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Artificial formate oxidase reactivity with nano-palladium embedded in intrinsically microporous polyamine (Pd@PIM-EA-TB) driving the H2O2 – 3,5,3′,5′-tetramethylbenzidine (TMB) colour reaction

Lina Wang, Mariolino Carta Orcid Logo, Richard Malpass-Evans, Neil B. McKeown, Philip J. Fletcher, Pedro Estrela, Alberto Roldan, Frank Marken

Journal of Catalysis, Volume: 416, Pages: 253 - 266

Swansea University Author: Mariolino Carta Orcid Logo

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Abstract

Surface cavities formed by molecularly rigid polymers of intrinsic microporosity affect catalytic processes. Palladium nanoparticles of typically 3 nm diameter are formed in an intrinsically microporous polyamine (PIM-EA-TB) by borohydride reduction. These particles are shown to indirectly catalyse...

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Published in: Journal of Catalysis
ISSN: 0021-9517
Published: Elsevier BV 2022
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa61964
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Abstract: Surface cavities formed by molecularly rigid polymers of intrinsic microporosity affect catalytic processes. Palladium nanoparticles of typically 3 nm diameter are formed in an intrinsically microporous polyamine (PIM-EA-TB) by borohydride reduction. These particles are shown to indirectly catalyse the oxidative colour change of indicator dye 3,5,3′,5′-tetramethylbenzidine (TMB) in the presence of formic acid via formation of H2O2. Investigation reveals that oxygen reduction on the palladium is rate limiting with optimised H2O2 production at approximately pH 3 to 4, and first order in formate, followed by purely homogeneous TMB oxidation. The H2O2 production is therefore studied separately as a nanozyme-like catalytic process equivalent to formate oxidase reactivity, linked to the molecularly rigid polyamine host (PIM-EA-TB) providing ammonium sites (in molecularly rigid surface cavities) that enhance both (i) 2-electron formate oxidation and (ii) 2-electron oxygen reduction to H2O2. Beneficial effects of hydrophobic ClO4- anions are noted as indirect evidence for the effect of ammonium sites in surface cavities. A computational DFT model for the artificial formate oxidase reactivity is developed to underpin and illustrate the hypothesis of PIM-EA-TB as an active catalyst component with implications for future nanozyme sensor development.
Keywords: Clark probe; Disinfection; Oxidase; Cavity catalysis; Bipolar catalyst; Nanozyme
College: Faculty of Science and Engineering
Funders: L.W. thanks the China Scholarship Council (201906870022) for a PhD stipend. F.M. thanks EPSRC for support under project EP/K004956/1. We also acknowledge Supercomputing Wales for access to the Hawk HPC facility, part-funded by the European Regional Development Fund via the Welsh Government.
Start Page: 253
End Page: 266