CuO–V<sub>2</sub>O<sub>5</sub> Composite vs Single-Phase Cu<sub>2</sub>V<sub>2</sub>O<sub>7</sub>: Understanding the Synergy of Mixed-Metal Oxides in Customizing Their Properties for Improved Hydrogen Evolution Reaction
Santhosh Kumar Jayaraj, Pratheep Panneerselvam, Meera Antony, Arvind H. Jadhav, P. Thangadurai, Sakar Mohan
Abstract
This study sheds light on how the electrochemical hydrogen evolution reaction (HER) properties of Cu–V–O-based mixed-metal oxides are influenced when they are constructed into composite (CuO–V 2 O 5 ) and single-phase (Cu 2 V 2 O 7 ) systems. The X-ray diffraction (XRD) analysis revealed the coexistence of CuO and V 2 O 5 in the composite and the formation of the single-phase structure of Cu 2 V 2 O 7 . The Raman spectrum of the CuO–V 2 O 5 composite showed dominant vibrations of V 2 O 5 over CuO, indicating its competitive properties in the composite. Optical analysis further confirmed the competitive properties of the CuO–V 2 O 5 composite, while the Cu 2 V 2 O 7 system exhibited synergistic properties. Accordingly, Cu 2 V 2 O 7 demonstrated the lowest overpotential of 161 mV at a current density of 10 mA/cm 2, compared to 203 mV for the CuO–V 2 O 5 composite, which is higher than its individual components (174 mV for CuO and 181 mV for V 2 O 5 ). Similarly, Tafel slope values of 128, 92, 102, and 76 mV/dec were estimated for CuO, V 2 O 5, CuO–V 2 O 5, and Cu 2 V 2 O 7, respectively. The corresponding double-layer capacitances of 0.86, 0.59, 0.47, and 0.97 mF/cm 2 were also estimated, associated with the respective electrochemical surface area of the systems. In addition, the charge transfer resistance of ∼0.4 kΩ was estimated for Cu 2 V 2 O 7, which is several times lower than those of the other systems. These results indicate that in mixed-metal oxides, unless the individual components are integrated through chemical interactions, the composite system exhibits competitive properties. In contrast, the chemically interacting Cu 2 V 2 O 7 system manifests synergistic properties, leading to excellent hydrogen evolution reaction (HER) efficiencies, as observed in this study.