Optimizing conditions for utilization of an H2 oxidation catalyst with outer coordination sphere functionalities

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dc.contributor.author Dutta, Arnab
dc.contributor.author Ginovska, Bojana
dc.contributor.author Raugei, Simone
dc.contributor.author Roberts, John A. S.
dc.contributor.author Shaw, Wendy J.
dc.date.accessioned 2016-03-16T17:08:10Z
dc.date.available 2016-03-16T17:08:10Z
dc.date.issued 2016-02
dc.identifier.citation Dutta, Arnab; Ginovska, Bojana; Raugei, Simone; Roberts, John A. S. and Shaw, Wendy J., “Optimizing conditions for utilization of an H2 oxidation catalyst with outer coordination sphere functionalities”, Dalton Transactions, DOI: 10.1039/C6DT00280C, vol. 45, no. 24, pp. 9786-9793, Feb. 2016.
dc.identifier.issn 1477-9226
dc.identifier.uri http://dx.doi.org/10.1039/C6DT00280C
dc.identifier.uri https://repository.iitgn.ac.in/handle/123456789/2123
dc.description.abstract As a starting point for evaluating a broader range of conditions for H2 oxidation complexes, in this work we investigate an efficient and reversible Ni-based H2 oxidation and production complex with an arginine in the outer coordination sphere, [Ni(PCy2NArginine2)2]7+ (CyArg). We tested this complex under a wide range of pressures and temperatures, in two different solvents (methanol and water), to determine if simultaneous improvements in rate and overpotential could be achieved. We found that the optimal conditions combined both high temperature (72 °C) and pressure (100 atm H2) in acidic aqueous solution (pH = 1), resulting in the fastest H2 oxidation reported for any homogeneous electrocatalyst to date (TOF 1.1 × 106 s−1) operating at 240 mV overpotential. The activation free energy in water was determined to be 10 kcal mol−1 at all pressures studied. Surprisingly, in methanol under the same temperature and pressure, CyArg had a TOF for H2 oxidation of only 280 s−1 at an overpotential of 750 mV. Comparisons to the data in water, and to a control complex, [Ni(PCy2NBenzyl2)2]2+ (CyBn; Bn = benzyl), suggest that this substantial difference is likely due to a change in rate limiting step from H2 addition to deprotonation. Importantly, the optimal conditions we identified for CyArg (elevated temperature and acidic aqueous solutions), are amenable to fuel cell technologies and provide an important advancement in implementing homogeneous synthetic catalysts for renewable energy. en_US
dc.description.statementofresponsibility by Arnab Dutta, Bojana Ginovska, Simone Raugei, John A. S. Roberts and Wendy J. Shaw
dc.format.extent vol. 45, no. 24, pp. 9786-9793
dc.language.iso en_US en_US
dc.publisher Royal Society of chemistry en_US
dc.subject H2 oxidation en_US
dc.subject Outer coordination en_US
dc.subject Sphere functionalities en_US
dc.title Optimizing conditions for utilization of an H2 oxidation catalyst with outer coordination sphere functionalities en_US
dc.type Article en_US
dc.relation.journal Dalton Transactions


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