Ahmed Abdo Hassan, Mostafa Farrag, Rabei M. Gabr, Mohamed I. Said
{"title":"改性Ce-UiO-66制备的CuO@纳米氧化铈表面协同作用增强2-丙醇脱氢","authors":"Ahmed Abdo Hassan, Mostafa Farrag, Rabei M. Gabr, Mohamed I. Said","doi":"10.1007/s10562-025-05161-y","DOIUrl":null,"url":null,"abstract":"<div><p>Dehydrogenation of alcohols to ketones and hydrogen offers a green and sustainable procedure for H<sub>2</sub> production as a best alternative for clean fuel. Researchers are challenged today to develop catalysts that possess remarkable conversion as well as high selectivity towards alcohol dehydration. CuO modified, structured cerias were successfully synthesized by carbonization of Ce-UiO-66 at 400–600 °C. The synthesized materials were characterized by XRD, XPS, TGA, TEM, EDX and FTIR spectroscopy. Surface texture also was investigated through N<sub>2</sub> adsorption at (77 <sup>°</sup>K). The catalysts were posted towards the dehydrogenation of 2-propanol in the gas phase. The catalytic performance could easily be tested by varying the Cu/Ce ratio, calcination temperature, and catalyst loading. The optimized CuO/CeO<sub>2</sub> ratio exhibited > 99% conversion and 100% selectivity for both H<sub>2</sub> and acetone at 225 °C. The characterization results showed that the synergetic effect between Cu<sup>2+</sup> and ceria existed and thus strengthening H<sub>2</sub> production, meanwhile following acetone generation. Kinetic analysis was studied isothermally at different temperatures which reveals that the dehydrogenation of 2-propanol behaves as first-order kinetics. The data was extended to determine the rate constant and the apparent activation energy (E<sub>a</sub>), which was found to be 19.48 kJ/mole. We proceeded further to compute ∆H, ∆S, and ∆G values. The values that confirm the thermodynamic spontaneity of the dehydrogenation pathway. The surface synergisms caused by the CuO modification, which increase the ratio of Ce(III) to Ce(IV) atoms and cause the creation of Cu(I) and Cu(II) sites, are responsible for the catalytic performance of the produced catalysts. Consequently, the CuO modification promotes the dehydrogenation pathway which needs these basic sites. Therefore, it is reasonable to propose that the most likely cause of the observed CuO enhancement of 2-propanol dehydrogenation is the improved production of Ce(III)/Ce(IV) and Cu(I)/Cu(II) redox couples. A Langmuir Hinshelwood mechanism was suggested, which included adsorbed IPA, H<sub>2</sub>, acetone, and isopropoxide into the site balance and supposed that the removal of the initial atom was the step that determined the reaction rate.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":508,"journal":{"name":"Catalysis Letters","volume":"155 10","pages":""},"PeriodicalIF":2.3000,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhanced Dehydrogenation of 2-Propanol via Surface Synergism of CuO@ Nanostructured Ceria Derived from Modified Ce-UiO-66\",\"authors\":\"Ahmed Abdo Hassan, Mostafa Farrag, Rabei M. Gabr, Mohamed I. Said\",\"doi\":\"10.1007/s10562-025-05161-y\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Dehydrogenation of alcohols to ketones and hydrogen offers a green and sustainable procedure for H<sub>2</sub> production as a best alternative for clean fuel. Researchers are challenged today to develop catalysts that possess remarkable conversion as well as high selectivity towards alcohol dehydration. CuO modified, structured cerias were successfully synthesized by carbonization of Ce-UiO-66 at 400–600 °C. The synthesized materials were characterized by XRD, XPS, TGA, TEM, EDX and FTIR spectroscopy. Surface texture also was investigated through N<sub>2</sub> adsorption at (77 <sup>°</sup>K). The catalysts were posted towards the dehydrogenation of 2-propanol in the gas phase. The catalytic performance could easily be tested by varying the Cu/Ce ratio, calcination temperature, and catalyst loading. The optimized CuO/CeO<sub>2</sub> ratio exhibited > 99% conversion and 100% selectivity for both H<sub>2</sub> and acetone at 225 °C. The characterization results showed that the synergetic effect between Cu<sup>2+</sup> and ceria existed and thus strengthening H<sub>2</sub> production, meanwhile following acetone