Electrocatalytic Coordination Networks

多孔配位网络(PCN)是选择性电催化转化的理想候选者，因为它们能够实现孔内小分子的高度选择性吸附分离，同时整合来自作为节点的过渡金属或产生可调氧化还原功能的掺杂剂的催化活性中心作为电催化配位网络的构建块。在第一个资助阶段开发的PCN作为高活性和选择性的电催化剂，但是现有CN体系的电导率的局限性和一些CNS对水溶液的不稳定性表明有必要探索新的PCN电催化剂的合成。作为一项技术挑战，将此类材料加工成薄膜电极是获得高性能催化剂的关键要求。电催化产生有价值的中间体，为利用可再生资源波动的能源供应中产生的低成本电能提供了巨大的潜力。电催化减少二氧化碳(CO2RR)等温室气体，并将其转化为甲醇和甲烷等有价值的燃料是一个很有前途的目标。氮气电还原(NRR)是降低化肥生产能耗的一个富有远见的目标。此外，对于精细化学中间体，例如从生物质中提取的多元醇的选择性氧化，预计高选择性碳纳米管具有很高的潜力。该项目将开发下一代电子导电配位网络(ECN)及其在电极中的集成用于电催化，其中CNs提高了产物的选择性，电子转移要么通过i)配位网络本身实现，要么通过ii)催化活性纳米材料(NM：纳米颗粒、石墨烯表面、MXene等)实现。使用复合方法。在跨学科的方法中，该项目将涵盖整个过程链，从分子构件的设计和合成、ECN的合成、所需工艺的开发和先进的现场表征技术，到选定的电催化模型反应的功能演示，包括二氧化碳和氮气的电还原和用于生产精细化学品的多元醇电氧化。

Porous coordination networks (PCNs) are ideal candidates for selective electrocatalytic transformations since they enable highly selective adsorptive separations of small molecules inside pores and at the same time the integration of catalytically active sites, originating from transition metals as nodes or dopants generating tunable redox functions as building blocks in electrocatalytic coordination networks. PCNs developed in the 1st funding phase perform as highly active and selective electrocatalysts, however limitations in electrical conductivity for established CN systems and the instability of some CNs towards aqueous electrolytes reveal the need for exploring the synthesis of new PCN electrocatalysts. As a technical challenge, processing such materials into thin film electrodes is a key requirement to achieve high performance catalysts. Electrocatalysis for the generation of valuable intermediates poses a huge potential for the use of low-cost electrical energy emerging from the fluctuating energy supply of renewable resources. Electrocatalytic reduction of greenhouse gases such as CO2 (CO2RR) and conversion into valuable fuels such as methanol and methane is a promising target. Electroreduction of N2 (NRR) is a visionary target to reduce energy consumption for fertilizer production. Moreover a high potential of highly selective CNs is anticipated for fine chemical intermediates, for example the selective oxidation of polyols derived from biomass. This project will develop the next generation of electronically conductive coordination networks (ECNs) and their integration into electrodes for electrocatalysis where the CN enhances the product selectivity and the electron transfer is realized either by the I) coordination network itself, or II) a catalytically active nanomaterial (NM: nanoparticle, graphene surface, MXene etc.) using a composite approach. In an interdisciplinary approach the project will cover the whole process chain from the design and synthesis of molecular building blocks, ECN synthesis, development of required processing and advanced in situ-characterization techniques towards function demonstration in selected electrocatalytic model reactions including, CO2 and N2 electroreduction and polyol electrooxidation for the production of fine chemicals.