Publication date: 21st July 2025
We present a photochemical oxidation strategy for the spatially controlled deposition of crystalline rhodium oxide (RhOx) co-catalysts on CdSe@CdS nanorods (SRs). Mechanistic investigations reveal that key reaction parameters - including pH, excitation wavelength, and electron acceptor identity - critically govern the site-selective heterogeneous nucleation of RhOx. Systematic tuning of these parameters during the photo-oxidative deposition process enables precise modulation of charge carrier dynamics within the semiconductor heterostructure. In particular, control over the directionality and density of photogenerated electron–hole pairs allow deterministic growth of Rh3O4 nanoparticles, yielding tunable co-catalyst architectures ranging from single-domain to multi-domain configurations. The refined synthetic protocol provides precise control over nanoparticle morphology, spatial positioning, and surface coverage, enabling the engineered formation of well-defined RhOx-SR interfaces through selective surface oxidation. These tailored heterojunctions exhibit optimized interfacial charge transfer kinetics and represent a significant advancement toward the rational design of efficient photocatalysts for overall water splitting. Such precise interfacial control is crucial for maximizing photocatalytic activity, accelerating the development of next-generation solar-to-fuel conversion technologies.
The authors gratefully acknowledge Dr. Kamira Cohen-Weinfeld for her invaluable contribution in acquiring X-ray photoelectron spectroscopy (XPS) data. We also thank Dr. Yael Etinger for performing the X-ray diffraction (XRD) analysis. Furthermore, we extend our sincere appreciation to Dr. Yaron Kaufmann for helping with the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDX) analyses.
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