Understanding Transient Ionic Diode Currents and Impedance Responses for Aquivion-Coated Microholes

Evaldo Batista Carneiro-Neto; Zhongkai Li; Ernesto Pereira; Klaus Mathwig; Philip J. Fletcher; Frank Marken

doi:10.1021/acsami.3c08543

Understanding Transient Ionic Diode Currents and Impedance Responses for Aquivion-Coated Microholes

Evaldo Batista Carneiro-Neto
, Zhongkai Li
, Ernesto Pereira
, Klaus Mathwig
, Philip J. Fletcher
, Frank Marken

Universidade Federal de São Carlos
OnePlanet Research Center
Material and Chemical Characterization Facility (MC2)

Research output: Contribution to journal › Article › peer-review

3 Citations (SciVal)

226 Downloads (Pure)

Abstract

Ionic diode based devices or circuits can be applied, for example, in electroosmotic pumps or in desalination processes. Aquivion ionomer coated asymmetrically over a Teflon film (5 μm thickness) with a laser-drilled microhole (approximately 10 μm diameter) gives a cationic diode with a rectification ratio of typically 10-20 (measured in 0.01 M NaCl with ±0.3 V applied bias). Steady state voltammetry, chronoamperometry, and electrochemical impedance spectroscopy data are employed to characterize the ionic diode performance parameters. Next, a COMSOL 6.0 finite element model is employed to quantitatively assess/compare transient phenomena and to extract mechanistic information by comparison with experimental data. The experimental diode time constant and diode switching process associated with a distorted semicircle (with a typical diode switching frequency of 10 Hz) in the Nyquist plot are reproduced by computer simulation and rationalized in terms of microhole diffusion-migration times. Fundamental understanding and modeling of the ionic diode switching process can be exploited in the rational/optimized design of new improved devices.

Original language	English
Pages (from-to)	39905-39914
Number of pages	10
Journal	ACS Applied Materials and Interfaces
Volume	15
Issue number	33
Early online date	11 Aug 2023
DOIs	https://doi.org/10.1021/acsami.3c08543
Publication status	Published - 23 Aug 2023

Funding

E.B.C.N. and E.C.P. acknowledge support from FAPESP (São Paulo Research Foundation, Grant Numbers 2013/07296-2, 2021/03592-2, 2022/06229-9), Shell, and the strategic importance of the support given by ANP (Brazil’s National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation, CNPq (Grant Number 407878/2022), and CAPES (Code 001). F.M. is grateful for the initial financial support by the EPSRC (EP/K004956/1).

Funders	Funder number
Natural Gas and Biofuels Agency
Shell
Engineering and Physical Sciences Research Council	EP/K004956/1
Fundação de Amparo à Pesquisa do Estado de São Paulo	2013/07296-2, 2022/06229-9, 2021/03592-2
Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior
Conselho Nacional de Desenvolvimento Cientifico e Tecnologico	407878/2022
Agência Nacional do Petróleo, Gás Natural e Biocombustíveis

Keywords

accumulation−depletion
desalination
diffusion−migration
electrochemical impedance spectroscopy
ionic diode

ASJC Scopus subject areas

General Materials Science

Access to Document

10.1021/acsami.3c08543

Diode transients 1ff_REVISION_nhAccepted author manuscript, 1.72 MBLicence: CC BY

Cite this

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title = "Understanding Transient Ionic Diode Currents and Impedance Responses for Aquivion-Coated Microholes",

abstract = "Ionic diode based devices or circuits can be applied, for example, in electroosmotic pumps or in desalination processes. Aquivion ionomer coated asymmetrically over a Teflon film (5 μm thickness) with a laser-drilled microhole (approximately 10 μm diameter) gives a cationic diode with a rectification ratio of typically 10-20 (measured in 0.01 M NaCl with ±0.3 V applied bias). Steady state voltammetry, chronoamperometry, and electrochemical impedance spectroscopy data are employed to characterize the ionic diode performance parameters. Next, a COMSOL 6.0 finite element model is employed to quantitatively assess/compare transient phenomena and to extract mechanistic information by comparison with experimental data. The experimental diode time constant and diode switching process associated with a distorted semicircle (with a typical diode switching frequency of 10 Hz) in the Nyquist plot are reproduced by computer simulation and rationalized in terms of microhole diffusion-migration times. Fundamental understanding and modeling of the ionic diode switching process can be exploited in the rational/optimized design of new improved devices.",

