Investigation of Metal Organic Frameworks for Renewable Energy Electrocatalysis

开发利用可再生能源的催化剂是一个紧迫的全球问题。我的研究计划的目标是研究具有合理设计的三维催化活性口袋的电催化金属有机骨架(MOF)，用于将电力转化为燃料和化学品。我的目标是证明有效地推动反应从二氧化碳和水的起始物质到所需的产品(即CH3OH，CH4，CH3CH2OH)。可以通过建立包含酶激发的反应效果的基于MOF的电化学系统来实现。这些包括中间稳定，质子接力，以及在受限的分子可调催化环境中的多个反应物结合位置。一个例子是使用带有氨基的MOF通过氢键相互作用稳定高能中间体，并使反应自由能图景变平以加速催化。较长期(3-5年)的目标包括结合近端活性中心以促进反应物二聚，以推动从二氧化碳到C2产物的反应途径。此外，还将开展纳米级MOF核壳材料的研究。这种系统允许对纳米颗粒催化活性表面和MOF壳层提供的即时反应环境进行独立调节。通过利用多孔MOF作为分子可调的电催化材料，结合了多相(可调性)和均相(活性、稳定性)催化剂的优点，同时还在研究中加入了一种新的生物启发元素。为了实现所提出的材料，我的研究团队将通过在导电衬底上直接生长MOF薄膜来构建MOF电极。这些MOF电极将直接用于催化水中电化学电池中的CO-2还原。它们的活性和选择性将用电化学方法进行评估，并用气相色谱和核磁共振相结合的方法检测反应产物。在合成和表征MOF电催化剂的同时，将对MOF在整个操作过程中的作用进行光谱和电分析研究。这类研究旨在现场提取反应路径、中间体和催化剂活性相的机理信息。这将提供有关生物启发效应如何影响反应性的直接信息。本文提出的研究集无机化学、纳米科学、催化和光谱学于一体。因此，在这一框架内从事项目工作的HQP将在加拿大学术界和行业环境中需求较高的领域接受培训。从科学上讲，这项工作将产生对利用受限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.