Investigation of Metal Organic Frameworks for Renewable Energy Electrocatalysis

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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.