{"title":"实验设计:Ce-UiO-67对环己烯烯丙基部分氧化的催化性能有价值的微调工具","authors":"Valeria Finelli , Federico Panagini , Reza K. Abasabadi , Francesca Rosso , Barbara Centrella , Matteo Signorile , Silvia Bordiga","doi":"10.1016/j.apcata.2025.120534","DOIUrl":null,"url":null,"abstract":"<div><div>Cyclohexene allylic partial oxidation is currently a relevant reaction yielding 2-cyclohexenol and 2-cyclohexenone, that are widely used intermediates in chemical industry. The reaction is presently performed in an uncatalyzed way and, due to the radical mechanism, the control on products selectivity and overall conversion is not optimal. In this contribution, we attempted to shift cyclohexene oxidation toward a heterogeneous catalytic process, by investigating the potential of Ce-based metal-organic frameworks as catalysts. This class of materials demonstrated promising performances in oxidation catalysis, and we focus herein on the prototypical UiO-67 framework. As an initial screening, we investigated the effect of reaction compositional variables (namely initiator and substrate amount) and oxygen partial pressure in the gas-phase on the performances under very mild conditions (room temperature and pressure). To consistently perform the assessment over this variables space, we took advantage of a Design of Experiments chemometric approach. This allowed us to significantly improve the reaction performances (<em>ca.</em> 50 % increase in overall productivity with respect to not optimized conditions from literature) by performing only a subset of all possible combinations in the variables space. This contribution represents a first step toward a rational development of a catalytic process for cyclohexene allylic oxidation, based on a robust statistical approach that will be extended in the future to the investigation of other reaction parameters.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"708 ","pages":"Article 120534"},"PeriodicalIF":4.8000,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Design of Experiments: A valuable tool for fine-tuning catalytic performances of Ce-UiO-67 for the allylic partial oxidation of cyclohexene\",\"authors\":\"Valeria Finelli , Federico Panagini , Reza K. Abasabadi , Francesca Rosso , Barbara Centrella , Matteo Signorile , Silvia Bordiga\",\"doi\":\"10.1016/j.apcata.2025.120534\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Cyclohexene allylic partial oxidation is currently a relevant reaction yielding 2-cyclohexenol and 2-cyclohexenone, that are widely used intermediates in chemical industry. The reaction is presently performed in an uncatalyzed way and, due to the radical mechanism, the control on products selectivity and overall conversion is not optimal. In this contribution, we attempted to shift cyclohexene oxidation toward a heterogeneous catalytic process, by investigating the potential of Ce-based metal-organic frameworks as catalysts. This class of materials demonstrated promising performances in oxidation catalysis, and we focus herein on the prototypical UiO-67 framework. As an initial screening, we investigated the effect of reaction compositional variables (namely initiator and substrate amount) and oxygen partial pressure in the gas-phase on the performances under very mild conditions (room temperature and pressure). To consistently perform the assessment over this variables space, we took advantage of a Design of Experiments chemometric approach. This allowed us to significantly improve the reaction performances (<em>ca.</em> 50 % increase in overall productivity with respect to not optimized conditions from literature) by performing only a subset of all possible combinations in the variables space. This contribution represents a first step toward a rational development of a catalytic process for cyclohexene allylic oxidation, based on a robust statistical approach that will be extended in the future to the investigation of other reaction parameters.</div></div>\",\"PeriodicalId\":243,\"journal\":{\"name\":\"Applied Catalysis A: General\",\"volume\":\"708 \",\"pages\":\"Article 120534\"},\"PeriodicalIF\":4.8000,\"publicationDate\":\"2025-08-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis A: General\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926860X25004351\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X25004351","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Design of Experiments: A valuable tool for fine-tuning catalytic performances of Ce-UiO-67 for the allylic partial oxidation of cyclohexene
Cyclohexene allylic partial oxidation is currently a relevant reaction yielding 2-cyclohexenol and 2-cyclohexenone, that are widely used intermediates in chemical industry. The reaction is presently performed in an uncatalyzed way and, due to the radical mechanism, the control on products selectivity and overall conversion is not optimal. In this contribution, we attempted to shift cyclohexene oxidation toward a heterogeneous catalytic process, by investigating the potential of Ce-based metal-organic frameworks as catalysts. This class of materials demonstrated promising performances in oxidation catalysis, and we focus herein on the prototypical UiO-67 framework. As an initial screening, we investigated the effect of reaction compositional variables (namely initiator and substrate amount) and oxygen partial pressure in the gas-phase on the performances under very mild conditions (room temperature and pressure). To consistently perform the assessment over this variables space, we took advantage of a Design of Experiments chemometric approach. This allowed us to significantly improve the reaction performances (ca. 50 % increase in overall productivity with respect to not optimized conditions from literature) by performing only a subset of all possible combinations in the variables space. This contribution represents a first step toward a rational development of a catalytic process for cyclohexene allylic oxidation, based on a robust statistical approach that will be extended in the future to the investigation of other reaction parameters.
期刊介绍:
Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications.
Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.