Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes

Fu, Kaiyu; Han, Donghoon; Kwon, Seung -Ryong; Bohn, Paul W.

doi:10.1021/acsnano.8b03751

Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes

Journal Article · Mon Aug 06 00:00:00 EDT 2018 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.8b03751· OSTI ID:1494075

^[1]; ^[2]; ^[2]; ^[2]

Univ. of Notre Dame, Notre Dame, IN (United States); University of Notre Dame
Univ. of Notre Dame, Notre Dame, IN (United States)

Inspired by the functioning of cellular ion channels, pore-based structures with nanoscale openings, have been fabricated and integrated into ionic circuits, e.g. ionic diodes and transistors, for signal processing and detection. In these systems, the nonlinear current responses arise either because asymmetric nanopore geometries break the symmetry of the ion distribution, creating unequal surface charge across the nanopore, or by coupling unidirectional electron transfer within a nanopore electrode. Here, we develop a high-performance redox cycling-based electrochemical diode by coating an asymmetric ion-exchange membrane, i.e. Nafion, on the top surface of a nanopore electrode array (Nafion@NEA), in which each pore in the array exhibits one or more annular electrodes. Nafion@NEAs exhibit highly sensitive and charge-selective electroanalytical measurements due to efficient redox cycling reaction, the permselectivity of Nafion, and strong confinement of redox species in the nanopore array. In addition, the top electrode of dual electrode Nafion@NEAs can serve as a voltage-controlled switch to gate ion transport within the nanopore. Thus, Nafion@NEAs can be operated as a diode by switching voltages applied to the top and bottom electrodes of the NEA, leading to a large rectification ratio, fast response times, and simplified circuitry without the need for external electrodes. Here by taking advantage of closely spaced and individually addressable electrodes, the redox cycling electrochemical diode has the potential for application to large-scale production and electrochemically-controlled circuit operations which go well beyond conventional electronic diodes or transistors.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Notre Dame, Notre Dame, IN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-07ER15851

