Linker modulated peroxide electrosynthesis using metal-organic nanosheets
Kirankumar Kuruvinashetti a, Nikolay Kornienko a
a University of Montreal, Department of Chemistry, Montreal, Canada
Online Conference
Proceedings of International Conference on Electrocatalysis for Energy Applications and Sustainable Chemicals (EcoCat)
Online, Spain, 2020 November 23rd - 25th
Organizers: Ward van der Stam, Marta Costa Figueiredo, Sixto Gimenez Julia, Núria López and Bastian Mei
Poster, Kirankumar Kuruvinashetti, 056
Publication date: 6th November 2020

Electrochemical oxygen reduction has achieved significant importance as a promising substitute for the conventional anthraquinone production process of hydrogen peroxide. Electrochemical synthesis offers an economical and environmentally friendly route through either H2O or O2.  The electrosynthesis of H2O2 is a relatively unusual process because it involves reversible redox reactions of starting materials, intermediates, and products. Herein linker modulated Ni-based metal-organic nanosheets (Ni-MONs) catalysts for a cost-effective electrosynthesis of H2O2 through an emerging electrochemical approach by oxygen reduction reaction is discussed as a modular system. The electronic structure of the Ni active sites was tuned by constructing analogous Ni-MONs with electron-withdrawing groups - fluorine (Ni-F-MON) and electron-donating groups (hydroxyl, amine) (Ni-OH-MON, Ni-Amine-MON) grafter onto their linkers. The electronic structures were examined through a series of cyclic voltammetric experiments and X-ray photoelectron spectroscopy. Our interpretation is modifying the Ni electronic structure modulates the binding energy to the *OOH intermediate. Further, the electron-donating group of hydroxyl and amine linkers has increased the electronic density of the Ni2+. Amongst the Ni-MONs studied, the Ni-MONs with an electron-donating group –hydroxyl and amine have demonstrated higher activity and selectivity (> 90 ±3 %)  towards the H2O2. Our understanding is that electron-donating groups ( hydroxyl and amine) linkers regulated the Ni catalytic activity. This study puts forward design principles towards attaining higher selectivity of electrosynthesis of H2O2 through rational modulation of electronic sites.

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