Protection of O2 Sensitive Catalysts under reductive Conditions

还原条件下保护 O2 敏感催化剂

• 批准号: 490864939
• 负责人: Professor Dr. Nicolas Plumeré
• 金额: --
• 依托单位: Bioénergétique et Ingénierie des Protéines (BIP) (UMR 7281)
• 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/490864939?language=en
• 关键词: Protection; O2; Sensitive; Catalysts; under

The implementation of energy conversion schemes involving dihydrogen and CO2 requires solutions that prevent the inactivation by oxygen of biological or synthetic catalysts that are based on cheap and abundant transition metals. The partners of the project have recently developed a strategy for using O2-sensitive catalysts of H2 oxidation under aerobic conditions, which consists in embedding the catalyst into a carefully designed micrometer-thick redox-polymer film supported into an electrode. They showed that self-protection occurs because in addition to catalytic hydrogen oxidation near the electrode, a fraction of the incoming H2 is catalytically oxidized near the film/solution interface to reduce the O2 molecules that penetrate the film (J. Am. Chem. Soc. 141 16734 2019). Newer results of the partners' demonstrate that a certain polymer design allows H2 oxidation and production to occur in the same film (Nature Catalysis 4 251 2021). This new result opens the possibility for a distinct protection concept, explored in PROSECCO, which should allow the protection of O2-sensitive catalysts under reductive conditions (e.g. for catalytic H2 evolution or CO2 reduction). This new protection mechanism requires that a fraction of the H2 that is catalytically produced near the electrode is reoxidized near the film/solution interface to eliminate the O2 molecules that attempt to penetrate the film. We will explore this protection strategy in the project, after having screened and optimized polymers and metalloenzymes that transform H2 or CO2 (task 1), and developed the kinetic models of bidirectional mediated catalysis in thin films in the absence of O2 (task 2). In task 3 we will explore the effect of O2 both experimentally and theoretically, using fragile but very efficient biological bidirectional catalysts of H2 production and CO2 reduction. We will use an approach that combines the expertise of the two partners in biochemistry (production and optimization of metalloenzymes), synthetic chemistry (redox polymers and dendrimers), physical chemistry (electrochemical characterization of the redox films) and modelisation (numerical and analytical and resolution of reaction-diffusion systems). Task 2 will deliver a very important and general piece of knowledge for the electrochemistry and catalysis scientific communities, which appears to be very timely when one considers the current interest in reversible catalysis (Fourmond et al, Nat. Rev. Chem. in press 2021). The results of Task 3 will also be useful and general, since we anticipate that the new protection strategy will prove operational for enzymes but also for O2-sensitive synthetic inorganic catalysts of very important reactions in the context of environment and energy.

涉及二氢和CO2的能量转换方案的实施需要防止基于廉价且丰富的过渡金属的生物或合成催化剂被氧灭活的解决方案。该项目的合作伙伴最近开发了一种在有氧条件下使用H2氧化的O2敏感催化剂的策略，该策略包括将催化剂嵌入精心设计的微米厚氧化还原聚合物膜中，该氧化还原聚合物膜支撑在电极中。他们表明，自保护的发生是因为除了电极附近的催化氢氧化之外，一部分进入的H2在膜/溶液界面附近被催化氧化以减少渗透膜的O2分子（J. Am. 141 16734 2019）。合作伙伴的新结果表明，某种聚合物设计允许在同一膜中发生H2氧化和生产（Nature Catalysis 4 251 2021）。这一新结果为PROSECCO中探索的独特保护概念提供了可能性，该概念应允许在还原条件下保护O2敏感性催化剂（例如催化H2释放或CO2还原）。这种新的保护机制要求在电极附近催化产生的一部分H2在膜/溶液界面附近被再氧化，以消除试图穿透膜的O2分子。我们将在项目中探索这种保护策略，在筛选和优化转化H2或CO2的聚合物和金属酶（任务1）之后，并在没有O2的情况下开发薄膜中双向介导催化的动力学模型（任务2）。在任务3中，我们将在实验和理论上探索O2的影响，使用脆弱但非常有效的生物双向催化剂H2生产和CO2还原。我们将使用一种方法，结合生物化学（金属酶的生产和优化），合成化学（氧化还原聚合物和树枝状聚合物），物理化学（氧化还原膜的电化学表征）和建模（反应扩散系统的数值和分析和分辨率）的两个合作伙伴的专业知识。任务2将为电化学和催化科学界提供一个非常重要和一般的知识，当人们考虑到目前对可逆催化的兴趣时，这似乎是非常及时的（Fourmond et al，Nat. Rev. Chem. in press 2021）。任务3的结果也将是有用的和一般的，因为我们预计，新的保护策略将证明可操作的酶，但也为O2敏感的合成无机催化剂的非常重要的反应，在环境和能源的背景下。