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dc.contributor.authorElouarzaki, Kamalen_US
dc.contributor.authorWang, Yianen_US
dc.contributor.authorKannan, Vishvaken_US
dc.contributor.authorXu, Haoxiangen_US
dc.contributor.authorCheng, Daojianen_US
dc.contributor.authorLee, Jong-Minen_US
dc.contributor.authorFisher, Adrian C.en_US
dc.identifier.citationElouarzaki, K., Wang, Y., Kannan, V., Xu, H., Cheng, D., Lee, J. & Fisher, A. C. (2019). Hydrogenase-like electrocatalytic activation and inactivation mechanism by three-dimensional binderless molecular catalyst. ACS Applied Energy Materials, 2(5), 3352-3362.
dc.description.abstractIn response to issues raised by modern energy challenges, molecular electrocatalysis is currently attracting a lot of attention to the tailoring of "model" catalysts, notably understanding the mechanisms and kinetic and thermodynamic parameters that occur during a catalytic reaction. In this regard, nature offers extremely efficient enzymes called hydrogenases. These enzymes that catalyze the reversible interconversions between H₂ and H⁺ at high turnover rates are inactivated by O₂. This inactivation yields odd cyclic voltammetric responses originating from a chemical inactivation-redox activation process (IAP). Although IAP has been extensively studied for hydrogenases, their catalytic mechanism is not fully understood because of the intricate but necessary electrical wiring, desorption, and complex biochemical environment required. Here, we report a unique example of IAP based on a nonenzymatic catalyst prepared by mixing rhodium-porphyrinic catalyst and an interconnected multiwalled carbon nanotubes matrix which presents an excellent and stable electron transfer. We combined organic synthesis, electrochemistry, mathematical models, and density functional theory calculations to uncover the molecular IAP at the catalytic metallic site. We present a mechanistic analysis of the noncatalytic and catalytic responses exhibited by this complex, enabling a comprehensive understanding of the thermodynamic and kinetic parameters that govern the IAP. These stepwise studies support a mechanism for glucose oxidation that proceeds most likely through an EC′CE scheme with catalytic steps similar to the ones reported for NiFe hydrogenases. The overall mechanism of the molecular IAP was detailed on the basis of our experimentally validated models and compared to NiFe hydrogenase IAP. Our findings offer novel perspectives to design finely optimized catalysts by eliminating the inactivation phenomena.en_US
dc.description.sponsorshipNational Research Foundation (NRF)en_US
dc.relation.ispartofACS Applied Energy Materialsen_US
dc.rights© 2019 American Chemical Society. All rights reserved.en_US
dc.subjectEngineering::Chemical engineeringen_US
dc.titleHydrogenase-like electrocatalytic activation and inactivation mechanism by three-dimensional binderless molecular catalysten_US
dc.typeJournal Articleen
dc.contributor.schoolSchool of Chemical and Biomedical Engineeringen_US
dc.contributor.organizationCambridge CARESen_US
dc.subject.keywordsMolecular Catalysten_US
dc.description.acknowledgementThis project is funded by the National Research Foundation (NRF), Prime Minister’s Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) program.en_US
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