Integrating polyoxometalate-single atom catalyst based (photo-) electrodes in flow reactors for reductive and oxidative nitrogen activation

将多金属氧酸盐-单原子催化剂基（光）电极集成到流动反应器中以进行还原和氧化氮活化

• 批准号: 501934135
• 负责人: Professor Dr. Carsten Streb
• 金额: --
• 依托单位: Department Chemie
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/501934135?language=en
• 关键词: Integrating; polyoxometalate; single; atom; catalyst

In this project, we propose the development of photo-electrochemically driven reactors capable of coupling the nitrogen-to-ammonium reduction reaction (NRR) and the nitrogen-to nitrate oxidation reaction (NOR), leading to autonomous flow photoreactors for ammonium nitrate production from nitrogen, water, sunlight, and sustainable electricity. The project combines concepts from novel catalyst synthesis and stable electrode deposition to reactor design and materials-in-reactor integration. The project combines expertise in metal oxide catalysts and (photo-)electrode functionalization (PI Streb) with expertise in reaction engineering, mass transport optimization and photoreactor design (PI Ziegenbalg). In the first funding period (36 months), the project will develop noble-metal-free single atom catalysts (SACs, 1 metal reaction center) and single-site catalysts (SSCs 2 metal reaction centers) anchored to molecular metal oxides (polyoxometalates, POMs). Variation of the SAC/SSC metal sites will allow control of NRR/NOR performance, while POM-anchoring will provide a stable, well-defined all-oxo coordination environment. Deposition of these molecular precursors on high-porosity (photo-)electrodes is achieved by wet-chemical, microwave or hydrothermal POM-conversion to solid-state oxides to facilitate stable mechanical and electrical linkage between catalyst and electrode. Electrode integration into 3D-printed flow photoreactors will enable rapid prototyping and fast matching of chemical and reaction-engineering requirements. The systems will be studied by in situ/operando (photo-)electrochemical studies and – in collaboration – by theoretical modelling. This will provide insights from the atomic to the reactor-level on the catalytic performance, its limitations, and enable us to identify key optimization parameters. The first funding period is focused on studying NRR and NOR in half-cell setups for mechanistic investigations and materials design/optimization, while the second funding period will target the integrated full-cell photoreactors. In sum, this project will develop flow photoreactors for decentralized ammonium nitrate production starting from molecular nitrogen, and uses modern materials design, advanced electrode fabrication and reaction engineering to address challenges from the molecular to the reactor level.

在这个项目中，我们提出了光电化学驱动的反应器的发展，能够耦合的氮到铵还原反应（NRR）和氮到硝酸盐氧化反应（NOR），导致自主流光反应器硝酸铵生产从氮，水，阳光，和可持续的电力。该项目结合了从新型催化剂合成和稳定电极沉积到反应器设计和反应器中材料集成的概念。该项目将金属氧化物催化剂和（光）电极功能化（PI Streb）的专业知识与反应工程，传质优化和光反应器设计（PI Ziegenbalg）的专业知识相结合。在第一个资助期（36个月），该项目将开发无贵金属的单原子催化剂（SAC，1个金属反应中心）和固定在分子金属氧化物（多氧酸盐，POM）上的单活性中心催化剂（SSC 2个金属反应中心）。SAC/SSC金属位点的变化将允许控制NRR/NOR性能，而POM锚定将提供稳定的、明确定义的全氧配位环境。这些分子前体在高孔隙率（光）电极上的沉积通过湿化学、微波或水热POM转化成固态氧化物来实现，以促进催化剂和电极之间的稳定机械和电连接。将电极集成到3D打印的流动光反应器中，将能够实现快速原型制作，并快速匹配化学和反应工程要求。该系统将进行研究，在现场/operando（光）电化学研究和-在合作-通过理论建模。这将提供从原子到反应器级别的催化性能及其局限性的见解，并使我们能够确定关键的优化参数。第一个资助期的重点是研究半电池设置中的NRR和NOR，用于机械研究和材料设计/优化，而第二个资助期将针对集成全电池光反应器。总之，该项目将开发用于从分子氮开始分散生产硝酸铵的流动光反应器，并使用现代材料设计，先进的电极制造和反应工程来解决从分子到反应器水平的挑战。