Structural Aspects of MoSx Prepared by Atomic Layer Deposition for Hydrogen Evolution Reaction

Miika Mattinen; Wei Chen; Rebecca A. Dawley; Marcel A. Verheijen; Emiel J.M. Hensen; W.M.M. Kessels; Ageeth A. Bol

doi:10.1021/acscatal.4c01445

Structural Aspects of MoSx Prepared by Atomic Layer Deposition for Hydrogen Evolution Reaction

Miika Mattinen, Wei Chen, Rebecca A. Dawley, Marcel A. Verheijen, Emiel J.M. Hensen, W.M.M. Kessels, Ageeth A. Bol (Corresponding author)

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Abstract

Molybdenum sulfides (MoSx) in both crystalline and amorphous forms are promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER) in acid. Plasma-enhanced atomic layer deposition was used to prepare thin films of both amorphous MoSx with adjustable S/Mo ratio (2.8–4.7) and crystalline MoS2 with tailored crystallinity, morphology, and electrical properties. All the amorphous MoSx films transform into highly HER-active amorphous MoS2 (overpotential 210–250 mV at 10 mA/cm2 in 0.5 M H2SO4) after electrochemical activation at approximately −0.3 V vs reversible hydrogen electrode. However, the initial film stoichiometry affects the structure and consequently the HER activity and stability. The material changes occurring during activation are studied using ex situ and quasi in situ X-ray photoelectron spectroscopy. Possible structures of as-deposited and activated catalysts are proposed. In contrast to amorphous MoSx, no changes in the structure of crystalline MoS2 catalysts are observed. The overpotentials of the crystalline films range from 300 to 520 mV at 10 mA/cm2, being the lowest for the most defective catalysts. This work provides a practical method for deposition of tailored MoSx HER electrocatalysts as well as new insights into their activity and structure.

Original language	English
Pages (from-to)	10089-10101
Number of pages	13
Journal	ACS Catalysis
Volume	14
Issue number	13
Early online date	20 Jun 2024
DOIs	https://doi.org/10.1021/acscatal.4c01445
Publication status	Published - 5 Jul 2024

Funding

The work has received funding from The Netherlands Organization for Scientific Research (NWO) through Vici project 17846 \u201CDefects, a curse or a blessing: tailoring defects in two-dimensional transition metal dichalcogenides by atomic layer deposition\u201D. The authors gratefully acknowledge B. Krishnamoorthy, C. A. A. van Helvoirt, C. O. van Bommel, and J. J. A. Zeebregts for technical assistance and support on PEALD and characterization at the Eindhoven University of Technology (TU/e). Dr. B. Barcones (TU/e) is acknowledged for FIB preparation of the TEM sample. The TEM facility has received funding from Solliance and the Dutch province of Noord-Brabant. J. J. P. M. Schulpen (TU/e) is thanked for MoS deposition on carbon fiber paper. Dr. Marta Costa Figueiredo (TU/e) is acknowledged for electrochemistry discussions. Dr. Giulio D\u2019Acunto (Stanford University) is thanked for XPS discussions. The authors are grateful to Roy Wentz from the University of Michigan glass shop for custom glassblowing services. x

Keywords

atomic layer deposition
electrocatalyst
electrochemical activation
hydrogen evolution reaction
molybdenum sulfide
water splitting

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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title = "Structural Aspects of MoSx Prepared by Atomic Layer Deposition for Hydrogen Evolution Reaction",

abstract = "Molybdenum sulfides (MoSx) in both crystalline and amorphous forms are promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER) in acid. Plasma-enhanced atomic layer deposition was used to prepare thin films of both amorphous MoSx with adjustable S/Mo ratio (2.8–4.7) and crystalline MoS2 with tailored crystallinity, morphology, and electrical properties. All the amorphous MoSx films transform into highly HER-active amorphous MoS2 (overpotential 210–250 mV at 10 mA/cm2 in 0.5 M H2SO4) after electrochemical activation at approximately −0.3 V vs reversible hydrogen electrode. However, the initial film stoichiometry affects the structure and consequently the HER activity and stability. The material changes occurring during activation are studied using ex situ and quasi in situ X-ray photoelectron spectroscopy. Possible structures of as-deposited and activated catalysts are proposed. In contrast to amorphous MoSx, no changes in the structure of crystalline MoS2 catalysts are observed. The overpotentials of the crystalline films range from 300 to 520 mV at 10 mA/cm2, being the lowest for the most defective catalysts. This work provides a practical method for deposition of tailored MoSx HER electrocatalysts as well as new insights into their activity and structure.",

keywords = "atomic layer deposition, electrocatalyst, electrochemical activation, hydrogen evolution reaction, molybdenum sulfide, water splitting",

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AB - Molybdenum sulfides (MoSx) in both crystalline and amorphous forms are promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER) in acid. Plasma-enhanced atomic layer deposition was used to prepare thin films of both amorphous MoSx with adjustable S/Mo ratio (2.8–4.7) and crystalline MoS2 with tailored crystallinity, morphology, and electrical properties. All the amorphous MoSx films transform into highly HER-active amorphous MoS2 (overpotential 210–250 mV at 10 mA/cm2 in 0.5 M H2SO4) after electrochemical activation at approximately −0.3 V vs reversible hydrogen electrode. However, the initial film stoichiometry affects the structure and consequently the HER activity and stability. The material changes occurring during activation are studied using ex situ and quasi in situ X-ray photoelectron spectroscopy. Possible structures of as-deposited and activated catalysts are proposed. In contrast to amorphous MoSx, no changes in the structure of crystalline MoS2 catalysts are observed. The overpotentials of the crystalline films range from 300 to 520 mV at 10 mA/cm2, being the lowest for the most defective catalysts. This work provides a practical method for deposition of tailored MoSx HER electrocatalysts as well as new insights into their activity and structure.

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Structural Aspects of MoSx Prepared by Atomic Layer Deposition for Hydrogen Evolution Reaction

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