OSTI ID:: 1494075

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 9 Vol. 12; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Single-Layer Pentacene Field-Effect Transistors Using Electrodes Modified With Self-assembled Monolayers Asadi, Kamal; Wu, Yu; Gholamrezaie, Fatemeh Advanced Materials, Vol. 21, Issue 41 https://doi.org/10.1002/adma.200803455	journal	November 2009
Ionic Circuits Based on Polyelectrolyte Diodes on a Microchip Han, Ji-Hyung; Kim, Kwang Bok; Kim, Hee Chan Angewandte Chemie International Edition, Vol. 48, Issue 21 https://doi.org/10.1002/anie.200900045	journal	May 2009
An Electrochemically Transduced XOR Logic Gate at the Molecular Level Liu, Yaqing; Offenhäusser, Andreas; Mayer, Dirk Angewandte Chemie International Edition, Vol. 49, Issue 14 https://doi.org/10.1002/anie.200906333	journal	March 2010
Transistor Functions Based on Electrochemical Rectification Liu, Yaqing; Wolfrum, Bernhard; Hüske, Martin Angewandte Chemie International Edition, Vol. 52, Issue 14 https://doi.org/10.1002/anie.201207778	journal	March 2013
Voltage-Gated Nanoparticle Transport and Collisions in Attoliter-Volume Nanopore Electrode Arrays Fu, Kaiyu; Han, Donghoon; Crouch, Garrison M. Small, Vol. 14, Issue 18 https://doi.org/10.1002/smll.201703248	journal	January 2018
Ion-exchange selectivity of Nafion films on electrode surfaces Szentirmay, Marilyn N.; Martin, Charles R. Analytical Chemistry, Vol. 56, Issue 11 https://doi.org/10.1021/ac00275a031	journal	August 1984
Nanoparticle Transport in Conical-Shaped Nanopores Lan, Wen-Jie; Holden, Deric A.; Zhang, Bo Analytical Chemistry, Vol. 83, Issue 10 https://doi.org/10.1021/ac200312n	journal	May 2011
Ion-Exchange Voltammetry at Polymer Film-Coated Nanoelectrode Ensembles Ugo, Paolo; Moretto, Ligia M.; Bellomi, Sara Analytical Chemistry, Vol. 68, Issue 23 https://doi.org/10.1021/ac960580b	journal	December 1996
Voltage-Rectified Current and Fluid Flow in Conical Nanopores Lan, Wen-Jie; Edwards, Martin A.; Luo, Long Accounts of Chemical Research, Vol. 49, Issue 11 https://doi.org/10.1021/acs.accounts.6b00395	journal	September 2016
Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids Byers, Joshua C.; Paulose Nadappuram, Binoy; Perry, David Analytical Chemistry, Vol. 87, Issue 20 https://doi.org/10.1021/acs.analchem.5b02569	journal	October 2015
Redox Cycling in Nanopore-Confined Recessed Dual-Ring Electrode Arrays Han, Donghoon; Zaino, Lawrence P.; Fu, Kaiyu The Journal of Physical Chemistry C, Vol. 120, Issue 37 https://doi.org/10.1021/acs.jpcc.6b01287	journal	May 2016
A Cationic Diode Based on Asymmetric Nafion Film Deposits He, Daping; Madrid, Elena; Aaronson, Barak D. B. ACS Applied Materials & Interfaces, Vol. 9, Issue 12 https://doi.org/10.1021/acsami.7b01774	journal	March 2017
Programmable Electrochemical Rectifier Based on a Thin-Layer Cell Park, Seungjin; Park, Jun Hui; Hwang, Seongpil ACS Applied Materials & Interfaces, Vol. 9, Issue 24 https://doi.org/10.1021/acsami.7b02215	journal	June 2017
Nanochannel Arrays for Molecular Sieving and Electrochemical Analysis by Nanosphere Lithography Templated Graphoepitaxy of Block Copolymers Fu, Kaiyu; Bohn, Paul W. ACS Applied Materials & Interfaces, Vol. 9, Issue 29 https://doi.org/10.1021/acsami.7b06794	journal	July 2017
Nanopore Electrochemistry: A Nexus for Molecular Control of Electron Transfer Reactions Fu, Kaiyu; Bohn, Paul W. ACS Central Science, Vol. 4, Issue 1 https://doi.org/10.1021/acscentsci.7b00576	journal	December 2017
Spearhead Nanometric Field-Effect Transistor Sensors for Single-Cell Analysis Zhang, Yanjun; Clausmeyer, Jan; Babakinejad, Babak ACS Nano, Vol. 10, Issue 3 https://doi.org/10.1021/acsnano.5b05211	journal	February 2016
Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength Ma, Chaoxiong; Xu, Wei; Wichert, William R. A. ACS Nano, Vol. 10, Issue 3 https://doi.org/10.1021/acsnano.6b00049	journal	February 2016
Slowing DNA Translocation in a Nanofluidic Field-Effect Transistor Liu, Yifan; Yobas, Levent ACS Nano, Vol. 10, Issue 4 https://doi.org/10.1021/acsnano.6b00610	journal	April 2016
Asymmetric Ion Transport through Ion-Channel-Mimetic Solid-State Nanopores Guo, Wei; Tian, Ye; Jiang, Lei Accounts of Chemical Research, Vol. 46, Issue 12 https://doi.org/10.1021/ar400024p	journal	January 2013
