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

IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL
Valeria Finelli , Federico Panagini , Reza K. Abasabadi , Francesca Rosso , Barbara Centrella , Matteo Signorile , Silvia Bordiga
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引用次数: 0

摘要

环己烯烯丙基部分氧化反应是目前化学工业中广泛应用的2-环己烯醇和2-环己烯酮的相关反应。目前该反应以非催化方式进行,由于自由基机制的存在,对产物选择性和总转化率的控制不是最优的。在这篇文章中,我们试图通过研究铈基金属有机框架作为催化剂的潜力,将环己烯氧化转变为非均相催化过程。这类材料在氧化催化方面表现出良好的性能,我们在此重点研究UiO-67框架的原型。作为初步筛选,我们考察了在非常温和的条件下(室温和常压),反应组成变量(即引发剂和底物的量)和气相氧分压对性能的影响。为了在这个变量空间上一致地进行评估,我们利用了实验设计化学计量学方法。这使我们能够通过在变量空间中仅执行所有可能组合的子集来显着提高反应性能(相对于文献中未优化的条件,总体生产率提高约50% %)。这一贡献代表了合理发展环己烯烯丙基氧化催化过程的第一步,基于一种强大的统计方法,将在未来扩展到其他反应参数的研究。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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.
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来源期刊
Applied Catalysis A: General
Applied Catalysis A: General 化学-环境科学
CiteScore
9.00
自引率
5.50%
发文量
415
审稿时长
24 days
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.
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