CuO/Sb2S3 Nanoarchitectures for Enhanced Charge Generation/Separation for Photoelectrochemical Hydrogen Evolution
Authors: Kumar Mohit , Subrahmanyam Challapali 
Published: August 2024

Developing an efficient photocathode system using abundant earth materials is crucial for the effective process of Photoelectrochemical (PEC) water splitting. Achieving successful charge transfer between heterojunctions is a key consideration in creating an innovative photocathode that considers cost-effectiveness, material abundance, and PEC performance. In our study, we synthesized a p-type narrow band gap photocathode using copper oxide (CuO) with an energy gap (Eg) of 1.5 eV through a hydrothermal method. We then enhanced its performance by decorating it with antimony sulfide (Sb2S3) nanospheres (NSs) using a simple chemical bath deposition (CBD) technique, resulting in the formation of a CuO/Sb2S3 NSs heterojunction.
The fabricated heterojunction demonstrated superior PEC performance compared to the bare CuO. Specifically, we observed a significant increase in photocurrent density for the CuO/Sb2S3 NSs photocathode (J = -1 mA.cm-2) compared to CuO alone (J = -0.3 mA.cm-2) at a standard potential of 0 V vs RHE in a 0.5 M Na2SO4 solution with a pH of 6.85. This improvement can be attributed to the enhanced generation and separation of charge carriers. Furthermore, the CuO/Sb2S3 heterojunction exhibited remarkable photostability over a period of 2.5 h, with no degradation in photocurrent density. The Sb2S3 acted as a sensitizer, reducing the recombination rate of electron-hole pairs (e-/h+) within the CuO/Sb2S3 NSs, thereby enhancing the overall performance. The CuO/Sb2S3 NSs photocathode exhibited an ABPE% of 0.1%, while the ABPE% for CuO alone was 0.03%. This indicates a significant improvement in the performance of the CuO/Sb2S3 NSs photocathode. Onset potential (Eonset) was also observed to shift in a positive direction in CuO/Sb2S3 NSs as compared to CuO only. Eonset for the films followed a trend having CuO/Sb2S3 NSs (0.85 VRHE) > CuO (0.78 VRHE). Notably, this improvement is attributed to increased light absorption and a reduced recombination rate compared to the pristine CuO photocathode. Moreover, electrochemical impedance spectroscopy (EIS) studies provided evidence of enhanced electron transfer rates occurring at the interface between the heterojunction and the electrode/electrolyte interface. UV-Visible and photoluminescence (PL) emission spectra results indicated that the CuO/Sb2S3 NSs heterojunction exhibited an extended absorption spectrum and a reduced rate of recombination, further supporting the enhanced performance. Additionally, electrochemical impedance spectroscopy studies revealed lower charge transfer resistance in the CuO/Sb2S3 NSs heterojunction compared to CuO alone.
These findings open up new avenues for the development of novel photocathodic materials and heterojunctions utilizing copper-based binary oxides/chalcogenides for efficient solar harvesting applications.
References
(1) Kumar, M.; Singh, A.; Meena, B.; Sahu, P. K.; Subrahmanyam, C. Decoration of Spherical Sb2S3 over CuO Nanoflakes for Efficient Photoelectrochemical Hydrogen Generation. Results Eng.
2023, 101513. https://doi.org/10.1016/j.rineng.2023.101513.
(2) Kumar, M.; Meena, B.; Subramanyam, P.; Suryakala, D.; Subrahmanyam, C. Emerging Copper-Based Semiconducting Materials for Photocathodic Applications in Solar Driven Water Splitting. Catalysts
2022, 12 (10), 1198. https://doi.org/10.3390/catal12101198.
(3) Kumar, M.; Meena, B.; Subramanyam, P.; Suryakala, D.; Subrahmanyam, C. Recent Trends in Photoelectrochemical Water Splitting: The Role of Cocatalysts. NPG Asia Mater.
2022, 14 (1), 88. https://doi.org/10.1038/s41427-022-00436-x.

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