State of Understanding of Nafion Mauritz, Kenneth A.; Moore, Robert B. Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr0207123	journal	October 2004
Rectifying interfaces using two-layer films of electrochemically polymerized vinylpyridine and vinylbipyridine complexes of ruthenium and iron on electrodes Abruna, H. D.; Denisevich, P.; Umana, M. Journal of the American Chemical Society, Vol. 103, Issue 1 https://doi.org/10.1021/ja00391a001	journal	January 1981
Polyelectrolyte Diode: Nonlinear Current Response of a Junction between Aqueous Ionic Gels Cayre, Olivier J.; Chang, Suk Tai; Velev, Orlin D. Journal of the American Chemical Society, Vol. 129, Issue 35 https://doi.org/10.1021/ja072449z	journal	September 2007
Enhanced Mass Transport of Electroactive Species to Annular Nanoband Electrodes Embedded in Nanocapillary Array Membranes Branagan, Sean P.; Contento, Nicholas M.; Bohn, Paul W. Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja3017158	journal	May 2012
Redox Cycling on Recessed Ring-Disk Nanoelectrode Arrays in the Absence of Supporting Electrolyte Ma, Chaoxiong; Contento, Nicholas M.; Bohn, Paul W. Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja502052s	journal	May 2014
Electrochemistry of Individual Molecules in Zeptoliter Volumes Sun, Peng; Mirkin, Michael V. Journal of the American Chemical Society, Vol. 130, Issue 26 https://doi.org/10.1021/ja711088j	journal	July 2008
Biosensing with Nanofluidic Diodes Vlassiouk, Ivan; Kozel, Thomas R.; Siwy, Zuzanna S. Journal of the American Chemical Society, Vol. 131, Issue 23 https://doi.org/10.1021/ja901120f	journal	June 2009
Single Molecule Electrochemistry Fan, Fu-Ren F.; Kwak, Juhyoun; Bard, Allen J. Journal of the American Chemical Society, Vol. 118, Issue 40 https://doi.org/10.1021/ja9610794	journal	January 1996
Electrochemical Rectification at a Monolayer-Modified Electrode Alleman, Kent S.; Weber, Kara; Creager, Stephen E. The Journal of Physical Chemistry, Vol. 100, Issue 42 https://doi.org/10.1021/jp962193b	journal	January 1996
Electrochemical Rectification Using Mixed Monolayers of Redox-Active Ferrocenyl Dendrimers and n-Alkanethiols Oh, Sang-Keun; Baker, Lane A.; Crooks, Richard M. Langmuir, Vol. 18, Issue 18 https://doi.org/10.1021/la020382h	journal	August 2002
Ion Transport in Nanofluidic Channels Daiguji, Hirofumi; Yang, Peidong; Majumdar, Arun Nano Letters, Vol. 4, Issue 1 https://doi.org/10.1021/nl0348185	journal	January 2004
Experimental Observation of Nonlinear Ionic Transport at the Nanometer Scale Krapf, Diego; Quinn, Bernadette M.; Wu, Meng-Yue Nano Letters, Vol. 6, Issue 11 https://doi.org/10.1021/nl0619453	journal	October 2006
Rectification of Ionic Current in a Nanofluidic Diode Karnik, Rohit; Duan, Chuanhua; Castelino, Kenneth Nano Letters, Vol. 7, Issue 3 https://doi.org/10.1021/nl062806o	journal	March 2007
Nanofluidic Diode Vlassiouk, Ivan; Siwy, Zuzanna S. Nano Letters, Vol. 7, Issue 3 https://doi.org/10.1021/nl062924b	journal	March 2007
Power Generation by Pressure-Driven Transport of Ions in Nanofluidic Channels van der Heyden, Frank H. J.; Bonthuis, Douwe Jan; Stein, Derek Nano Letters, Vol. 7, Issue 4 https://doi.org/10.1021/nl070194h	journal	April 2007
Charge Transport and Rectification in Arrays of SAM-Based Tunneling Junctions Nijhuis, Christian A.; Reus, William F.; Barber, Jabulani R. Nano Letters, Vol. 10, Issue 9 https://doi.org/10.1021/nl101918m	journal	August 2010
Ionic Field Effect Transistors with Sub-10 nm Multiple Nanopores Nam, Sung-Wook; Rooks, Michael J.; Kim, Ki-Bum Nano Letters, Vol. 9, Issue 5 https://doi.org/10.1021/nl900309s	journal	May 2009
Control of DNA Capture by Nanofluidic Transistors Paik, Kee-Hyun; Liu, Yang; Tabard-Cossa, Vincent ACS Nano, Vol. 6, Issue 8 https://doi.org/10.1021/nn3014917	journal	July 2012
Redox Cycling in Nanoscale-Recessed Ring-Disk Electrode Arrays for Enhanced Electrochemical Sensitivity Ma, Chaoxiong; Contento, Nicholas M.; Gibson, Larry R. ACS Nano, Vol. 7, Issue 6 https://doi.org/10.1021/nn401542x	journal	May 2013
Electrochemical Single-Molecule Detection in Aqueous Solution Using Self-Aligned Nanogap Transducers Kang, Shuo; Nieuwenhuis, Ab F.; Mathwig, Klaus ACS Nano, Vol. 7, Issue 12 https://doi.org/10.1021/nn404440v	journal	November 2013
