Transition-metal dichalcogenides (TMDs) are at the forefront of research for their promising catalytic abilities and unique materials properties. With great interest in the study of mono- or few-layered TMDs, we seek to fundamentally explore the effects of doping on bulk TMDs, particularly MoS2 and WS2 for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) with p-dopants Nb and Ta. Despite promises reported in the computational studies of doped TMDs on the HER, our results show otherwise. Doped bulk TMDs display less catalytic activity in comparison to their undoped counterparts for the HER. A similar effect is observed for ORR catalysis. Characterization was done to shed light on its surface elemental composition, properties, and morphologies. It was found that doped WS2 has a high percentage of 1T phase but this does not correlate with a lower overpotential for the HER at −10 mA cm–2, which contradicts the general consensus. We therefore show that p-dopants have a negative electrocatalytic effect on the HER. These findings are of high importance for the field of TMD electrochemistry, as they challenge the current consensus that doping always improves the electrocatalysis of TMDs.
The layered structure of molybdenum disulfide (MoS2 ) is structurally similar to that of graphite, with individual sheets strongly covalently bonded within but held together through weak van der Waals interactions. This results in two distinct surfaces of MoS2 : basal and edge planes. The edge plane was theoretically predicted to be more electroactive than the basal plane, but evidence from direct experimental comparison is elusive. Herein, the first study comparing the two surfaces of MoS2 by using macroscopic crystals is presented. A careful investigation of the electrochemical properties of macroscopic MoS2 pristine crystals with precise control over the exposure of one plane surface, that is, basal plane or edge plane, was performed. These crystals were characterized thoroughly by AFM, Raman spectroscopy, X-ray photoelectron spectroscopy, voltammetry, digital simulation, and DFT calculations. In the Raman spectra, the basal and edge planes show anisotropy in the preferred excitation of E2g and A1g phonon modes, respectively. The edge plane exhibits a much larger heterogeneous electron transfer rate constant k(0) of 4.96×10(-5) and 1.1×10(-3) cm s(-1) for [Fe(CN)6 ](3-/4-) and [Ru(NH3 )6 ](3+/2+) redox probes, respectively, compared to the basal plane, which yielded k(0) tending towards zero for [Fe(CN)6 ](3-/4-) and about 9.3×10(-4) cm s(-1) for [Ru(NH3 )6 ](3+/2+) . The industrially important hydrogen evolution reaction follows the trend observed for [Fe(CN)6 ](3-/4-) in that the basal plane is basically inactive. The experimental comparison of the edge and basal planes of MoS2 crystals is supported by DFT calculations.
Though many studies examined the properties of the class of IIIA-VIA and IVA-VIA layered materials, few have delved into the electrochemical aspect of such materials. In light of the burgeoning interest in layered structures towards various electrocatalytic applications, we endeavored to study the inherent electrochemical properties of representative layered materials of this class, GaSe and GeS, and their impact towards electrochemical sensing of redox probes as well as catalysis of oxygen reduction, oxygen evolution and hydrogen evolution reactions. In contrast to the typical sandwich structure of MoS2 layered materials, GeS is isoelectronic to black phosphorus with the same structure; GaSe is a layered material consisting of GaSe sheets bonded in the sequence Se-Ga-Ga-Se. We characterized GaSe and GeS by employing scanning electron microscopy, X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy complemented by electronic structure calculations. It was found that the encompassing surface oxide layers on GaSe and GeS greatly influenced their electrochemical properties, especially their electrocatalytic capabilities towards hydrogen evolution reaction. These findings provide fresh insight into the electrochemical properties of these IIIA-VIA and IVA-VIA layered structures which enables development for future applications.
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