{"title":"在衍生自氢化talcite的铜钴铝催化剂上将γ-戊内酯选择性氢化为 1,4-戊二醇","authors":"Jiebang Peng , Donghong Zhang , Xin Tian , Mingyue Ding","doi":"10.1016/j.fuproc.2024.108068","DOIUrl":null,"url":null,"abstract":"<div><p>In this study, a series of CuCoAl catalysts with different Cu/Co molar ratios were prepared from hydrotalcite-like precursors and then adopted for <em>γ</em>-valerolactone (GVL) hydrogenation to 1,4-pentanediol (1,4-PeD). By tuning the Cu/Co ratio in the CuCoAl catalysts and optimizing the reaction conditions, nearly 100% yield of 1,4-PeD was finally achieved with the Cu<sub>0.2</sub>Co<sub>0.8</sub>Al catalyst (Cu/Co = 1: 4) at 433 K and 4 MPa H<sub>2</sub>. The high activity of the Cu<sub>0.2</sub>Co<sub>0.8</sub>Al catalyst was attributed to the existence of Cu-CoO<sub>x</sub> synergistic active sites and the abundant surface acidity. The electron transfer from Cu to Co resulted in the formation oxygen-defected CoO<sub>x</sub> sites and surface acidic sites, which were beneficial for the adsorption of GVL and the activation of C-O/C=O bonds. The proximity between Cu particles and defective CoO<sub>x</sub> facilitated the dissociative adsorption of H<sub>2</sub> on Cu<sup>0</sup> and the subsequent hydrogen spillover to CoO<sub>x</sub> sites, thereby significantly promoted the selective hydrogenation of GVL to 1,4-PeD. In addition, applications of the Cu<sub>0.2</sub>Co<sub>0.8</sub>Al catalyst to the ring-opening reactions of other lactones (including α-adamyllactone, γ-caprolactone, δ-pentyllactone, and ε-caprolactone) were further investigated. Eventually, high yields (> 93%) of the corresponding diols were attained, demonstrating the excellent catalytic versatility of Cu<sub>0.2</sub>Co<sub>0.8</sub>Al in selective hydrogenation of lactones. Overall, this work shows high potential of hydrotalcite-derived CuCoAl catalysts for selective hydrogenation of GVL to 1,4-PeD, and provides insights for the design of efficient bimetallic catalysts in lactone hydrogenolysis.</p></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"256 ","pages":"Article 108068"},"PeriodicalIF":7.2000,"publicationDate":"2024-02-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0378382024000389/pdfft?md5=52126577db00b0d8ee7cd76baaf8fb95&pid=1-s2.0-S0378382024000389-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Selective hydrogenation of γ-valerolactone to 1,4-pentanediol over hydrotalcite-derived CuCoAl catalysts\",\"authors\":\"Jiebang Peng , Donghong Zhang , Xin Tian , Mingyue Ding\",\"doi\":\"10.1016/j.fuproc.2024.108068\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In this study, a series of CuCoAl catalysts with different Cu/Co molar ratios were prepared from hydrotalcite-like precursors and then adopted for <em>γ</em>-valerolactone (GVL) hydrogenation to 1,4-pentanediol (1,4-PeD). By tuning the Cu/Co ratio in the CuCoAl catalysts and optimizing the reaction conditions, nearly 100% yield of 1,4-PeD was finally achieved with the Cu<sub>0.2</sub>Co<sub>0.8</sub>Al catalyst (Cu/Co = 1: 4) at 433 K and 4 MPa H<sub>2</sub>. The high activity of the Cu<sub>0.2</sub>Co<sub>0.8</sub>Al catalyst was attributed to the existence of Cu-CoO<sub>x</sub> synergistic active sites and the abundant surface acidity. The electron transfer from Cu to Co resulted in the formation oxygen-defected CoO<sub>x</sub> sites and surface acidic sites, which were beneficial for the adsorption of GVL and the activation of C-O/C=O bonds. The proximity between Cu particles and defective CoO<sub>x</sub> facilitated the dissociative adsorption of H<sub>2</sub> on Cu<sup>0</sup> and the subsequent hydrogen spillover to CoO<sub>x</sub> sites, thereby significantly promoted the selective hydrogenation of GVL to 1,4-PeD. In addition, applications of the Cu<sub>0.2</sub>Co<sub>0.8</sub>Al