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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
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URI: https://cronfa.swan.ac.uk/Record/cronfa61964
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spelling 2022-12-15T18:05:32.2250456 v2 61964 2022-11-21 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 56aebf2bba457f395149bbecbfa6d3eb 0000-0003-0718-6971 Mariolino Carta Mariolino Carta true false 2022-11-21 CHEM 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. Journal Article Journal of Catalysis 416 253 266 Elsevier BV 0021-9517 Clark probe; Disinfection; Oxidase; Cavity catalysis; Bipolar catalyst; Nanozyme 1 12 2022 2022-12-01 10.1016/j.jcat.2022.11.015 COLLEGE NANME Chemistry COLLEGE CODE CHEM Swansea University 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. 2022-12-15T18:05:32.2250456 2022-11-21T09:48:14.3140967 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Lina Wang 1 Mariolino Carta 0000-0003-0718-6971 2 Richard Malpass-Evans 3 Neil B. McKeown 4 Philip J. Fletcher 5 Pedro Estrela 6 Alberto Roldan 7 Frank Marken 8 61964__25848__3657a2f611db483c90d035e3e8188820.pdf 61964.pdf 2022-11-21T09:49:59.0551802 Output 5112511 application/pdf Version of Record true Copyright 2022 The Author(s). This is an open access article under the CC BY license true eng http://creativecommons.org/licenses/by/4.0/
title 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
spellingShingle 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
Mariolino Carta
title_short 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
title_full 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
title_fullStr 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
title_full_unstemmed 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
title_sort 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
author_id_str_mv 56aebf2bba457f395149bbecbfa6d3eb
author_id_fullname_str_mv 56aebf2bba457f395149bbecbfa6d3eb_***_Mariolino Carta
author Mariolino Carta
author2 Lina Wang
Mariolino Carta
Richard Malpass-Evans
Neil B. McKeown
Philip J. Fletcher
Pedro Estrela
Alberto Roldan
Frank Marken
format Journal article
container_title Journal of Catalysis
container_volume 416
container_start_page 253
publishDate 2022
institution Swansea University
issn 0021-9517
doi_str_mv 10.1016/j.jcat.2022.11.015
publisher Elsevier BV
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
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description 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.
published_date 2022-12-01T04:12:55Z
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