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

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-06-20 DOI:10.1021/acscatal.4c01445

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

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Abstract

Molybdenum sulfides (MoS_x) 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 MoS_x with adjustable S/Mo ratio (2.8–4.7) and crystalline MoS₂ with tailored crystallinity, morphology, and electrical properties. All the amorphous MoS_x 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 MoS_x, 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 MoS_x HER electrocatalysts as well as new insights into their activity and structure.

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通过原子层沉积制备的用于氢气进化反应的 MoSx 的结构特性

晶态和非晶态硫化钼（MoSx）是酸中氢进化反应（HER）很有前途的富土电催化剂。等离子体增强原子层沉积技术可用于制备 S/Mo 比可调（2.8-4.7）的非晶态 MoSx 薄膜和具有定制结晶度、形态和电性能的晶体 MoS2 薄膜。所有无定形 MoSx 薄膜在大约 -0.3 V 对可逆氢电极进行电化学活化后，都会转化为具有高度氢转换活性的无定形 MoS2（在 0.5 M H2SO4 中 10 mA/cm2 的过电位为 210-250 mV）。然而，初始薄膜的化学计量会影响其结构，进而影响 HER 的活性和稳定性。我们使用原位和准原位 X 射线光电子能谱对活化过程中发生的材料变化进行了研究。提出了沉积和活化催化剂的可能结构。与无定形 MoSx 不同，晶体 MoS2 催化剂的结构没有发生变化。在 10 mA/cm2 的条件下，晶体薄膜的过电位在 300 至 520 mV 之间，其中缺陷最大的催化剂的过电位最低。这项工作为沉积量身定制的 MoSx HER 电催化剂提供了一种实用方法，并对其活性和结构有了新的认识。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.