Electro- und photoreduction of carbon dioxide with heterodinuclear complexes

二氧化碳与异双核配合物的电还原和光还原

• 批准号: 5383668
• 负责人: Professor Dr. Wolfgang Kaim
• 金额: --
• 依托单位: Institut für Anorganische Chemie (IAC)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2002
• 资助国家: 德国
• 起止时间: 2001-12-31 至 2007-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/5383668?language=en
• 关键词: Electro; und; photoreduction; carbon; dioxide

The project is directed at the synthesis and the investigation of physicochemical, photo- and electrochemical properties of heterodinuclear complexes which will to be used as novel catalysts for the electro- and photocatalysis of CO2 reduction. The multielectron reduction of CO2, preferentially leading to the production of hydrocarbons or alcohols, remains a fundamental challenge in the chemical activation of CO2. New kinds of supramolecular multifunctional heterobimetallic complexes which combine in the same molecular matrix a hydride transfer catalyst such as [MCp*(L)Cl+ (M = Ir(III) or Rh(III); L = bidentate ligand) and an electrocatalyst or photocatalyst like the metal carbonyl complexes Ru(L)(CO)2Cl2 or Re(L)(CO)3Cl, capable of reducing CO2 to CO, are proposed as effective materials for this type of catalytic activity. The presence of two different complex functions, coupled electronically by p-bridging ligands, and the proximity of the two metal centres in a closed molecular structure during the photo- and electrocatalysis of CO2 reduction is believed to induce a cooperative effect with the result of direct hydrogenation of CO (the primary two-electron reduction product), allowing for the production of hydrogenated compounds, e.g. methanol. The synthesis and the detailed physicochemical study (electrochemistry spectroscopy) of such new kinds of heterobimetallic complex catalysts of CO2 reduction are the principal objective of this project. To conduct this research, the scientifically complementary skills of both groups will be brought together in a synergistic function to design, synthesize and study in detail the new bifunctional molecular systems. Mechanistic studies of multielectron reactivity, including quantum-chemical calculations of precursors and essential intermediates will accompany the actual tests of the catalytic properties of the new systems in order to improve their performance.

该项目旨在合成和研究异双核配合物的物理化学，光和电化学性质，这些配合物将用作CO2还原的电催化剂和电催化剂。CO2的多电子还原，优先导致烃或醇的产生，仍然是CO2化学活化中的基本挑战。新型的超分子多功能杂环化合物是将[MCp*（L）Cl+]等氢转移催化剂联合收割机结合在同一分子基质中，（M = Ir（III）或Rh（III）; L =双齿配体）和电催化剂或光催化剂如金属羰基络合物Ru（L）（CO）2Cl 2或Re（L）（CO）3Cl，其能够将CO2还原成CO，被认为是这种催化活性的有效材料。两个不同的复杂功能的存在下，电子耦合的p-桥接配体，并在一个封闭的分子结构中的两个金属中心的光催化和电催化的CO2还原过程中的接近被认为是诱导协同效应的结果直接氢化CO（主要的两个电子还原产物），允许生产氢化化合物，如甲醇。本项目的主要目标是合成和详细的物理化学研究（电化学光谱），这类新型的杂多配合物催化剂的CO2还原。为了进行这项研究，两个小组的科学互补技能将被汇集在一起，协同设计，合成和详细研究新的双功能分子系统。多电子反应性的机理研究，包括前体和必要中间体的量子化学计算，将伴随着新系统催化性能的实际测试，以提高其性能。