2024.100258","DOIUrl":null,"url":null,"abstract":"<div><p>The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO<sub>2</sub> capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (<sup>1</sup>H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br<sup>−</sup>, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO<sub>2</sub> capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":null,"pages":null},"PeriodicalIF":5.4000,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524000237/pdfft?md5=30a42f121cc921ad375eece1b4b67236&pid=1-s2.0-S2666542524000237-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Solvent-free conversion of CO2 in carbonates through a sustainable macroporous catalyst\",\"authors\":\"Sandro Dattilo , Chiara Zagni , Tommaso Mecca , Vincenzo Patamia , Giuseppe Floresta , Pietro Nicotra , Sabrina C. Carroccio , Antonio Rescifina\",\"doi\":\"10.1016/j.giant.2024.100258\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO<sub>2</sub> capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (<sup>1</sup>H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br<sup>−</sup>, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO<sub>2</sub> capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.</p></div>\",\"PeriodicalId\":34151,\"journal\":{\"name\":\"GIANT\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.4000,\"publicationDate\":\"2024-04-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2666542524000237/pdfft?md5=30a42f121cc921ad375eece1b4b67236&pid=1-s2.0-S2666542524000237-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"GIANT\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2666542524000237\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"GIANT","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2666542524000237","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Solvent-free conversion of CO2 in carbonates through a sustainable macroporous catalyst
The novelty of this work consists of synthesizing and exploiting a heterogeneous catalyst containing ammonium chloride as part of the polymeric sponge sites for CO2 capture. To this aim, the polymerization of 2-acryloyl(oxyethyl)trimethylammonium chloride was performed in cryo-condition, in the presence of a crosslinking agent, obtaining a lightweight macroporous freestanding material. Its efficiency in converting aromatic and aliphatic epoxides to the corresponding carbonates was successfully proved by using proton Nuclear Magnetic Resonance (1H NMR). Remarkably, the conversion of styrene oxide (SO) to styrene carbonate (SC) reached a yield of 99 % after 24 h of reaction. The calculated yield versus the aliphatic cyclohexene oxide is 71 %. Similar results were obtained by substituting the resin counter anion with Br−, although the conversion kinetic was slower than the chloride. It is worth noticing that reactions took place in the mixture without adding the tetrabutylammonium bromide (TBAB), typically used as a co-catalyst to convert epoxides into carbonates. The recyclability of the as-prepared catalyst was evaluated for four reaction cycles, evidencing stable properties without significant depletion of CO2 capture efficiency. Most importantly, the post-cleaning of the catalytic sponge is not required to be reused. Finally, the green chemistry metrics applied to the process demonstrated that our approach significantly mitigates risks and reduces environmental impact, thus elevating the overall cleanliness of our proof of concept.
期刊介绍:
Giant is an interdisciplinary title focusing on fundamental and applied macromolecular science spanning all chemistry, physics, biology, and materials aspects of the field in the broadest sense. Key areas covered include macromolecular chemistry, supramolecular assembly, multiscale and multifunctional materials, organic-inorganic hybrid materials, biophysics, biomimetics and surface science. Core topics range from developments in synthesis, characterisation and assembly towards creating uniformly sized precision macromolecules with tailored properties, to the design and assembly of nanostructured materials in multiple dimensions, and further to the study of smart or living designer materials with tuneable multiscale properties.