keywords = "accumulation−depletion, desalination, diffusion−migration, electrochemical impedance spectroscopy, ionic diode",

author = "Carneiro-Neto, \{Evaldo Batista\} and Zhongkai Li and Ernesto Pereira and Klaus Mathwig and Fletcher, \{Philip J.\} and Frank Marken",

year = "2023",

month = aug,

day = "23",

doi = "10.1021/acsami.3c08543",

language = "English",

volume = "15",

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journal = "ACS Applied Materials and Interfaces",

issn = "1944-8244",

publisher = "American Chemical Society",

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AU - Carneiro-Neto, Evaldo Batista

AU - Li, Zhongkai

AU - Pereira, Ernesto

AU - Mathwig, Klaus

AU - Fletcher, Philip J.

AU - Marken, Frank

PY - 2023/8/23

Y1 - 2023/8/23

N2 - Ionic diode based devices or circuits can be applied, for example, in electroosmotic pumps or in desalination processes. Aquivion ionomer coated asymmetrically over a Teflon film (5 μm thickness) with a laser-drilled microhole (approximately 10 μm diameter) gives a cationic diode with a rectification ratio of typically 10-20 (measured in 0.01 M NaCl with ±0.3 V applied bias). Steady state voltammetry, chronoamperometry, and electrochemical impedance spectroscopy data are employed to characterize the ionic diode performance parameters. Next, a COMSOL 6.0 finite element model is employed to quantitatively assess/compare transient phenomena and to extract mechanistic information by comparison with experimental data. The experimental diode time constant and diode switching process associated with a distorted semicircle (with a typical diode switching frequency of 10 Hz) in the Nyquist plot are reproduced by computer simulation and rationalized in terms of microhole diffusion-migration times. Fundamental understanding and modeling of the ionic diode switching process can be exploited in the rational/optimized design of new improved devices.

AB - Ionic diode based devices or circuits can be applied, for example, in electroosmotic pumps or in desalination processes. Aquivion ionomer coated asymmetrically over a Teflon film (5 μm thickness) with a laser-drilled microhole (approximately 10 μm diameter) gives a cationic diode with a rectification ratio of typically 10-20 (measured in 0.01 M NaCl with ±0.3 V applied bias). Steady state voltammetry, chronoamperometry, and electrochemical impedance spectroscopy data are employed to characterize the ionic diode performance parameters. Next, a COMSOL 6.0 finite element model is employed to quantitatively assess/compare transient phenomena and to extract mechanistic information by comparison with experimental data. The experimental diode time constant and diode switching process associated with a distorted semicircle (with a typical diode switching frequency of 10 Hz) in the Nyquist plot are reproduced by computer simulation and rationalized in terms of microhole diffusion-migration times. Fundamental understanding and modeling of the ionic diode switching process can be exploited in the rational/optimized design of new improved devices.

KW - accumulation−depletion

KW - desalination

KW - diffusion−migration

KW - electrochemical impedance spectroscopy

KW - ionic diode

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DO - 10.1021/acsami.3c08543

M3 - Article

C2 - 37567567

AN - SCOPUS:85168784416

SN - 1944-8244

VL - 15

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EP - 39914

JO - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

IS - 33

ER -

Understanding Transient Ionic Diode Currents and Impedance Responses for Aquivion-Coated Microholes

Abstract

Funding

Keywords

ASJC Scopus subject areas

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Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

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Understanding Transient Ionic Diode Currents and Impedance Responses for Aquivion-Coated Microholes

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

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Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Cite this