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.

尽管过去几年在可见光光催化剂的性能中取得了重大进展，但必须提高耐用性和翻转数字以达到应用，并且二氧化基因和二氢生成步骤的结合仍然是一个挑战。用于水分解的分子光催化剂通常由几个组成部分组成。我们提出了将光活性两亲成分共同插入水 - 脂质界面处的膜结构，从而使组件容易组装，使多组分催化剂系统的两个维度阵列具有两个维度的阵列。界面处的催化剂亚基的近距离和局部浓度高会增加光催化性能。嵌入式染料，催化剂和膜两亲物组成的简单变化允许快速优化多组分催化剂。根据所施加的两亲性的性质，化合物在界面处的空间分布可能会影响导致高活性的催化剂斑块。由于组件的动态性质，聚集体的自我修复应导致光催化剂的稳定性延长。催化剂属于当前已知的最佳性能系统。德国群体具有金属络合物膜嵌入和使用有机染料作为光传感器的经验。理想的完整专业知识将结合使用，以开发具有嵌入式多组分光催化剂的功能化蔬菜和机制，并优化其性能。一项已经完成的联合初步研究表明，这种功能化的蔬菜使用蓝光显示了光催化水的氧化，并超过了均匀溶液中成分的性能。一部分金属复合物光催化剂将被氧化还原活性有机染料取代，以减少系统的整体金属含量。氢产生催化剂将被共插入以获得同时氧和氢产生的机制。功能化的蔬菜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。这将允许使用分层体系结构轻松制备复杂的多组分光活性设备。通过在参与小组和年度联合研讨会之间交换博士生和博士学位，可以确保项目内的知识转移和密集合作。

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

Functionalized membranes for photocatalytic hydrogen production.

• DOI: 10.1002/chem.201404480
• 发表时间: 2014-11
• 期刊: Chemistry
• 作者: Stefan Troppmann;B. König