Functional Polymers and Nanoparticles for Sustainable Reaction Control in Electrosynthesis

用于电合成可持续反应控制的功能聚合物和纳米颗粒

• 批准号: 405986400
• 负责人: Professor Dr. Robert Francke
• 金额: --
• 依托单位: Bereich Elektrochemie & Katalyse
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/405986400?language=en
• 关键词: Functional; Polymers; Nanoparticles; Sustainable; Reaction

Organic electrosynthesis is often described as “green” or “intrinsically sustainable”. However, this assessment cannot be readily generalized, since large amounts of (often hydrophobic) supporting electrolytes must be used, which are difficult to remove after electrolysis. The same applies to high mediator loadings, which are often needed to control selectivity. The present renewal proposal addresses these challenges and aims to advance a strategy for sustainable reaction control that was elaborated in the first project stage. The approach involves the use of so-called polymediators and polyelectrolytes. Their difference in size relative to typical product molecules enables recovery by dialysis or membrane filtration. The concept was successfully established by us using TEMPO-mediated anodic oxidation of alcohols as a test case. Our studies also provided insights into the mechanisms of the processes involved and the influence of the molecular weight of the polymers. The second stage of the project is intended to further advance the developed approach. Both a deeper mechanistic understanding as well as extension and optimization of the concept will be targeted. First, the strategy will be extended by including electrochemically stable polymer-supported bases. Such polybases may become useful as proton scavengers in TEMPO-mediated alcohol oxidation and in a variety of other anodic syntheses. In the next step, the scope will be broadened by developing new synthetic applications. For this purpose, polymethacrylate active esters will serve as a flexible platform for the preparation of new polymediators via post-polymerization functionalization. Another key question is how the spatial arrangement of the mediator units affects charge transport and catalytic activity. Our previous work has been based on polymer chains, which tend to have a randomly coiled conformation in solution. In this regard, it will be interesting to examine whether conformational changes can affect the catalytic activity of a polymediator. For this purpose, dendrimer structures exhibiting a rigid spherical conformation in which all mediator units are exposed to the solution will be investigated. Finally, an adjacent topic will be explored to provide new impetus for future research. In this context, the use of dispersed nanoparticles loaded with mediators and supporting electrolyte units is planned. To ensure good electron transfer kinetics between mediator and electrode, the use of electrically conductive carbon nanotubes is proposed. The approach should enable the use of simple mechanical separation processes (centrifugation, filtration) without the necessity for using co-mediators.

有机电合成通常被描述为“绿色”或“本质上可持续的”。然而，这种评估不能容易地概括，因为必须使用大量的（通常是疏水的）支持电解质，其在电解后难以去除。这同样适用于高介体负载，这通常需要控制选择性。目前的更新提案针对这些挑战，旨在推进项目第一阶段制定的可持续反应控制战略。该方法涉及使用所谓的聚合介质和聚合电解质。它们相对于典型产物分子的尺寸差异使得能够通过透析或膜过滤进行回收。我们使用TEMPO介导的醇类阳极氧化作为测试案例成功地建立了这一概念。我们的研究还提供了有关过程的机制和聚合物分子量的影响的见解。该项目的第二阶段旨在进一步推进所制定的方法。既有更深层次的机械理解，也有概念的扩展和优化。首先，该策略将通过包括电化学稳定的聚合物支撑的碱来扩展。此类聚碱可能在TEMPO介导的醇氧化和各种其他阳极合成中用作质子清除剂。下一步，将通过开发新的合成应用来扩大范围。为此，聚甲基丙烯酸酯活性酯将作为一个灵活的平台，通过后聚合功能化制备新的polymediators。另一个关键问题是介体单元的空间排列如何影响电荷传输和催化活性。我们以前的工作是基于聚合物链，这往往有一个随机卷曲构象在溶液中。在这方面，它将是有趣的，以检查是否构象变化可以影响催化活性的多介体。为了这个目的，树枝状大分子结构表现出刚性的球形构象，其中所有的调解员单位暴露于解决方案将进行调查。最后，我们将探讨一个邻近的主题，为未来的研究提供新的动力。在这种情况下，计划使用分散的纳米粒子加载介质和支持电解质单元。为了确保介体和电极之间良好的电子转移动力学，提出使用导电碳纳米管。该方法应能够使用简单的机械分离过程（离心、过滤），而无需使用共介质。