catalyst to the ring-opening reactions of other lactones (including α-adamyllactone, γ-caprolactone, δ-pentyllactone, and ε-caprolactone) were further investigated. Eventually, high yields (> 93%) of the corresponding diols were attained, demonstrating the excellent catalytic versatility of Cu<sub>0.2</sub>Co<sub>0.8</sub>Al in selective hydrogenation of lactones. Overall, this work shows high potential of hydrotalcite-derived CuCoAl catalysts for selective hydrogenation of GVL to 1,4-PeD, and provides insights for the design of efficient bimetallic catalysts in lactone hydrogenolysis.</p></div>\",\"PeriodicalId\":326,\"journal\":{\"name\":\"Fuel Processing Technology\",\"volume\":\"256 \",\"pages\":\"Article 108068\"},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-02-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0378382024000389/pdfft?md5=52126577db00b0d8ee7cd76baaf8fb95&pid=1-s2.0-S0378382024000389-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Fuel Processing Technology\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0378382024000389\",\"RegionNum\":2,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Fuel Processing Technology","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0378382024000389","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Selective hydrogenation of γ-valerolactone to 1,4-pentanediol over hydrotalcite-derived CuCoAl catalysts
In this study, a series of CuCoAl catalysts with different Cu/Co molar ratios were prepared from hydrotalcite-like precursors and then adopted for γ-valerolactone (GVL) hydrogenation to 1,4-pentanediol (1,4-PeD). By tuning the Cu/Co ratio in the CuCoAl catalysts and optimizing the reaction conditions, nearly 100% yield of 1,4-PeD was finally achieved with the Cu0.2Co0.8Al catalyst (Cu/Co = 1: 4) at 433 K and 4 MPa H2. The high activity of the Cu0.2Co0.8Al catalyst was attributed to the existence of Cu-CoOx synergistic active sites and the abundant surface acidity. The electron transfer from Cu to Co resulted in the formation oxygen-defected CoOx sites and surface acidic sites, which were beneficial for the adsorption of GVL and the activation of C-O/C=O bonds. The proximity between Cu particles and defective CoOx facilitated the dissociative adsorption of H2 on Cu0 and the subsequent hydrogen spillover to CoOx sites, thereby significantly promoted the selective hydrogenation of GVL to 1,4-PeD. In addition, applications of the Cu0.2Co0.8Al catalyst to the ring-opening reactions of other lactones (including α-adamyllactone, γ-caprolactone, δ-pentyllactone, and ε-caprolactone) were further investigated. Eventually, high yields (> 93%) of the corresponding diols were attained, demonstrating the excellent catalytic versatility of Cu0.2Co0.8Al in selective hydrogenation of lactones. Overall, this work shows high potential of hydrotalcite-derived CuCoAl catalysts for selective hydrogenation of GVL to 1,4-PeD, and provides insights for the design of efficient bimetallic catalysts in lactone hydrogenolysis.
期刊介绍:
Fuel Processing Technology (FPT) deals with the scientific and technological aspects of converting fossil and renewable resources to clean fuels, value-added chemicals, fuel-related advanced carbon materials and by-products. In addition to the traditional non-nuclear fossil fuels, biomass and wastes, papers on the integration of renewables such as solar and wind energy and energy storage into the fuel processing processes, as well as papers on the production and conversion of non-carbon-containing fuels such as hydrogen and ammonia, are also welcome. While chemical conversion is emphasized, papers on advanced physical conversion processes are also considered for publication in FPT. Papers on the fundamental aspects of fuel structure and properties will also be considered.