Logic gates based on ion transistors Tybrandt, Klas; Forchheimer, Robert; Berggren, Magnus Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms1869	journal	January 2012
Monolayer coverage and channel length set the mobility in self-assembled monolayer field-effect transistors Mathijssen, Simon G. J.; Smits, Edsger C. P.; van Hal, Paul A. Nature Nanotechnology, Vol. 4, Issue 10 https://doi.org/10.1038/nnano.2009.201	journal	August 2009
Principles and applications of nanofluidic transport Sparreboom, W.; van den Berg, A.; Eijkel, J. C. T. Nature Nanotechnology, Vol. 4, Issue 11 https://doi.org/10.1038/nnano.2009.332	journal	November 2009
Decoding DNA, RNA and peptides with quantum tunnelling Di Ventra, Massimiliano; Taniguchi, Masateru Nature Nanotechnology, Vol. 11, Issue 2 https://doi.org/10.1038/nnano.2015.320	journal	February 2016
Nanopore extended field-effect transistor for selective single-molecule biosensing Ren, Ren; Zhang, Yanjun; Nadappuram, Binoy Paulose Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00549-w	journal	September 2017
Ion transport in nanofluidic channels Daiguji, Hirofumi Chem. Soc. Rev., Vol. 39, Issue 3 https://doi.org/10.1039/B820556F	journal	January 2010
Nanofluidic diodes Cheng, Li-Jing; Guo, L. Jay Chem. Soc. Rev., Vol. 39, Issue 3 https://doi.org/10.1039/B822554K	journal	January 2010
Nanofluidics, from bulk to interfaces Bocquet, Lydéric; Charlaix, Elisabeth Chem. Soc. Rev., Vol. 39, Issue 3 https://doi.org/10.1039/B909366B	journal	January 2010
Electrochemistry at single molecule occupancy in nanopore-confined recessed ring-disk electrode arrays Fu, Kaiyu; Han, Donghoon; Ma, Chaoxiong Faraday Discussions, Vol. 193 https://doi.org/10.1039/C6FD00062B	journal	January 2016
Field effect nanofluidics Prakash, Shaurya; Conlisk, A. T. Lab on a Chip, Vol. 16, Issue 20 https://doi.org/10.1039/C6LC00688D	journal	January 2016
Bioinspired smart asymmetric nanochannel membranes Zhang, Zhen; Wen, Liping; Jiang, Lei Chemical Society Reviews, Vol. 47, Issue 2 https://doi.org/10.1039/C7CS00688H	journal	January 2018
Ion selective redox cycling in zero-dimensional nanopore electrode arrays at low ionic strength Fu, Kaiyu; Han, Donghoon; Ma, Chaoxiong Nanoscale, Vol. 9, Issue 16 https://doi.org/10.1039/C7NR00206H	journal	January 2017
Chemoresponsive monolayer transistors Guo, X.; Myers, M.; Xiao, S. Proceedings of the National Academy of Sciences, Vol. 103, Issue 31 https://doi.org/10.1073/pnas.0601675103	journal	July 2006
Ion bipolar junction transistors Tybrandt, K.; Larsson, K. C.; Richter-Dahlfors, A. Proceedings of the National Academy of Sciences, Vol. 107, Issue 22 https://doi.org/10.1073/pnas.0913911107	journal	May 2010
Transport in nanofluidic systems: a review of theory and applications Sparreboom, W.; van den Berg, A.; Eijkel, J. C. T. New Journal of Physics, Vol. 12, Issue 1 https://doi.org/10.1088/1367-2630/12/1/015004	journal	January 2010
Surface-Charge-Governed Ion Transport in Nanofluidic Channels Stein, Derek; Kruithof, Maarten; Dekker, Cees Physical Review Letters, Vol. 93, Issue 3 https://doi.org/10.1103/PhysRevLett.93.035901	journal	July 2004
Iontronics Chun, Honggu; Chung, Taek Dong Annual Review of Analytical Chemistry, Vol. 8, Issue 1 https://doi.org/10.1146/annurev-anchem-071114-040202	journal	July 2015

Cited By (1)

Nanopore-Templated Silver Nanoparticle Arrays Photopolymerized in Zero-Mode Waveguides Han, Donghoon; Crouch, Garrison M.; Chao, Zhongmou Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00216	journal	April 2019

Similar Records

Ion Accumulation and Migration Effects on Redox Cycling in Nanopore Electrode Arrays at Low Ionic Strength

Journal Article · Tue Feb 23 23:00:00 EST 2016 · ACS Nano · OSTI ID:1808196

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries

Journal Article · Mon Jan 27 23:00:00 EST 2020 · Accounts of Chemical Research · OSTI ID:1762420

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY
Nafion
ionic diode
nanopore electrode arrays
nanoscale electrochemistry
permselectivity
redox cycling

Asymmetric Nafion-Coated Nanopore Electrode Arrays as Redox-Cycling-Based Electrochemical Diodes

Citation Formats

References (56)

Cited By (1)

Similar Records

Related Subjects