Investigation of Metal Organic Frameworks for Renewable Energy Electrocatalysis

可再生能源利用催化剂的开发是一个紧迫的全球性问题。我的研究计划的目标是研究电催化金属有机框架（MOFs），其具有合理设计的三维催化活性口袋，用于将电力转化为燃料和化学品。我的目标是证明，有效地驱动反应从CO2和H2O的起始材料所需的产品（即CH 3OH，CH 4，CH 3CH 2 OH。）可以通过建立包含酶激发反应效应的基于MOF的电化学系统来实现。这些包括中间稳定，质子中继，和多个反应物结合位点内的限制，分子可调的催化环境的MOFs。一个例子是使用用氨基官能化的MOF通过氢键相互作用稳定高能中间体并使反应自由能景观平坦化以加速催化。长期（3-5年）目标包括结合近端活性位点，以促进反应物二聚化，从而驱动反应途径从CO2生成C2产物。此外，还将开展纳米@MOF核@壳材料的研究。这样的系统允许独立调节纳米颗粒催化活性表面和由MOF壳赋予的直接反应环境。通过利用多孔MOFs作为分子可调的电催化材料，结合了非均相（调谐）和均相（活性，稳定性）催化剂的优势，同时还将一种新的生物启发元素纳入研究。为了实现所提出的材料，我的研究团队将通过直接在导电衬底上生长MOF薄膜来构建MOF电极。这些MOF电极将直接用于在水性电化学电池中催化CO-2还原。它们的活性和选择性将通过电化学方法以及气相色谱和NMR的组合来检测反应产物进行评估。在串联的MOF电催化剂的合成和表征，在整个操作过程中的MOF功能的光谱和电分析研究将进行。这类研究旨在原位提取反应途径、中间体和催化剂活性相的机理信息。这将提供关于生物启发效应如何影响反应性的直接信息。这里提出的研究整合了无机化学，纳米科学，催化和光谱学。因此，在这一框架内从事项目工作的总部合格人员将接受加拿大学术界和工业界高需求领域的培训。从科学角度来看，这项工作将产生对利用封闭环境控制电催化的基本理解，同时提供将电力转化为燃料和化学品的途径。

Catalyst development for renewable energy utilization is a pressing global issue. The goal for my research program is to investigate electrocatalytic metal organic frameworks (MOFs) with rationally designed three dimensional catalytically active pockets for conversion of electricity to fuels and chemicals. My objective is to demonstrate that efficiently driving reactions from CO2 and H2O starting materials to the desired products (i.e. CH3OH, CH4, CH3CH2OH.) can be accomplished by establishing MOF-based electrochemical systems that incorporate enzyme-inspired reaction effects. These include intermediate stabilization, proton relays, and multiple reactant binding sites within the confined, molecularly tunable catalytic environments of the MOFs. An example is the use of a MOF functionalized with amino groups to stabilize high energy intermediates through hydrogen-bonding interactions and flatten the reaction free energy landscape to accelerate catalysis. Longer term (3-5 year) goals include incorporating proximal active sites to facilitate reactant dimerization to drive the reaction pathway towards C2 products from CO2. In addition, the invesitgation of nanoparticle@MOF core@shell materials will be undertaken. Such systems allow for independent tuning of a nanoparticle catalytically active surface and the immediate reaction environment conferred by the MOF shell. By utilizing the porous MOFs as molecularly tunable electrocatalytic materials, the strengths of heterogeneous (tuneability) and homogeneous (activity, stability) catalysts are combined while also incorporating a new bio-inspired element into the research. To realize the proposed materials, my research team will construct MOF-electrodes by growing MOF thin films directly on conductive substrates. These MOF electrodes will be used directly to catalyze CO-2 reduction in an aqueous electrochemical cell. Their activity and selectivity will be evaluated with electrochemical methods and with a combination of gas chromatography and NMR to detect reaction products. In tandem to synthesis and characterization of MOF electrocatalysts, spectroscopic and electroanalytical studies of the MOF function throughout the course of operation will be carried out. Such studies aim to extract mechanistic information of reaction pathways, intermediates and catalysts' active phase in-situ. This will provide direct information regarding how the bio-inspired effects affect reactivity. The research proposed here integrates inorganic chemistry, nanoscience, catalysis and spectroscopy. As such, HQPs working on the projects within this framework will receive training in areas of high demand in both academic and industry settings in Canada. Scientifically, this work will generate a fundamental understanding towards utilizing confined environments in controlling electrocatalysis while simultaneously offering pathways for conversion of electricity to fuels and chemicals.