With the growing demand for sustainable energy, developing new technologies based on biomass has caused deep interest. Glucose conversion into fructose is a crucial step in the sustainable biorefinery industry. Metal–organic frameworks with abundant active metal centers have shown potential, but their specific contribution is not yet fully understood. In this study, mesoporous Zr-NU-1008 with hexanuclear clusters (M) exhibited a higher glucose conversion of 54.7 % with a fructose selectivity of 85.3 % under optimized conditions compared with its hafnium counterpart, highlighting the significance of strong Lewis acidity of metal species. By adjusting the amount of the capped formate on the hexanuclear zirconium (IV) cluster (Zr) of Zr-NU-1008, a positive correlation with the catalytic activity was realized, suggesting the lability of the capping modulator during catalysis, which enables tuning the activity by manipulating the capping modulator. Further saturating the Zr cluster with the electron-withdrawing trifluoroacetate modulator achieved an excellent glucose conversion of 63.3 % with a superior fructose selectivity of 86.0 %. Besides, the recovered catalyst can be easily regenerated by reinstalling the modulator on the M cluster, restoring its catalytic activity.

中文翻译：

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揭示六核簇对金属有机框架上高选择性葡萄糖转化的贡献

随着对可持续能源的需求不断增长，开发基于生物质的新技术引起了人们的浓厚兴趣。将葡萄糖转化为果糖是可持续生物精炼行业的关键一步。具有丰富活性金属中心的金属有机框架已显示出潜力，但其具体贡献尚未完全了解。在这项研究中，与铪对应物相比，具有六核簇（M）的介孔Zr-NU-1008在优化条件下表现出更高的葡萄糖转化率54.7％，果糖选择性为85.3％，凸显了金属物种强路易斯酸性的重要性。通过调节Zr-NU-1008的六核锆(IV)簇(Zr)上的封端甲酸盐的量，实现了与催化活性的正相关，这表明封端调节剂在催化过程中的不稳定性，从而能够调节通过操纵封端调节器来调节活性。用吸电子三氟乙酸酯调节剂进一步饱和 Zr 簇，实现了 63.3% 的出色葡萄糖转化率和 86.0% 的卓越果糖选择性。此外，回收的催化剂可以通过在M团簇上重新安装调节剂来轻松再生，恢复其催化活性。