Combined impact of pH, catalyst, and strongly non-ideal solvent mixtures (SNISMs) towards boosting acid-catalyzed reactions

反应介质和催化剂之间的相互作用极大地决定了化学合成过程的效率。均相催化需要单相条件，因此，底物溶解度高，动力学快，产率高，溶剂和催化剂的可回收性突出。无水条件下的化学反应需要一种反应介质，使水的热力学活度尽可能低，以克服热力学平衡带来的产率限制，而反应物的热力学活度和催化剂的热力学活度（如质子的活度）必须尽可能高。使用单一溶剂通常只允许调整这些性质中的一种，例如，降低水消除反应中的水活度可能只会以降低反应物或催化剂活性的动力学为代价。因此，在这个项目中，我们建议探索强非理想溶剂混合物（SNISMs），这些溶剂混合物显示出与拉乌尔定律的明显负偏差，并且它们在消除水的反应中有用。snism可以或多或少亲水性，取决于它们的成分。到目前为止，SNISMs对反应混合物中的相行为以及反应的产率和动力学的影响尚不清楚。SNISMs在其他参数（温度、压力、pH）之上对相行为和反应效率的多方面影响不能仅通过实验来研究。因此，需要一种预测工具来深入了解强酸性催化剂如杂多酸（HPAs）的机制，并预测HPA-SNISM梦之队。这将允许在相对较低的温度下在水消除下催化反应，并可调节催化剂的分离和回收。本项目的新思路是将hpa -催化剂的热力学性质（物理相互作用）和解离平衡（特别是催化剂）与反应效率作为反应介质（SNISM组分和浓度）的函数联系起来。解离平衡和HPA相互作用将通过电解质热力学模型进行预测，并通过IR表征进行验证。我们假设，如果反应速度与催化剂的热力学活性有关，则动力学曲线将落在一起。综上所述，我们的目标是为液相反应定制SNISMs，揭示水和hpa -催化剂对SNISMs相行为的影响，SNISMs和hpa -催化剂对反应热力学和动力学的影响，并利用收集的数据验证预测电解质模型，最终建立预测动力学模型。此外，我们旨在建立SNISMs和hpa -催化剂的可回收性概念，并提高吨收率、tof收率和时空收率。我们将通过将获得的知识应用于水消除下的另一个反应体系来验证我们的发现。

The interplay between reaction medium and catalyst tremendously dictates the efficiency of processes involving chemical syntheses. Homogenous catalysis requires monophasic conditions and thus, a high substrate solubility, fast kinetics, high yield, and outstanding recyclability of solvent and catalyst. Chemical reactions under elimination of water require a reaction medium that keeps thermodynamic water activity as low as possible in order to overcome yield limitations caused by thermodynamic equilibrium, while the thermodynamic reactant activity and thermodynamic catalyst activity (e.g., proton’s activity) must be as high as possible. The use of single solvents usually allows tuning only one of these properties, e.g. decreasing water activity in water-elimination reactions might be possible only at cost of decreased kinetics by negative impact on the activity of reactant or catalyst. Thus, in this project we suggest exploring strongly non-ideal solvent mixtures (SNISMs) that show pronounced negative deviations from Raoult’s law and their usefulness in reactions under elimination of water. SNISMs can be more or less hydrophilic, depending on their constituents. So far, the influence of SNISMs on the phase behavior in reaction mixtures as well as yield and kinetics of the reaction is not well known. The multifacetted influence of SNISMs on phase behaviour and reaction efficiency on top of other parameters (temperature, pressure, pH) cannot be investigated by experiments only. Thus, a predictive tool is required to gain insight into the mechanism of strongly acidic catalysts like heteropolyacids (HPAs) and to predictively tailor HPA-SNISM dream teams. These will allow catalyzing reactions under water elimination at comparably low temperatures and a tuneable separation and recycling of the catalyst. The new idea of this project is to link thermodynamic properties of the HPA-catalyst (physical interactions) and the dissociation equilibria (especially of the catalyst) with the reaction efficiency as function of the reaction media (SNISM constituents and concentrations). The dissociation equilibria and the HPA interactions will be predicted by electrolyte thermodynamic models, validated by IR characterization. We postulate that kinetic curves will fall together if the reaction velocity is related to the thermodynamic activity of the catalyst. To sum up, we aim at tailoring SNISMs for liquid-phase reactions, revealing the influence of water and of HPA-catalyst on the phase behaviour of the SNISMs and the influence of SNISMs and of HPA-catalysts on reaction thermodynamics and kinetics, and to validate predictive electrolyte models using the gathered data to finally develop predictive kinetic models. Further, we aim at establishing recyclability concepts for SNISMs and HPA-catalysts and to improve TONs, TOFs, and spacetime yield. We will validate our findings by applying the gained knowledge to another reaction system under water elimination.