Photoelectrocatalysis with Porous Coordination Polymers - Architectural Design, Morphology Control and Transport Properties

多孔配位聚合物光电催化——结构设计、形态控制和传输特性

• 批准号: 316685525
• 负责人: Dr. Matthias Thomas Elm
• 金额: --
• 依托单位: Max-Planck-Institut für Festkörperforschung (MPI-FKF)
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/316685525?language=en
• 关键词: Photoelectrocatalysis; Porous; Coordination; Polymers; Architectural

The overall goal of this project is to establish an integrated metal-organic framework (MOF) platform for photoelectrocatalytic water splitting to overcome the need for sacrificial donor/acceptor schemes prevailing in particulate systems. Our approach thus addresses the uncharted interface between MOF photocatalysis and electrocatalysis by elucidating and controlling the very fundamentals of light-driven charge transport and redox catalysis in bio-inspired MOF-co-catalyst hybrid architectures based on porphyrin linkers. A prerequisite for the design of efficient photoelectrochemical cells will be the development of (i) highly porous MOF systems with light harvesting and electronically communicating subunits, and of (ii) synthesis strategies for high quality homogeneous, oriented MOF thin film electrodes. Our approach will be guided by insights into structure, dynamics, optical characteristics and electronic as well as ionic transport properties of the MOF films by solid-state NMR spectroscopy and impedance spectroscopy, as well as (photo)electrochemical analysis of the light-induced redox processes, feeding back into the design loop to create MOF photoelectrodes with high activity for hydrogen and oxygen evolution, reduced overpotentials and long-term stability. To accomplish this highly interdisciplinary task the research groups of B. V. Lotsch, M. T. Elm and J. Senker add their complementary skills in the synthesis and characterization of structural and transport properties. The Lotsch group has long standing expertise on the synthesis of MOF nanomaterials, the growth of MOF thin films and their post-synthetic modification of MOFs. The Lotsch group will develop photoactive porphyrin- and pyrene-based MOF systems, which will be interfaced with molecular and heterogeneous co-catalysts to orchestrate the light-induced multi-electron redox processes, and cast into high quality thin film architectures. For the structure elucidation of the MOF architectures the Senker group will provide a large repertoire of state-of-the art NMR crystallographic strategies. A thin film NMR probe will be developed in his group to analyze the structural integrity and porosity of the MOF films, to characterize the impact of confinement on the catalytic conversion, and to study the mechanism of light-induced charge carrier generation, to follow their mobility, and to probe the localization of excitons/polarons. Complementary experiments are carried out by M. T. Elm who is an expert on characterizing the electronic and ionic transport properties based on (photo)electrochemical techniques including impedance spectroscopy in various environments. In this way the nature of charge carriers, their concentrations and long-range transport, as well as the influence of defects on the transport and efficiency of the catalytic conversion will be probed.

该项目的总体目标是建立一个集成的金属有机框架（MOF）平台，用于光电催化水分割，以克服在颗粒系统中占上风的牺牲供体/受体方案的需求。因此，我们的方法通过阐明并控制了基于生物启发的MOF-CO-CATALYST混合体系结构中的光驱动电荷转运和氧化还原催化的基本原理，从而解决了MOF光催化与电催化之间的未知界面。设计有效的光电化学细胞设计的先决条件是（i）具有光收集和电子通信亚基的高度多孔MOF系统的开发，以及（II）用于高质量同质，定向的MOF MOF薄膜电极的合成策略。我们的方法将通过对结构，动力学，光学特性和电子传输以及MOF膜的离子传输特性以及通过固态NMR光谱和阻抗光谱以及（照片）光化REDOX的电化学分析（照片）进行引导的指导。过程，回到设计循环中以创建具有高活性的MOF光电子，用于氢和氧气的演化，减少了电势和长期稳定性。为了完成这项高度跨学科的任务。 Lotsch小组在MOF纳米材料的合成，MOF薄膜的生长以及其MOF的合成后修饰方面具有长期的专业知识。 Lotsch组将开发基于光活化的卟啉和基于pyrene的MOF系统，该系统将与分子和异质共催化剂连接，以协调光诱导的多电子氧化还原过程，并铸造成高质量的薄膜体系结构。对于MOF体系结构的结构，Senker Group将提供大量的NMR晶体学策略。他的小组将开发薄膜NMR探针，以分析MOF膜的结构完整性和孔隙率，以表征约束对催化转化的影响，并研究光诱导的电荷载体产生的机制移动性，并探测激子/极性子的定位。互补实验是由M. T. Elm进行的，他是基于（照片）电化学技术（包括在各种环境中的阻抗光谱法）的电子和离子传输性能的专家。通过这种方式，将探测电荷载体的性质，它们的浓度和远距离运输，以及缺陷对催化转化率的运输和效率的影响。