Advanced nanostructured materials for energy storage and conversion
Date
2015
Authors
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Publisher
University of Delaware
Abstract
Due to a global effort to reduce greenhouse gas emissions and to utilize renewable sources of energy, much effort has been directed towards creating new alternatives to fossil fuels. Identifying novel materials for energy storage and conversion can enable radical changes to the current fuel production infrastructure and energy utilization. The use of engineered nanostructured materials in these systems unlocks unique catalytic activity in practical configurations. In this work, research efforts have been focused on the development of nanostructured materials to address the need for both better energy conversion and storage, with applications toward Li-O2 battery electrocatalysts, electrocatalytic generation of H2, conversion of furfural to useful chemicals and fuels, and Li battery anode materials. Highly-active α-MnO2 materials were synthesized for use as bifunctional oxygen reduction (ORR) and evolution (OER) catalysts in Li-O2 batteries, and were evaluated under operating conditions with a novel in situ X-ray absorption spectroscopy configuration. Through detailed analysis of local coordination and oxidation states of Mn atoms at key points in the electrochemical cycle, a self-switching behavior affecting the bifunctional activity was identified and found to be critical. In an additional study of materials for lithium batteries, nanostructured TiO2 anode materials doped with first-row transition metals were synthesized and evaluated for improving battery discharge capacity and rate performance, with Ni and Co doping at low levels found to cause the greatest enhancement. In addition to battery technology research, I have also sought to find inexpensive and earth-abundant electrocatalysts to replace state-of-the-art Pt/C in the hydrogen evolution reaction (HER), a systematic computational study of Cu-based bimetallic electrocatalysts was performed. During the screening of dilute surface alloys of Cu mixed with other first-row transition metals, materials with ideal hydrogen binding energies were identified. Bulk alloy electrocatalysts with comparable compositions to the model surfaces were synthesized and tested for performance in alkaline, neutral, and acidic conditions. Cu-Ti was found to exhibit the lowest overpotentials and highest overall performance, and was redesigned as a nanoporous catalyst which achieved higher current at lower overpotentials than even commercial Pt/C, with remarkably high stability. Through applying design principles developed during the HER work, self-supported nanoporous Cu-Co alloy catalysts were synthesized for the improvement of product selectivity and overall conversion of reactants in furfural hydro(deoxy)genation. Under vapor-phase reaction conditions, it was found that adding 1% to 10% oxophilic Co in a solid solution with Cu enhanced overall conversion towards products. In particular, a Cu95Co5 alloy produced 64.9% yield of 2-methylfuran at a high sustained total conversion of 85.0% and under moderate temperature conditions, which is the highest 2-methylfuran production reported for non-precious catalysts. Further analysis at a wider range of temperature conditions and sustained reaction time on stream provided a more detailed understanding of the behavior of these nanoporous materials, and possible mechanistic explanations of the high activity for Cu-Co are proposed to aid in the design of new materials with even higher product selectivities. Future directions will include tracking the catalyst state in situ with X-ray absorption spectroscopy and computational assessment of the surface reaction mechanisms.