Hydrogel shields to support and protect catalysts of H2 oxidation and CO2 reduction.

水凝胶屏蔽支持和保护 H2 氧化和 CO2 还原催化剂。

• 批准号: 283974326
• 负责人: Professor Dr. Nicolas Plumeré
• 金额: --
• 依托单位: Agence Nationale de la Recherche
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/283974326?language=en
• 关键词: Hydrogel; shields; support; protect; catalysts

The use of metalloenzymes or synthetic inorganic complexes as catalysts in fuels cells or photoelectrochemical cells may open key routes in energy production and in industrial synthesis. However, the intrinsic fragility and oxygen sensitivity of these catalysts has been an obstacle. The German partner in this project has recently demonstrated that hydrogenases, the very efficient but very fragile biological catalysts of H2 oxidation, could be protected from O2 damage upon integration into a specifically designed redox hydrogel, which reduces oxygen at the polymer surface and thus provides self-activated protection from oxygen [Plumeré et al, Nature Chemistry, 2014]. Following the publication of this result, the French and German partners have initiated a collaboration, which already proved fruitful [Fourmond et al, J. Am. Chem Soc., 2015], to rationalize the protection mechanism and optimize the design of the catalyst-polymer films. These recently published results have set the stage for the full investigation that is the goal of this international and interdisciplinary ANR/DFG project.We plan to explore this new concept by examining a variety of configurations (oxidative or reductive catalysis in thick or thin films), using enzymes such as hydrogenases and CO dehydrogenases as models of fragile catalysts. The enzymes, which will be prepared by the French partner, have been selected because they exhibit various properties (reversible or irreversible catalysis, reversible or irreversible inhibition by O2, rates of inactivation and reactivation that can be tuned by protein engineering). A tight collaboration between the two partners is absolutely crucial in this project because understanding how the hydrogel protects the catalysts requires that the kinetic and geometrical properties of the film be determined, and used in realistic mathematical models that take into account the various chemical reactions and diffusion processes occurring in the depth of the film; the models should then be validated by experimental measurements of how the presence of O2 affects the catalytic current, before the knowledge that has been acquired is used to guide the new design of the film (hydrophobicity of the polymer backbone, redox potential of the redox moieties, thickness, load, etc.). The two partners have demonstrated that they have the right expertise to accomplish their parts in the project, and that they can unite their force and knowledge (biochemistry and mathematical modelling in France, polymer design and physical electrochemistry in Germany) by working together.Our ultimate goal is to fully understand the function of these complex systems where the catalysts is embedded into a protective redox-active hydrogel, in order to achieve the best compromise between overall performance, catalyst use and resistance to O2, and thus maximize the utilisation of the catalyst.

在燃料电池或光电化学电池中使用金属酶或合成无机络合物作为催化剂可能会打开能源生产和工业合成的关键路线。然而，这些催化剂固有的脆性和氧敏感性一直是一个障碍。该项目的德国合作伙伴最近证明，氢化酶是H2氧化的非常有效但非常脆弱的生物催化剂，在整合到专门设计的氧化还原水凝胶中后，可以保护其免受O2损伤，该水凝胶减少聚合物表面的氧，从而提供自激活的氧气保护[Plumeré et al，Nature Chemistry，2014]。在该结果发表之后，法国和德国合作伙伴发起了一项合作，该合作已经证明是富有成效的[Fourmond等人，J. Am.化学学会，2015]，使保护机制合理化并优化催化剂-聚合物膜的设计。这些最近发表的结果已经为全面调查奠定了基础，这是这个国际和跨学科ANR/DFG项目的目标。我们计划通过检查各种配置（厚膜或薄膜中的氧化或还原催化）来探索这一新概念，使用酶，如氢化酶和CO还原酶作为易碎催化剂的模型。选择将由法国合作伙伴制备的酶是因为它们具有各种特性（可逆或不可逆的催化作用，O2的可逆或不可逆抑制作用，可以通过蛋白质工程调节的失活和再活化速率）。这两个合作伙伴之间的紧密合作在该项目中至关重要，因为要了解水凝胶如何保护催化剂，就需要确定薄膜的动力学和几何特性，并将其用于现实的数学模型中，这些模型考虑到薄膜深度中发生的各种化学反应和扩散过程;然后，在利用已经获得的知识指导新的薄膜设计之前，应该通过实验测量来验证这些模型，以确定O2的存在如何影响催化电流（聚合物主链的疏水性、氧化还原部分的氧化还原电位、厚度、负载等）。这两个合作伙伴已经证明，他们有正确的专业知识来完成他们在项目中的部分，他们可以团结他们的力量和知识（法国的生物化学和数学建模，德国的聚合物设计和物理电化学）。我们的最终目标是充分了解这些复杂系统的功能，其中催化剂嵌入到保护性氧化还原活性水凝胶中，以便在总体性能、催化剂使用和耐O2性之间实现最佳折衷，从而使催化剂的利用率最大化。

项目成果

A novel versatile microbiosensor for local hydrogen detection by means of scanning photoelectrochemical microscopy.

• DOI: 10.1016/j.bios.2017.03.037
• 发表时间: 2017-08
• 期刊: Biosensors & bioelectronics
• 影响因子: 12.6
• 作者: Fangyuan Zhao;F. Conzuelo;Volker Hartmann;Huaiguang Li;Stefanie Stapf;M. Nowaczyk;M. Rögner;N. Plumeré;W. Lubitz;W. Schuhmann

Complete Protection of O2-Sensitive Catalysts in Thin Films

• DOI: 10.1021/jacs.9b06790
• 发表时间: 2019-10-23
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Li, Huaiguang;Buesen, Darren;Plumere, Nicolas
• 通讯作者: Plumere, Nicolas

Protection and Reactivation of the [NiFeSe] Hydrogenase from Desulfovibrio vulgaris Hildenborough under Oxidative Conditions

• DOI: 10.1021/acsenergylett.7b00167
• 发表时间: 2017-05-01
• 期刊: ACS ENERGY LETTERS
• 影响因子: 22
• 作者: Ruff, Adrian;Szczesny, Julian;Schuhmann, Wolfgang
• 通讯作者: Schuhmann, Wolfgang