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（mof），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，通过建立基于mof的电化学系统，结合酶激发的反应效应，可以有效地驱动从CO2和H2O原料到所需产物（即CH3OH， CH4, CH3CH2OH）的反应。这些包括中间稳定，质子继电器，以及在受限的，分子可调的mof催化环境中的多个反应物结合位点。一个例子是使用氨基功能化的MOF通过氢键相互作用稳定高能量中间体，并使反应自由能景观平坦以加速催化。长期（3-5年）目标包括纳入近端活性位点，以促进反应物二聚化，推动反应途径从CO2生成C2产物。此外，还将对nanoparticle@MOF core@shell资料进行调查。这样的系统允许独立调整纳米粒子催化活性表面和MOF壳赋予的直接反应环境。通过利用多孔mof作为分子可调谐的电催化材料，将非均相（可调谐）和均相（活性、稳定性）催化剂的优势结合起来，同时也将一种新的生物启发元素纳入研究中。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电极将直接用于催化水电化学电池中CO-2的还原。它们的活性和选择性将用电化学方法进行评估，并结合气相色谱和核磁共振来检测反应产物。在合成和表征MOF电催化剂的同时，将对整个操作过程中的MOF功能进行光谱和电分析研究。这些研究旨在现场提取反应途径、中间体和催化剂活性相的机理信息。这将提供关于生物激发效应如何影响反应性的直接信息。这里提出的研究综合无机化学，纳米科学，催化和光谱学。因此，在这一框架内从事项目的HQPs将在加拿大学术和工业环境的高需求领域接受培训。从科学上讲，这项工作将产生对利用有限环境来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.