Abstract A class of Bronsted–Lewis acid bifunctionalized ionic liquids based heteropolyacid hybrid (BLA-ILs-HPA) solid acids were developed by combining the double sulfonic groups grafted, ionic liquids based heteropolyacid hybrid with Lewis acidic centers (M = Zn, Co, Fe, Ni, Cu). The prepared BLA-ILs-HPA show both Bronsted and Lewis acidic sites with extremely-high acid strength and enhanced stabilities, as determined by FT-IR, Py-IR, TG, XPS and 31P solid state NMR results. BLA-ILs-HPA were successfully applied in esterification camphene with acetic acid to produce isobornyl acetate, and dehydration of glucose to produce 5-hydrozymethylfural. BLA-ILs-HPA show enhanced catalytic activities in comparison with various acid catalysts. The effects of reaction temperatures, initial reactant molar ratio, catalyst dosage, and reaction time were studied in detail. The optimal reaction conditions were obtained, and the experimental data was successfully correlated by a pseudohomogeneous (PH) reaction kinetic model in the temperature range of 313.15–333.15 K. The calculated values obtained by the reaction kinetic model were in good agreement with the experimental data. Moreover, as a heterogeneous reaction catalyst, BLA-ILs-HPA can be recovered by simple treatment. After six times cycling, the decreasing in the catalytic activity of BLA-ILs-HPA could not be observed significantly, suggesting their good reusability.

中文翻译：

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开发基于 Brønsted-Lewis 酸双官能化离子液体的杂多酸杂化物作为酯化和生物质转化中的高效固体酸

摘要 通过将双磺酸基接枝的离子液体基杂多酸杂化物与路易斯酸性中心（M = Zn、Co、Fe 、镍、铜）。FT-IR、Py-IR、TG、XPS 和 31P 固态核磁共振结果表明，制备的 BLA-ILs-HPA 显示出布朗斯台德和路易斯酸性位点，具有极高的酸强度和增强的稳定性。BLA-ILs-HPA成功应用于莰烯与乙酸酯化生成乙酸异冰片酯，葡萄糖脱水生成5-羟甲基糠醛。与各种酸催化剂相比，BLA-ILs-HPA 显示出增强的催化活性。反应温度、初始反应物摩尔比、催化剂用量、和反应时间进行了详细研究。获得了最佳反应条件，并在313.15-333.15 K的温度范围内通过拟均相（PH）反应动力学模型成功关联了实验数据。反应动力学模型计算值与实验数据吻合良好. 此外，作为非均相反应催化剂，BLA-ILs-HPA 可以通过简单的处理回收。循环6次后，BLA-ILs-HPA的催化活性没有明显降低，表明它们具有良好的可重复使用性。反应动力学模型得到的计算值与实验数据吻合良好。此外，作为非均相反应催化剂，BLA-ILs-HPA 可以通过简单的处理回收。循环6次后，BLA-ILs-HPA的催化活性没有明显降低，表明它们具有良好的可重复使用性。反应动力学模型得到的计算值与实验数据吻合良好。此外，作为非均相反应催化剂，BLA-ILs-HPA 可以通过简单的处理回收。循环6次后，BLA-ILs-HPA的催化活性没有明显降低，表明它们具有良好的可重复使用性。