Enhanced Photoelectrochemical Performance in Engineered Interface 2D Metal Sulfide Heterostructures for Water Splitting
Authors: Velpandian Muthuraja , Meduri Praveen 
Published: July 2022

Photoelectrochemical water splitting (PEC) is a viable solution for addressing future environmental and energy concerns. However, due to the high cost of photoelectrodes and the limitations of sluggish kinetics, practical applications are limited. To achieve that goal, effective solutions are still needed to create low-cost photoelectrodes suited for PEC. Transistion metal sulfides (TMS) materials have a high potential for use as photoelectrodes due to their favorable and impressive properties1. The photoactivity of TMS is typically unlimited due to low reflection at the grain boundary. The individual atomic thin sheets with higher surface area compared to bulk materials allow for faster diffusion of photoinduced charge carriers primarily due to the less interface between their grains. Their lower interfacial contact resistance enables enhanced charge dynamics and, as a result, improved electrochemical reaction kinetics. When compared to other TMS, CdS has a direct bandgap and excellent photoactivity. However, its toxicity and photocorrosion make it unsuitable for long-term practical use. WS2 is well-known layered transition metal sulfide that has a 2D molybdenite structure. It is non-toxic in acidic/neutral solutions that are chemically stable. It has been demonstrated to be more stable against oxidation and photo corrosion than CdS, which is extensively employed in photocatalysis2. However, because of the recombination of photoinduced charge carriers, pure WS2 exhibits relatively poor photocatalytic efficiency and stability. As a result, combining WS2 based photoactive nanomaterials with other suitable materials has helped overcome this challenge. Transistion metal sulfides with acceptable band structures for heterostructure construction with WS2 may enable breakthroughs in photocatalytic and photo-electrochemical processes.

The primary focus of this work is to construct heterostructures by combining CdS and WS2 and to investigate their role as photoanodes of semiconductor materials in PEC water splitting. In this work, we have synthesised heterostructures using a facile solution-reaction method and Successive Ionic Layer Adsorption Reaction deposition (SILAR) technique which is intrinsically cost effective and scalable3. The heterostructure is characterised by XRD, SEM and TEM. We also studied the performance enhancement of this heterostructure using Linear sweep voltammetry and Electrochemical impedance spectroscopy. Pristine WS2 and CdS showed photocurrent densities of 3 μA cm-2 and 20 μA cm-2. However, heterostructures formation led to much improved photocurrents. Photocurrent densities of 151 μA cm-2 were observed for WS2/CdS heterostructures respectively at 1.23 V vs RHE. The enhanced improvement in photoelectrochemical performance in the case of the heterostructures could be due to the following factors: (a) the intimate interaction of this unique heterostructure improves adhesion and lowers the photoinduced charge transfer barrier; (b) increased light harvesting capability; and (c) improved charge dynamics of photoinduced charge carriers due to proper band alignment. The current study paves the way for further research into the creation of metal sulfide heterostructures that generate analogous photoelectrode materials.

Keywords: Photoelectrochemical water splitting, metal sulfides, photoelectrodes.

References:

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M. Velpandian, S. Pulipaka, A. Tikoo, and P. Meduri, Improved charge carrier dynamics of WS2 nanostructures by the way of CdS@WS2 heterostructures for use in water splitting and water purification, Sustain. Energy Fuels, 2020, 4, 4096-4107, DOI:10.1039/d0se00533a.

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