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Updated: May 24, 2025
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Published on: October 5, 2019
3d-2p-5d Orbital Synergy in Electrocatalytic Hydrazine Oxidation Assisted Water Splitting with Industrial Scale
Pragya Arora1, Kiran Bhadauriya1, Labham Singh1
1Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India.
Abstract:
The hydrazine oxidation reaction (HzOR) is a promising alternative to the oxygen evolution reaction (OER) in electrolyzers due to its lower oxidation potential than water, which significantly reduces energy demands and enhances hydrogen production efficiency. Incorporating high-valent 5d metals into 3d metal hydroxides has shown great potential for enhancing water-splitting performance through strong 3d-2p-5d orbital interactions, improving charge transfer, intermediate adsorption, and reducing overpotentials. This study showcases an innovative approach to enhance the electrocatalytic performance of Co(OH)2 through the incorporation of a high-valent 5d metal, tungsten (W6+), using a straightforward electrochemical synthesis method. The incorporation of W6+ into Co(OH)2 led to significant Co3d-O2p-W5d orbital coupling, strengthening the electronic interactions between Co and W. The high-valent W6+ facilitated electron withdrawal from Co2+, promoting easier access to Co3+ sites enhancing the catalytic performance. The W-Co(OH)2 achieved a current density of 100 mA cm-2 at a potential of 1.00 V versus RHE for the HzOR, which is notably lower than the 1.54 V versus RHE required for the OER. In a two-electrode system, substituting OER with HzOR resulted in a significant reduction in cell voltage by 0.50 V.
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