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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Engineering antibonding orbital occupancy of NiMoO4-supported Ru nanoparticles for enhanced chlorine evolution
Dianzhi Zhang1, Haiming Gong1, Tao Liu1
1Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan 430078, China.
Abstract:
Chlorine evolution reaction (CER) is crucial for industrial-scale production of high-purity Cl2. Despite the development of classical dimensionally stable anodes to enhance CER efficiency, the competitive oxygen evolution reaction (OER) remains a barrier to achieving high Cl2 selectivity. Herein, a binder-free electrode, Ru nanoparticles (NPs)-decorated NiMoO4 nanorod arrays (NRAs) supported on Ti foam (Ru-NiMoO4/Ti), was designed for active CER in saturated NaCl solution (pH = 2). The Ru-NiMoO4/Ti electrode exhibits a low overpotential of 20 mV at 10 mA cm-2 current density, a high Cl2 selectivity exceeding 90%, and robust durability for 90h operation. The marked difference in Tafel slopes between CER and OER indicates the high Cl2 selectivity and superior reaction kinetics of Ru-NiMoO4/Ti electrode. Further studies reveal a strong metal-support interaction (SMSI) between Ru and NiMoO4, facilitating electron transfer through the Ru-O bridge bond and increasing the Ru 3d-Cl 2p antibonding orbital occupancy, which eventually results in weakened Ru-Cl bonding, promoted Cl desorption, and enhanced Cl2 evolution. Our findings provide new insights into developing electrodes with enhanced CER performance through antibonding orbital occupancy engineering.
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