Intrinsically Porous Polymer Protects Catalytic Gold Particles for Enzymeless Glucose Oxidation

Rong, Yuanyang; Malpass‐Evans, Richard; Carta, Mariolino; McKeown, Neil B.; Attard, Gary Anthony; Marken, Frank

doi:10.1002/elan.201400085

Cited by 39 publications

(36 citation statements)

References 27 publications

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“…Recently, a novel class of microporous organic materials, polymers with intrinsic microporosity (PIM), has been developed. There are a range of potential applications in gas membrane technology [15,16], in electrolyte media as ionic diode [17], and in electrochemical technology [18,19]. The structurally highly…”

Section: Introductionmentioning

confidence: 99%

Intrinsically microporous polymer slows down fuel cell catalyst corrosion

Rong

et al. 2015

Electrochemistry Communications

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The limited stability of fuel cell cathode catalysts causes a significant loss of operational cell voltage with commercial Pt-based catalysts, which hinders the wider commercialization of fuel cell technologies. We demonstrate beneficial effects of a highly rigid and porous polymer of intrinsic microporosity (PIM-EA-TB with BET surface area 1027 m 2 g -1 ) in accelerated catalyst corrosion experiments. Porous films of PIM-EA-TB offer an effective protective matrix for the prevention of Pt/C catalyst corrosion without impeding flux of reagents. The results of electrochemical cycling testsshow that the PIM-EA-TB protected Pt/C (denoted here as PIM@Pt/C) exhibit a significantly enhanced durability as compared to a conventional Pt/C catalyst.

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Section: Introductionmentioning

confidence: 99%

Intrinsically microporous polymer slows down fuel cell catalyst corrosion

Rong

et al. 2015

Electrochemistry Communications

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“…PIMs [23,24] provide a new generation of highly rigid microporous materials with (i) excellent processability, (ii) highly rigid pore structures in which guest catalyst molecules can be readily embedded, (iii) good access of solvent and substrate to the catalyst through rigid pores and (iv) robustness towards corrosion. In our previous work, the poly-amine structure PIM-EA-TB [25] (synthesised based on a Tröger's base reaction [26][27][28]) has been employed to electrochemically grow palladium lamellae [29], to act as a host for molecular Fe(II)-porphyrinato electrocatalyst [30] and to protect gold nanoparticles [31] and fuel cell catalysts [32]. Recently, we have demonstrated proof of concept for the immobilisation of the molecular electrocatalyst 4-benzoyloxy-TEMPO (or 4B-TEMPO) into a porous PIM-EA-TB host film for the electrocatalytic oxidation of saccharides [33].…”

Section: Introductionmentioning

confidence: 99%

Polymer of Intrinsic Microporosity Induces Host-Guest Substrate Selectivity in Heterogeneous 4-Benzoyloxy-TEMPO-Catalysed Alcohol Oxidations

et al. 2015

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The free radical 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4B-TEMPO) is active as an electrocatalyst for primary alcohol oxidations when immobilised at an electrode surface and immersed into an aqueous carbonate buffer solution. In order to improve the catalytic process, a composite film electrode is developed based on (i) carbon microparticles of 2-12 μm diameter to enhance charge transport and (ii) a polymer of intrinsic microporosity (here PIM-EA-TB with a BET surface area of 1027 m 2 g −1 ). The latter acts as a highly rigid molecular framework for the embedded free radical catalyst with simultaneous access to aqueous phase and substrate. The resulting mechanism for the oxidation of primary alcohols is shown to switch in reaction order from first to zeroth with increasing substrate concentration consistent with a kinetically limited process with competing diffusion of charge at the polymer layer-electrode interface (here the BLEk^case in Albery-Hillman notation). Reactivity optimisation and screening for a wider range of primary alcohols in conjunction with DFT-based relative reactivity correlation reveals substrate hydrophobicity as an important factor for enhancing catalytic currents. The PIM-EA-TB host matrix is proposed to control substrate partitioning and thereby catalyst reactivity and selectivity.

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“…As a result, voltammetric responses for the silver microparticles are more stable and repeatable. Within the potential range studied here PIM-EA-TB has no direct electrochemical activity [13,14] and it can be considered both cation and anion conducting [15]. Generally, with the PIM-EA-TB coating applied features such as the position of oxidation and back-reduction voltammetric responses are maintained and also the complex peak shape observed during the reduction is retained.…”

Section: Resultsmentioning

confidence: 97%

“…It has been demonstrated that metal nanoparticle catalysts can be PIM-coated and thereby protected against poisoning [13] and against detrimental loss and corrosion processes [14]. Here, we employ an intrinsically microporous polymer (PIM) material based on an ethanoanthracene (EA) building block that was synthesised employing a Tröger base (TB) method (PIM-EA-TB [15], see molecular structure in Fig.…”

Section: Introductionmentioning

confidence: 99%

Redox reactivity at silver microparticle—glassy carbon contacts under a coating of polymer of intrinsic microporosity (PIM)

Rauwel

Malpass‐Evans

et al. 2017

J Solid State Electrochem

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Silver microparticles (ca. 1 μm average size clustered into cage-like aggregates of 10-20 μm diameter) are shown to adhere to a glassy carbon electrode surface to give voltammetric current responses, which are considerably enhanced/stabilised when applying a coating with a molecularly rigid polymer of intrinsic microporosity (PIM-EA-TB). In preliminary voltammetric experiments characteristic Ag(0/I) surface oxidation and back-reduction processes are observed in aqueous phosphate buffer (associated with silver phosphate layer formation on the silver surface). In contrast to the oxidation, which is dominated by a nucleation process causing a sharp well-defined current signal, for the back-reduction stochastic current responses are observed possibly associated with density fluctuations in the surrounding liquid phase (BBrownian activation^) as an essential part of the mechanism of conversion of surface-oxidised silver back to silver metal.

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Intrinsically Porous Polymer Protects Catalytic Gold Particles for Enzymeless Glucose Oxidation

Cited by 39 publications

References 27 publications

Intrinsically microporous polymer slows down fuel cell catalyst corrosion

Intrinsically microporous polymer slows down fuel cell catalyst corrosion

Polymer of Intrinsic Microporosity Induces Host-Guest Substrate Selectivity in Heterogeneous 4-Benzoyloxy-TEMPO-Catalysed Alcohol Oxidations

Redox reactivity at silver microparticle—glassy carbon contacts under a coating of polymer of intrinsic microporosity (PIM)

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