Photochemical Water Splitting at Soft Interfaces

软界面处的光化学分解水

• 批准号: 232235263
• 负责人: Professor Dr. Burkhard König
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/232235263?language=en
• 关键词: Photochemical; Water; Splitting; Soft; Interfaces

Although significant progress was made over the last years in the performance of visible light photocatalysts for direct water splitting, durability and turn over numbers must be improved to reach applications and the combination of the dioxygen and the dihydrogen generating steps remains a challenge. Molecular photocatalysts for water splitting typically consist of several components. We proposed the co-embedding of photoactive amphiphilic components into membrane structures at the water-lipid interface allowing facile assembly of two dimensional arrays of multi-component catalyst systems. The close proximity and the high local concentration of the catalyst subunits at the interface increase the photocatalytic performance. Simple variation of the composition of the embed¬ded dyes, catalysts and membrane amphiphiles allows the rapid optimization of the multi component catalysts. Depending on the nature of the applied amphiphiles the spatial distribution of compounds at the interface can be influenced leading to catalyst patches of high activity. Due to the dynamic nature of the assemblies self-repair of the aggregates should lead to a prolonged stability of the photocatalysts.The Chinese applicants have developed metal complex based multi-component catalysts for visible light driven water oxidation and hydrogen generation. The catalysts belong to the best performing systems currently known. The German group has experience in membrane embedding of metal complexes and the use of organic dyes as photosensitizers. The ideally complementary expertise will be combined to develop functionalized vesicles and membranes with embedded multi-component photocatalysts and the optimization of their performance. An already completed joint initial study revealed that such functionalized vesicles show photocatalytic water oxidation using blue light and exceed the performance of the components in homogeneous solution. Part of the metal complex photocatalysts will be replaced by redox active organic dyes to reduce the overall metal content of the system. Hydrogen generating catalysts will be co-embedded to obtain membranes performing simultaneous oxygen and hydrogen generation. Functionalized vesicles will be investigated and optimized in homogeneous solution, and then transferred onto surfaces or processed using printing technology. This will allow the facile preparation of complex multi-component photoactive devices with hierarchical architecture. Knowledge transfer and intensive collaboration within the project is ensured by exchange of PhD students and postdocs between the participating groups and an annual joint workshop of the groups.

尽管在过去几年中在用于直接水裂解的可见光光催化剂的性能方面取得了显著进展，但必须改进耐久性和周转次数以达到应用，并且双氧和二氢产生步骤的组合仍然是一个挑战。用于水裂解的分子光催化剂通常由几种组分组成。我们提出了在水-脂质界面处将光敏两亲组分共嵌入膜结构中，从而允许多组分催化剂体系的二维阵列的容易组装。界面处催化剂亚单元的紧密接近和高局部浓度增加了光催化性能。嵌入染料、催化剂和膜两亲物的组成的简单变化允许多组分催化剂的快速优化。取决于所施加的两亲物的性质，化合物在界面处的空间分布可以受到影响，从而导致高活性的催化剂贴片。中国申请人已经开发了用于可见光驱动的水氧化和氢生成的基于金属络合物的多组分催化剂。该催化剂属于目前已知的性能最好的系统。该德国小组在金属络合物的膜包埋和使用有机染料作为光敏剂方面具有经验。理想的互补专业知识将结合起来，开发嵌入多组分光催化剂的功能化囊泡和膜，并优化其性能。一项已经完成的联合初步研究表明，这种功能化的囊泡显示出使用蓝光的光催化水氧化作用，并超过了均匀溶液中组分的性能。部分金属络合物光催化剂将被氧化还原活性有机染料取代，以降低系统的总金属含量。氢生成催化剂将被共嵌入以获得同时进行氧和氢生成的膜。功能化囊泡将在均匀溶液中进行研究和优化，然后转移到表面上或使用印刷技术进行处理。这将允许容易地制备具有分层结构的复杂的多组分光活性器件。通过参与小组之间交换博士生和博士后以及小组年度联合研讨会，确保了项目内的知识转移和密切合作。

项目成果

Light Upconverting soft particles: Triplet-triplet annihilation in the phospholipid bilayer of self-assembled vesicles

光上转换软粒子：自组装囊泡磷脂双层中的三重态-三重态湮灭

• DOI: 10.1039/c6ra07666a
• 发表时间: 2016
• 期刊: RSC Advances
• 影响因子: 3.9
• 作者: M. Poznik;U. Faltermeier;B. Dick;B. König
• 通讯作者: B. König

Functionalized Vesicles with Co‐Embedded CdSe Quantum Dots and [FeFe]‐Hydrogenase Mimic for Light‐Driven Hydrogen Production

• DOI: 10.1002/slct.201600032
• 发表时间: 2016-05
• 作者: Stefan Troppmann;B. König

Enhanced Photocatalytic Hydrogen Production by Adsorption of an [FeFe]‐Hydrogenase Subunit Mimic on Self‐Assembled Membranes

• DOI: 10.1002/ejic.201501377
• 发表时间: 2016-01
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: Stefan Troppmann;Evan B. Brandes;H. Motschmann;Fei Li;Mei Wang;Licheng Sun;B. König

Photocatalytic water oxidation at soft interfaces

• DOI: 10.1039/c4sc01018c
• 发表时间: 2014-01-01
• 期刊: CHEMICAL SCIENCE
• 影响因子: 8.4
• 作者: Hansen, Malte;Li, Fei;Koenig, Burkhard
• 通讯作者: Koenig, Burkhard

Immobilisation of water-oxidising amphiphilic ruthenium complexes on unmodified silica gel

水氧化两亲性钌络合物在未改性硅胶上的固定化

• DOI: 10.1039/c5ra24088c
• 发表时间: 2016
• 期刊: RSC Advances
• 影响因子: 3.9
• 作者: A. Králík;M. Hansen;B. König
• 通讯作者: B. König