Structure-activity relationships of ZrO2 crystalline phases in the catalytic transfer hydrogenation of methyl levulinate with ethanol
Structure-activity relationships of ZrO2 crystalline phases in the catalytic transfer hydrogenation of methyl levulinate with ethanol
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DOI：
10.1016/j.jcat.2023.115177
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发表时间：
2023-10
影响因子：
7.3
通讯作者：
Riccardo Bacchiocchi;Alessia Ventimiglia;Andrea Canciani;Giorgia Peroni;T. Tabanelli;S. Albonetti;N. Dimitratos;I. Rivalta;Shima Zainal;Luke Forster;C. D'agostino;F. Cavani
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文献类型：
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作者：
Riccardo Bacchiocchi;Alessia Ventimiglia;Andrea Canciani;Giorgia Peroni;T. Tabanelli;S. Albonetti;N. Dimitratos;I. Rivalta;Shima Zainal;Luke Forster;C. D'agostino;F. Cavani
化石资源的枯竭正在推动对可再生替代品的研究，如木质纤维素生物质。因此，开发高效的连续流工艺，使其能够实现比间歇工艺更高的生产率，将在促进可持续转型方面发挥至关重要的作用。在这种情况下，我们报告的连续流，气相，催化转移氢化（CTH）的乙酰丙酸甲酯和乙醇在氧化锆催化剂，特别是专注于两种不同的晶相（即单斜晶系，m-ZrO 2，和tetrahydroxide，t-ZrO 2）对催化剂性能的影响。一个深入的催化剂表征与计算和1H NMR弛豫研究相结合，以评估结构-活性关系，为催化过程和未来的催化剂优化提供基本的见解。结果表明，较高的刘易斯酸性和碱性沿着与乙醇的较低亲和力的m-ZrO 2相对于t-ZrO 2是负责促进当归内酯的不希望的低聚反应，负责催化剂失活。
The depletion of fossil resources is driving the research towards renewable alternatives, like lignocellulosic biomass. Therefore, the development of efficient continuous-flow processes, allowing to achieve better productivity compared to batch processes, will play a crucial role in promoting a sustainable transition. In this context, we report on the continuous-flow, gas-phase, catalytic transfer hydrogenation (CTH) of methyl levulinate and ethanol over zirconia catalysts, in particular focusing on the effect of two different crystalline phases (i.e. monoclinic,m-ZrO2, and tetragonal,t-ZrO2) on catalyst performance. An in-depth catalyst characterisation was coupled with both computational and1H NMR relaxation studies to assess the structure-activity relationship, providing fundamental insights into the catalytic process and future catalyst optimization. The results, indicate that the higher Lewis acidity and basicity along with the lower affinity with ethanol ofm-ZrO2with respect tot-ZrO2are responsible for the promotion of undesired oligomerisation reactions of angelica lactones responsible for catalyst deactivation.