Xiaonan Xu, Nana Luo, Wan-Hui Wang, Ming Bao, Jiasheng Wang
{"title":"揭示Mo掺杂Ni对催化脂肪酸加氢制脂肪醇的影响","authors":"Xiaonan Xu, Nana Luo, Wan-Hui Wang, Ming Bao, Jiasheng Wang","doi":"10.1021/acsami.4c13926","DOIUrl":null,"url":null,"abstract":"Fatty acid hydrogenation is an important method for the production of fatty alcohols. The combination of Ni and Mo has been reported to be an effective and low-cost catalyst. However, the effect of Mo doping has yet to be fully understood. Here Ni-MoO<sub><i>x</i></sub>/TiO<sub>2</sub> catalysts were prepared via simple impregnation. and the enhancement effects of Mo doping were comprehensively revealed. First, MoO<sub><i>x</i></sub> can attract electrons from Ni, reduce the electron density of Ni to improve the intrinsic activity of Ni, and form a Ni<sup>δ+</sup>-(MoO<sub><i>x</i></sub>)<sup>δ−</sup> heterojunction to induce H<sub>2</sub> heterolytic cleavage to active hydrogen ions. Second, the reduction of MoO<sub><i>x</i></sub> generates oxygen vacancies, which can absorb C═O of the fatty acid and facilitate the reaction progression. Third, a Ni<sub>1–<i>x</i></sub>Mo<sub><i>x</i></sub> solid solution can be formed, which can increase the hydrogen adsorption quantity and accelerate the reaction rate. Finally, the bond strength of Mo–O is found to be the most optimum that can absorb the fatty acids while releasing the alcohols so as to recover the oxygen vacancies and avoid overhydrogenation. Therefore, high activity and selectivity for the hydrogenation of carboxylic acid substrates to alcohols can be obtained. Under significantly milder conditions (155 °C, 3 MPa H<sub>2</sub>) the catalyst provided a 98% yield of lauryl alcohol from lauric acid hydrogenation with a low activation energy of 40.1 kJ/mol. This work could provide an insightful understanding about the effects of Mo doping to Ni on catalyzing hydrogenation reactions.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"21 1","pages":""},"PeriodicalIF":8.2000,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Revealing the Effects of Mo Doping to Ni on Catalyzing Hydrogenation of Fatty Acids to Fatty Alcohols\",\"authors\":\"Xiaonan Xu, Nana Luo, Wan-Hui Wang, Ming Bao, Jiasheng Wang\",\"doi\":\"10.1021/acsami.4c13926\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Fatty acid hydrogenation is an important method for the production of fatty alcohols. The combination of Ni and Mo has been reported to be an effective and low-cost catalyst. However, the effect of Mo doping has yet to be fully understood. Here Ni-MoO<sub><i>x</i></sub>/TiO<sub>2</sub> catalysts were prepared via simple impregnation. and the enhancement effects of Mo doping were comprehensively revealed. First, MoO<sub><i>x</i></sub> can attract electrons from Ni, reduce the electron density of Ni to improve the intrinsic activity of Ni, and form a Ni<sup>δ+</sup>-(MoO<sub><i>x</i></sub>)<sup>δ−</sup> heterojunction to induce H<sub>2</sub> heterolytic cleavage to active hydrogen ions. Second, the reduction of MoO<sub><i>x</i></sub> generates oxygen vacancies, which can absorb C═O of the fatty acid and facilitate the reaction progression. Third, a Ni<sub>1–<i>x</i></sub>Mo<sub><i>x</i></sub> solid solution can be formed, which can increase the hydrogen adsorption quantity and accelerate the reaction rate. Finally, the bond strength of Mo–O is found to be the most optimum that can absorb the fatty acids while releasing the alcohols so as to recover the oxygen vacancies and avoid overhydrogenation. Therefore, high activity and selectivity for the hydrogenation of carboxylic acid substrates to alcohols can be obtained. Under significantly milder conditions (155 °C, 3 MPa H<sub>2</sub>) the catalyst provided a 98% yield of lauryl alcohol from lauric acid hydrogenation with a low activation energy of 40.1 kJ/mol. This work could provide an insightful understanding about the effects of Mo doping to Ni on catalyzing hydrogenation reactions.\",\"PeriodicalId\":5,\"journal\":{\"name\":\"ACS Applied Materials & Interfaces\",\"volume\":\"21 1\",\"pages\":\"\"},\"PeriodicalIF\":8.2000,\"publicationDate\":\"2024-12-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Materials & Interfaces\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acsami.4c13926\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Materials & Interfaces","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acsami.4c13926","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Revealing the Effects of Mo Doping to Ni on Catalyzing Hydrogenation of Fatty Acids to Fatty Alcohols
Fatty acid hydrogenation is an important method for the production of fatty alcohols. The combination of Ni and Mo has been reported to be an effective and low-cost catalyst. However, the effect of Mo doping has yet to be fully understood. Here Ni-MoOx/TiO2 catalysts were prepared via simple impregnation. and the enhancement effects of Mo doping were comprehensively revealed. First, MoOx can attract electrons from Ni, reduce the electron density of Ni to improve the intrinsic activity of Ni, and form a Niδ+-(MoOx)δ− heterojunction to induce H2 heterolytic cleavage to active hydrogen ions. Second, the reduction of MoOx generates oxygen vacancies, which can absorb C═O of the fatty acid and facilitate the reaction progression. Third, a Ni1–xMox solid solution can be formed, which can increase the hydrogen adsorption quantity and accelerate the reaction rate. Finally, the bond strength of Mo–O is found to be the most optimum that can absorb the fatty acids while releasing the alcohols so as to recover the oxygen vacancies and avoid overhydrogenation. Therefore, high activity and selectivity for the hydrogenation of carboxylic acid substrates to alcohols can be obtained. Under significantly milder conditions (155 °C, 3 MPa H2) the catalyst provided a 98% yield of lauryl alcohol from lauric acid hydrogenation with a low activation energy of 40.1 kJ/mol. This work could provide an insightful understanding about the effects of Mo doping to Ni on catalyzing hydrogenation reactions.
期刊介绍:
ACS Applied Materials & Interfaces is a leading interdisciplinary journal that brings together chemists, engineers, physicists, and biologists to explore the development and utilization of newly-discovered materials and interfacial processes for specific applications. Our journal has experienced remarkable growth since its establishment in 2009, both in terms of the number of articles published and the impact of the research showcased. We are proud to foster a truly global community, with the majority of published articles originating from outside the United States, reflecting the rapid growth of applied research worldwide.