generation. Kinetic analysis was studied isothermally at different temperatures which reveals that the dehydrogenation of 2-propanol behaves as first-order kinetics. The data was extended to determine the rate constant and the apparent activation energy (E<sub>a</sub>), which was found to be 19.48 kJ/mole. We proceeded further to compute ∆H, ∆S, and ∆G values. The values that confirm the thermodynamic spontaneity of the dehydrogenation pathway. The surface synergisms caused by the CuO modification, which increase the ratio of Ce(III) to Ce(IV) atoms and cause the creation of Cu(I) and Cu(II) sites, are responsible for the catalytic performance of the produced catalysts. Consequently, the CuO modification promotes the dehydrogenation pathway which needs these basic sites. Therefore, it is reasonable to propose that the most likely cause of the observed CuO enhancement of 2-propanol dehydrogenation is the improved production of Ce(III)/Ce(IV) and Cu(I)/Cu(II) redox couples. A Langmuir Hinshelwood mechanism was suggested, which included adsorbed IPA, H<sub>2</sub>, acetone, and isopropoxide into the site balance and supposed that the removal of the initial atom was the step that determined the reaction rate.</p><h3>Graphical Abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":508,\"journal\":{\"name\":\"Catalysis Letters\",\"volume\":\"155 10\",\"pages\":\"\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2025-09-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Catalysis Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10562-025-05161-y\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Letters","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s10562-025-05161-y","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Enhanced Dehydrogenation of 2-Propanol via Surface Synergism of CuO@ Nanostructured Ceria Derived from Modified Ce-UiO-66
Dehydrogenation of alcohols to ketones and hydrogen offers a green and sustainable procedure for H2 production as a best alternative for clean fuel. Researchers are challenged today to develop catalysts that possess remarkable conversion as well as high selectivity towards alcohol dehydration. CuO modified, structured cerias were successfully synthesized by carbonization of Ce-UiO-66 at 400–600 °C. The synthesized materials were characterized by XRD, XPS, TGA, TEM, EDX and FTIR spectroscopy. Surface texture also was investigated through N2 adsorption at (77 °K). The catalysts were posted towards the dehydrogenation of 2-propanol in the gas phase. The catalytic performance could easily be tested by varying the Cu/Ce ratio, calcination temperature, and catalyst loading. The optimized CuO/CeO2 ratio exhibited > 99% conversion and 100% selectivity for both H2 and acetone at 225 °C. The characterization results showed that the synergetic effect between Cu2+ and ceria existed and thus strengthening H2 production, meanwhile following acetone generation. Kinetic analysis was studied isothermally at different temperatures which reveals that the dehydrogenation of 2-propanol behaves as first-order kinetics. The data was extended to determine the rate constant and the apparent activation energy (Ea), which was found to be 19.48 kJ/mole. We proceeded further to compute ∆H, ∆S, and ∆G values. The values that confirm the thermodynamic spontaneity of the dehydrogenation pathway. The surface synergisms caused by the CuO modification, which increase the ratio of Ce(III) to Ce(IV) atoms and cause the creation of Cu(I) and Cu(II) sites, are responsible for the catalytic performance of the produced catalysts. Consequently, the CuO modification promotes the dehydrogenation pathway which needs these basic sites. Therefore, it is reasonable to propose that the most likely cause of the observed CuO enhancement of 2-propanol dehydrogenation is the improved production of Ce(III)/Ce(IV) and Cu(I)/Cu(II) redox couples. A Langmuir Hinshelwood mechanism was suggested, which included adsorbed IPA, H2, acetone, and isopropoxide into the site balance and supposed that the removal of the initial atom was the step that determined the reaction rate.
期刊介绍：
Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis.
The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
