NSF-DFG Echem: Cooperativity between immobilized redox mediators for selective anodic biomass valorization

NSF-DFG Echem：固定化氧化还原介体之间的协同作用，用于选择性阳极生物质增值

• 批准号: 460129901
• 负责人: Professor Dr. Robert Francke
• 金额: --
• 依托单位: College of Engineering and Applied Science
• 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/460129901?language=en
• 关键词: NSF; DFG; Echem; Cooperativity; between

A long-standing goal of catalysis science is the at-will design of active sites that exhibit substrate specificity, rate, and product selectivity on par with what is afforded by natural enzymatic catalysts. The performance of such structures, having tailored substrate binding environments with multiple participant functional groups, is difficult to imitate with homogeneous molecular catalysts, and arguably even more challenging using heterogeneous catalyst materials, desirable for their ease of separability. Nonetheless, increasing efforts to design heterogeneous, three-dimensional catalytic environments with multiple “cooperative” catalytically participating moieties have seen great progress in recent years. This proposal aims to understand and develop cooperative electrocatalytic sites, comprised of an organic redox mediator and redox-active metal center, both performing electron transfer to achieve multi-electron oxidation reactions at smaller driving potential than what the constituent moieties can achieve alone. We seek to develop the fundamental understanding and methodologies to effectively immobilize cooperative catalysts onto (a) soluble (but easily separated) polymers and (b) heterogeneous electrodes. These two platforms will provide complementary means to identify constraints imposed by immobilization and understand how best to retain cooperativity.

催化科学的一个长期目标是随意设计活性位点，使其表现出与天然酶催化剂相同的底物特异性、速率和产物选择性。具有带有多个参与官能团的定制基底结合环境的此类结构的性能难以用均相分子催化剂来模仿，并且可以说使用非均相催化剂材料甚至更具挑战性，因为它们易于分离。尽管如此，近年来，越来越多的努力来设计具有多个“合作”催化参与部分的多相三维催化环境已经取得了很大进展。该提议旨在理解和开发合作的电催化位点，其由有机氧化还原介体和氧化还原活性金属中心组成，两者都执行电子转移以在比组成部分可以单独实现的更小的驱动电位下实现多电子氧化反应。我们寻求发展基本的理解和方法，以有效地将合作催化剂分散到（a）可溶性（但容易分离）聚合物和（B）异质电极上。这两个平台将提供互补的手段，以确定固定化所施加的限制，并了解如何最好地保持合作性。