Femtosecond Laser-Ablated Copper Surface as a Substrate for a MoS2-Based Hydrogen Evolution Reaction Electrocatalyst

One of the methods to improve the performance of a heterogeneous electrocatalyst is the dispersion of a catalytic material on a suitable substrate. In this study, femtosecond laser ablation was used to prepare very rough but also ordered copper surfaces consisting of vertical, parallel ridges. Then, a molybdenum sulfide coating was electrochemically deposited onto these surfaces. It was observed by profilometry that the average roughness of the surface after coating with MoS2 had decreased, but the developed surface area still remained significantly larger than the projected surface area. The electrodes were then used as an electrocatalyst for the hydrogen evolution reaction in acidic media. These were highly efficient, reaching 10 mA cm−2 of HER current at a −181 mV overpotential and a Tafel slope of ~39 mV dec−1. Additionally, scanning electrochemical microscopy was used to observe whether hydrogen evolution would preferentially occur in certain spots, for example, on the peaks, but the obtained results suggest that the entire surface is active. Finally, the electrochemical impedance spectroscopy data showed the difference in the double-layer capacitance between the ablated and non-ablated surfaces (up to five times larger) as well as the parameters that describe the improved catalytic activity of fs-Cu/MoS2 electrodes

The characterisation of electrodeposited MoS2 thin films on a foam-based electrode for hydrogen evolution

Molybdenum sulphide is an emerging precious-metal-free catalyst for cathodic water splitting. As its active sites catalyse the Volmer hydrogen adsorption step, it is particularly active in acidic media. This study focused on the electrochemical deposition of MoS2 on copper foam electrodes and the characterisation of their electrocatalytic properties. In addition, the electrodeposition was modified by adding a reducing agent—sodium hypophosphite—to the electrolyte. To reveal the role of hypophosphite, X-ray photoelectron spectroscopy (XPS) analysis was carried out in addition to scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). MoS2 films, electrodeposited at various charges passed through the cell (catalyst loadings), were tested for their catalytic activity towards hydrogen evolution in 0.5 M H2SO4. Polarisation curves and Tafel slope analysis revealed that the electrodeposited MoS2 films are highly active. Namely, Tafel slopes fell within the 40–50 mV dec−1 range. The behaviour of as-deposited films was also evaluated by electrochemical impedance spectroscopy over a wide overpotential range (0 to −0.3 V), and two clear time constants were distinguished. Through equivalent electrical circuit analysis, the experimental data were fitted to the appropriate model, and the obtained values of the circuit components were examined as a function of overpotential. It was found that the addition of NaH2PO2 into the electrodeposition solution affects the intrinsic activity of the material. Finally, a method is proposed to approximate the number of active sites from impedance dat

Femtosecond laser-ablated copper surface as a substrate for a MoS2-based hydrogen evolution reaction electrocatalyst

One of the methods to improve the performance of a heterogeneous electrocatalyst is the dispersion of a catalytic material on a suitable substrate. In this study, femtosecond laser ablation was used to prepare very rough but also ordered copper surfaces consisting of vertical, parallel ridges. Then, a molybdenum sulfide coating was electrochemically deposited onto these surfaces. It was observed by profilometry that the average roughness of the surface after coating with MoS2 had decreased, but the developed surface area still remained significantly larger than the projected surface area. The electrodes were then used as an electrocatalyst for the hydrogen evolution reaction in acidic media. These were highly efficient, reaching 10 mA cm−2 of HER current at a −181 mV overpotential and a Tafel slope of ~39 mV dec−1. Additionally, scanning electrochemical microscopy was used to observe whether hydrogen evolution would preferentially occur in certain spots, for example, on the peaks, but the obtained results suggest that the entire surface is active. Finally, the electrochemical impedance spectroscopy data showed the difference in the double-layer capacitance between the ablated and non-ablated surfaces (up to five times larger) as well as the parameters that describe the improved catalytic activity of fs-Cu/MoS2 electrodes

Electrochemical synthesis of a WO3/MoSx heterostructured bifunctional catalyst for efficient overall water splitting

Photo-/electrochemical water splitting can be a suitable method to produce “green” hydrogen and oxygen by utilizing renewable energy or even direct sunlight. In order to carry out photoelectrochemical (PEC) water splitting, a photoanode based on transition metal oxides, which absorbs photons and produces photoexcited electron–hole pairs, is needed. The positively charged holes can then participate in the water oxidation reaction. Meanwhile, a cathodic hydrogen evolution reaction (HER) can occur more efficiently with electrocatalytic materials that enhance the adsorption of H+, such as MoS2. In this study, it was shown that WO3/MoSx heterostructured materials can be synthesized by an electrochemical method called plasma electrolytic oxidation (PEO). During this process, many micro-breakdowns of the oxide layer occur, causing ionization of the oxide and electrolyte. The ionized mixture then cools and solidifies, resulting in crystalline WO3 with incorporated MoSx. The surface and cross-sectional morphology were characterized by SEM-FIB, and the coatings could reach up to 3.48 μm thickness. Inclusion of MoSx was confirmed by EDX as well as XPS. Synthesis conditions were found to have an influence on the band gap, with the lowest value being 2.38 eV. Scanning electrochemical microscopy was used to map the local HER activity and correlate the activity hotspots to MoSx’s content and surface topography. The bifunctional catalyst based on a WO3/MoSx heterostructure was evaluated for PEC and HER water-splitting activities. As a photoanode, it could reach up to 6% photon conversion efficiency. For HER in acidic media, a Tafel slope of 42.6 mV·dec−1 can be reached