Continuous and Reversible Tuning of Electrochemical Reaction Kinetics on Back-Gated 2D Semiconductor Electrodes: Steady-State Analysis Using a Hydrodynamic Method

Chang Hyun Kim, Yan Wang, Daniel Frisbie

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3 Citations (Scopus)

Abstract

Here we report the steady state kinetic analysis of field-effect-controlled outer-sphere electrochemistry on ultrathin back-gated ZnO working electrodes (i.e., 5 nm ZnO electrodes prepared on SiO 2 /degenerate Si back gates). To achieve steady state conditions in the electrolyte phase, gate-tunable electrochemical flow cells were prepared by integrating a silicone microfluidic channel on the back-gated ZnO electrode. In these flow cells, continuous supply of fresh electrolyte generates time-invariant diffusion layers near the ZnO surface, allowing steady-state kinetic analysis as in other hydrodynamic methods. From the steady-state analysis, it was found that the electron density on the ZnO surface increases with the voltage bias, V BG , applied to the back gate, while the rate constant for electron transfer decreases with V BG . The observed trend can be explained as a result of the field-effect-induced band alignment shift at the ZnO/electrolyte interface which is predicted by our conceptual model; a positive back gate bias shifts the conduction band edge down at a given working electrode potential, leading to an increased surface electron density on ZnO, but simultaneously less overlap of the band edge with the electron acceptor states in solution, which means a lower electron transfer rate constant. Overall, the results quantitatively demonstrate that back gates and the ensuing field effect can be used to control kinetics of interfacial electron transfer at two-dimensional (2D) semiconductor electrodes.

Original languageEnglish (US)
Pages (from-to)1627-1635
Number of pages9
JournalAnalytical chemistry
Volume91
Issue number2
DOIs
StatePublished - Jan 15 2019

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Reaction kinetics
Hydrodynamics
Tuning
Semiconductor materials
Electrodes
Electrolytes
Kinetics
Carrier concentration
Electrons
Rate constants
Electrochemistry
Silicones
Bias voltage
Conduction bands
Microfluidics
Electron energy levels

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Cite this

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title = "Continuous and Reversible Tuning of Electrochemical Reaction Kinetics on Back-Gated 2D Semiconductor Electrodes: Steady-State Analysis Using a Hydrodynamic Method",
abstract = "Here we report the steady state kinetic analysis of field-effect-controlled outer-sphere electrochemistry on ultrathin back-gated ZnO working electrodes (i.e., 5 nm ZnO electrodes prepared on SiO 2 /degenerate Si back gates). To achieve steady state conditions in the electrolyte phase, gate-tunable electrochemical flow cells were prepared by integrating a silicone microfluidic channel on the back-gated ZnO electrode. In these flow cells, continuous supply of fresh electrolyte generates time-invariant diffusion layers near the ZnO surface, allowing steady-state kinetic analysis as in other hydrodynamic methods. From the steady-state analysis, it was found that the electron density on the ZnO surface increases with the voltage bias, V BG , applied to the back gate, while the rate constant for electron transfer decreases with V BG . The observed trend can be explained as a result of the field-effect-induced band alignment shift at the ZnO/electrolyte interface which is predicted by our conceptual model; a positive back gate bias shifts the conduction band edge down at a given working electrode potential, leading to an increased surface electron density on ZnO, but simultaneously less overlap of the band edge with the electron acceptor states in solution, which means a lower electron transfer rate constant. Overall, the results quantitatively demonstrate that back gates and the ensuing field effect can be used to control kinetics of interfacial electron transfer at two-dimensional (2D) semiconductor electrodes.",
author = "Kim, {Chang Hyun} and Yan Wang and Daniel Frisbie",
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AU - Frisbie, Daniel

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AB - Here we report the steady state kinetic analysis of field-effect-controlled outer-sphere electrochemistry on ultrathin back-gated ZnO working electrodes (i.e., 5 nm ZnO electrodes prepared on SiO 2 /degenerate Si back gates). To achieve steady state conditions in the electrolyte phase, gate-tunable electrochemical flow cells were prepared by integrating a silicone microfluidic channel on the back-gated ZnO electrode. In these flow cells, continuous supply of fresh electrolyte generates time-invariant diffusion layers near the ZnO surface, allowing steady-state kinetic analysis as in other hydrodynamic methods. From the steady-state analysis, it was found that the electron density on the ZnO surface increases with the voltage bias, V BG , applied to the back gate, while the rate constant for electron transfer decreases with V BG . The observed trend can be explained as a result of the field-effect-induced band alignment shift at the ZnO/electrolyte interface which is predicted by our conceptual model; a positive back gate bias shifts the conduction band edge down at a given working electrode potential, leading to an increased surface electron density on ZnO, but simultaneously less overlap of the band edge with the electron acceptor states in solution, which means a lower electron transfer rate constant. Overall, the results quantitatively demonstrate that back gates and the ensuing field effect can be used to control kinetics of interfacial electron transfer at two-dimensional (2D) semiconductor electrodes.

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