Metal cooperativity for visible-light driven CO2 reduction with new photosensitizers and catalysts (CO2-COP)

新型光敏剂和催化剂对可见光驱动二氧化碳还原的金属协同作用（CO2-COP）

• 批准号: 428643898
• 负责人: Professor Dr. Ulf-Peter Apfel
• 金额: --
• 依托单位: Anorganische Chemie I: Lehrstuhl für Bioanorganische Chemie
• 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/428643898?language=en
• 关键词: Metal; cooperativity; visible; light; driven

The catalytic reduction of carbon dioxide (CO2) represents a highly active and challenging research field. Especially the photocatalytic recycling of CO2 and its utilization as a carbon feedstock could show severe impact on the global carbon balance as it allows to lower greenhouse gas emissions analog to natural photosynthesis pathways. Towards that end, chemistry plays a key role in developing such technologies by addressing the fundamental scientific challenges. Herein, pre-eminent catalyst development is of paramount importance and both homogenous and heterogeneous approaches are widely pursued. Due to the numerous spectroscopic techniques available and ease of synthetic alterations, studies on molecular transition metal complexes are vital for obtaining mechanistic insight on structurally very well-defined systems and are thus highly attractive to develop fundamental strategies for selective CO2 reduction processes. This approach requires the know-how of synthetic coordination chemists, photochemists, electrochemists and spectroscopists and will herein be attempted by joint efforts of the Wenger, Apfel and Robert groups. Inspired by Nature that enables selective activation of CO2 utilizing enzymatic bi-metallic active sites with a facilitated and selective multi-electron/multi-proton reduction through metal cooperativity, synthetic bi-metallic complexes will be rationally developed employing only earth-abundant metals. Furthermore, by tuning and controlling the metal cooperativity by targeted design of ligand backbone structures, we will aim at a selective synthesis of methanol, methane or short-chain hydrocarbons from CO2 in visible-light driven processes. To enable a light-driven CO2 reduction, these novel catalytic systems, however, likewise require novel suitable and potent photosensitizers. Thus, photosensitizers made from earth abundant transition metals will be synthesized and investigated for their photophysical properties. Consequently, the photosensitizers and catalysts will be synchronized in an iterative process between all groups. These findings will have far-reaching implications for photochemistry in general, as well as for CO2 reduction and activation in particular.

二氧化碳（CO2）的催化还原是一个非常活跃和具有挑战性的研究领域。特别是CO2的光催化回收及其作为碳原料的利用可能会对全球碳平衡产生严重影响，因为它可以降低温室气体排放，类似于自然光合作用途径。为此，化学通过应对基本的科学挑战，在开发此类技术方面发挥着关键作用。在此，卓越的催化剂开发是至关重要的，均相和非均相方法都被广泛采用。由于许多可用的光谱技术和易于合成的改变，对分子过渡金属络合物的研究对于获得结构上非常明确的系统的机理见解至关重要，因此对于开发选择性CO2还原过程的基本策略具有高度吸引力。这种方法需要合成配位化学家，光化学家，电化学家和光谱学家的专业知识，并将在这里尝试由温格，Apfel和罗伯特集团的共同努力。受大自然的启发，利用酶促双金属活性位点，通过金属协同性进行促进和选择性的多电子/多质子还原，能够选择性地活化CO2，将仅采用地球上丰富的金属来合理地开发合成双金属络合物。此外，通过有针对性地设计配体骨架结构来调节和控制金属协同性，我们的目标是在可见光驱动的过程中从CO2选择性合成甲醇、甲烷或短链烃。然而，为了实现光驱动的CO2还原，这些新型催化体系同样需要新型合适且有效的光敏剂。因此，由地球丰富的过渡金属制成的光敏剂将被合成并研究其物理性质。因此，光敏剂和催化剂将在所有组之间的迭代过程中同步。 这些发现将对光化学产生深远的影响，特别是对CO2的还原和活化。