Xiaomin Zhang , Mo Zhou , Yujia Zhao , Jifeng Pang , Pengfei Wu , Zhen Guo , Mingyuan Zheng
{"title":"稳定Cu-Zr /介孔SiO2催化剂上乙醇脱氢胺化选择性生产乙腈的研究","authors":"Xiaomin Zhang , Mo Zhou , Yujia Zhao , Jifeng Pang , Pengfei Wu , Zhen Guo , Mingyuan Zheng","doi":"10.1039/d5gc01047k","DOIUrl":null,"url":null,"abstract":"<div><div>Production of acetonitrile from ethanol <em>via</em> the non-oxidative dehydroamination process provides an attractive route for converting biomass-derived substrates into high-value chemical compounds. Conventional copper-based catalysts exhibit excellent activity and product selectivity at low-temperatures (≤330 °C), but they suffer from the challenge of deactivation. Herein, a binary Cu<sub>10</sub>–Zr<sub>2</sub>/meso SiO<sub>2</sub>-UP catalyst was prepared <em>via</em> a facile urea-assisted precipitation method for ethanol dehydroamination to acetonitrile. Under the optimal reaction condition (265 °C, ethanol WHSV of 0.8 h<sup>−1</sup> and NH<sub>3</sub>/ethanol molar ratio of 9), 95% product selectivity for acetonitrile with over 90% ethanol conversion was realized and maintained for more than 116 h, which was 48-fold longer than that of the conventional counterpart. According to the systematic characterizations, the introduction of Zr exhibited multifunctionality by (1) enhancing the copper species dispersion, (2) preventing the Cu nanoparticle from sintering, (3) adjusting the Cu<sup>+</sup>/Cu<sup>0</sup> ratio, (4) modifying the acidity, and (5) regulating the adsorption–desorption behavior of the organics. The apparent activation energy (<em>Ea</em>) for ethanol conversion dropped by 22.3 kJ mol<sup>−1</sup>, from 69.3 kJ mol<sup>−1</sup> over the conventional monometallic catalyst to 47.0 kJ mol<sup>−1</sup> over the as-prepared Cu–Zr binary catalyst. Notably, the catalyst demonstrated excellent substrate compatibility in transforming a series of aliphatic alcohols and benzyl alcohol into the corresponding nitriles with over 85% yields.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 20","pages":"Pages 5795-5809"},"PeriodicalIF":9.2000,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Selective production of acetonitrile via dehydroamination of ethanol over a stable Cu–Zr/meso SiO2 catalyst†\",\"authors\":\"Xiaomin Zhang , Mo Zhou , Yujia Zhao , Jifeng Pang , Pengfei Wu , Zhen Guo , Mingyuan Zheng\",\"doi\":\"10.1039/d5gc01047k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Production of acetonitrile from ethanol <em>via</em> the non-oxidative dehydroamination process provides an attractive route for converting biomass-derived substrates into high-value chemical compounds. Conventional copper-based catalysts exhibit excellent activity and product selectivity at low-temperatures (≤330 °C), but they suffer from the challenge of deactivation. Herein, a binary Cu<sub>10</sub>–Zr<sub>2</sub>/meso SiO<sub>2</sub>-UP catalyst was prepared <em>via</em> a facile urea-assisted precipitation method for ethanol dehydroamination to acetonitrile. Under the optimal reaction condition (265 °C, ethanol WHSV of 0.8 h<sup>−1</sup> and NH<sub>3</sub>/ethanol molar ratio of 9), 95% product selectivity for acetonitrile with over 90% ethanol conversion was realized and maintained for more than 116 h, which was 48-fold longer than that of the conventional counterpart. According to the systematic characterizations, the introduction of Zr exhibited multifunctionality by (1) enhancing the copper species dispersion, (2) preventing the Cu nanoparticle from sintering, (3) adjusting the Cu<sup>+</sup>/Cu<sup>0</sup> ratio, (4) modifying the acidity, and (5) regulating the adsorption–desorption behavior of the organics. The apparent activation energy (<em>Ea</em>) for ethanol conversion dropped by 22.3 kJ mol<sup>−1</sup>, from 69.3 kJ mol<sup>−1</sup> over the conventional monometallic catalyst to 47.0 kJ mol<sup>−1</sup> over the as-prepared Cu–Zr binary catalyst. Notably, the catalyst demonstrated excellent substrate compatibility in transforming a series of aliphatic alcohols and benzyl alcohol into the corresponding nitriles with over 85% yields.</div></div>\",\"PeriodicalId\":78,\"journal\":{\"name\":\"Green Chemistry\",\"volume\":\"27 20\",\"pages\":\"Pages 5795-5809\"},\"PeriodicalIF\":9.2000,\"publicationDate\":\"2025-04-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Green Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1463926225003279\",\"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://www.sciencedirect.com/org/science/article/pii/S1463926225003279","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Selective production of acetonitrile via dehydroamination of ethanol over a stable Cu–Zr/meso SiO2 catalyst†
Production of acetonitrile from ethanol via the non-oxidative dehydroamination process provides an attractive route for converting biomass-derived substrates into high-value chemical compounds. Conventional copper-based catalysts exhibit excellent activity and product selectivity at low-temperatures (≤330 °C), but they suffer from the challenge of deactivation. Herein, a binary Cu10–Zr2/meso SiO2-UP catalyst was prepared via a facile urea-assisted precipitation method for ethanol dehydroamination to acetonitrile. Under the optimal reaction condition (265 °C, ethanol WHSV of 0.8 h−1 and NH3/ethanol molar ratio of 9), 95% product selectivity for acetonitrile with over 90% ethanol conversion was realized and maintained for more than 116 h, which was 48-fold longer than that of the conventional counterpart. According to the systematic characterizations, the introduction of Zr exhibited multifunctionality by (1) enhancing the copper species dispersion, (2) preventing the Cu nanoparticle from sintering, (3) adjusting the Cu+/Cu0 ratio, (4) modifying the acidity, and (5) regulating the adsorption–desorption behavior of the organics. The apparent activation energy (Ea) for ethanol conversion dropped by 22.3 kJ mol−1, from 69.3 kJ mol−1 over the conventional monometallic catalyst to 47.0 kJ mol−1 over the as-prepared Cu–Zr binary catalyst. Notably, the catalyst demonstrated excellent substrate compatibility in transforming a series of aliphatic alcohols and benzyl alcohol into the corresponding nitriles with over 85% yields.
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.