Edge-site nano-engineering of WS2 by low temperature plasma-enhanced atomic layer deposition for electrocatalytic hydrogen evolution

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Abstract

Edge-enriched transition metal dichalcogenides, such as WS 2, are promising electrocatalysts for sustainable production of H 2 through the electrochemical hydrogen evolution reaction (HER). The reliable and controlled growth of such edge-enriched electrocatalysts at low temperatures has, however, remained elusive. In this work, we demonstrate how plasma-enhanced atomic layer deposition (PEALD) can be used as a new approach to nanoengineer and enhance the HER performance of WS 2 by maximizing the density of reactive edge sites at a low temperature of 300 °C. By altering the plasma gas composition from H 2S to H 2 + H 2S during PEALD, we could precisely control the morphology and composition and, consequently, the edge-site density as well as chemistry in our WS 2 films. The precise control over edge-site density was verified by evaluating the number of exposed edge sites using electrochemical copper underpotential depositions. Subsequently, we demonstrate the HER performance of the edge-enriched WS 2 electrocatalyst, and a clear correlation among plasma conditions, edge-site density, and the HER performance is obtained. Additionally, using density functional theory calculations we provide insights and explain how the addition of H 2 to the H 2S plasma impacts the PEALD growth behavior and, consequently, the material properties, when compared to only H 2S plasma.

Original languageEnglish
Pages (from-to)5104-5115
Number of pages12
JournalChemistry of Materials
Volume31
Issue number14
DOIs
Publication statusPublished - 25 Jun 2019

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Atomic layer deposition
Hydrogen
Plasmas
Electrocatalysts
Temperature
Plasma Gases
Chemical analysis
Transition metals
Density functional theory
Copper
Materials properties
Gases

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@article{ab52c828199948e8b9b18c4f9ec8a4ab,
title = "Edge-site nano-engineering of WS2 by low temperature plasma-enhanced atomic layer deposition for electrocatalytic hydrogen evolution",
abstract = "Edge-enriched transition metal dichalcogenides, such as WS 2, are promising electrocatalysts for sustainable production of H 2 through the electrochemical hydrogen evolution reaction (HER). The reliable and controlled growth of such edge-enriched electrocatalysts at low temperatures has, however, remained elusive. In this work, we demonstrate how plasma-enhanced atomic layer deposition (PEALD) can be used as a new approach to nanoengineer and enhance the HER performance of WS 2 by maximizing the density of reactive edge sites at a low temperature of 300 °C. By altering the plasma gas composition from H 2S to H 2 + H 2S during PEALD, we could precisely control the morphology and composition and, consequently, the edge-site density as well as chemistry in our WS 2 films. The precise control over edge-site density was verified by evaluating the number of exposed edge sites using electrochemical copper underpotential depositions. Subsequently, we demonstrate the HER performance of the edge-enriched WS 2 electrocatalyst, and a clear correlation among plasma conditions, edge-site density, and the HER performance is obtained. Additionally, using density functional theory calculations we provide insights and explain how the addition of H 2 to the H 2S plasma impacts the PEALD growth behavior and, consequently, the material properties, when compared to only H 2S plasma.",
author = "Shashank Balasubramanyam and Mahdi Shirazi and Matthew Bloodgood and Longfei Wu and Marcel Verheijen and Vincent Vandalon and Erwin Kessels and Hofmann, {Jan Philipp} and Bol, {Ageeth A.}",
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T1 - Edge-site nano-engineering of WS2 by low temperature plasma-enhanced atomic layer deposition for electrocatalytic hydrogen evolution

AU - Balasubramanyam, Shashank

AU - Shirazi, Mahdi

AU - Bloodgood, Matthew

AU - Wu, Longfei

AU - Verheijen, Marcel

AU - Vandalon, Vincent

AU - Kessels, Erwin

AU - Hofmann, Jan Philipp

AU - Bol, Ageeth A.

PY - 2019/6/25

Y1 - 2019/6/25

N2 - Edge-enriched transition metal dichalcogenides, such as WS 2, are promising electrocatalysts for sustainable production of H 2 through the electrochemical hydrogen evolution reaction (HER). The reliable and controlled growth of such edge-enriched electrocatalysts at low temperatures has, however, remained elusive. In this work, we demonstrate how plasma-enhanced atomic layer deposition (PEALD) can be used as a new approach to nanoengineer and enhance the HER performance of WS 2 by maximizing the density of reactive edge sites at a low temperature of 300 °C. By altering the plasma gas composition from H 2S to H 2 + H 2S during PEALD, we could precisely control the morphology and composition and, consequently, the edge-site density as well as chemistry in our WS 2 films. The precise control over edge-site density was verified by evaluating the number of exposed edge sites using electrochemical copper underpotential depositions. Subsequently, we demonstrate the HER performance of the edge-enriched WS 2 electrocatalyst, and a clear correlation among plasma conditions, edge-site density, and the HER performance is obtained. Additionally, using density functional theory calculations we provide insights and explain how the addition of H 2 to the H 2S plasma impacts the PEALD growth behavior and, consequently, the material properties, when compared to only H 2S plasma.

AB - Edge-enriched transition metal dichalcogenides, such as WS 2, are promising electrocatalysts for sustainable production of H 2 through the electrochemical hydrogen evolution reaction (HER). The reliable and controlled growth of such edge-enriched electrocatalysts at low temperatures has, however, remained elusive. In this work, we demonstrate how plasma-enhanced atomic layer deposition (PEALD) can be used as a new approach to nanoengineer and enhance the HER performance of WS 2 by maximizing the density of reactive edge sites at a low temperature of 300 °C. By altering the plasma gas composition from H 2S to H 2 + H 2S during PEALD, we could precisely control the morphology and composition and, consequently, the edge-site density as well as chemistry in our WS 2 films. The precise control over edge-site density was verified by evaluating the number of exposed edge sites using electrochemical copper underpotential depositions. Subsequently, we demonstrate the HER performance of the edge-enriched WS 2 electrocatalyst, and a clear correlation among plasma conditions, edge-site density, and the HER performance is obtained. Additionally, using density functional theory calculations we provide insights and explain how the addition of H 2 to the H 2S plasma impacts the PEALD growth behavior and, consequently, the material properties, when compared to only H 2S plasma.

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