Metal electrocatalysts have been reported to improve the electron transfer kinetics of aqueous redox flow battery electrolytes on various types of carbon electrodes. In this work, we electrodeposited bismuth metal onto a carbon paper anode of a redox flow battery containing our previously reported polyaminocarboxylate-chelated chromium electrolyte. Depositing 0.58 mg cm–2 of bismuth metal enabled an electrochemically reversible electron transfer for the Cr(II) / Cr(III) couple, resulting in a 3.9% voltage efficiency increase over ten cycles at 100 mA cm–2 across an 80% state of charge window, while maintaining >99% current efficiency. The bismuth electrocatalyst provided other improvements, such as a 13% increase in average discharge power density when cycling at 80% energy efficiency, along with a 60% decrease in charge transfer resistance and 12% decrease in the full cell area specific resistance. A chelated bismuth complex was also utilized as a bismuth source for electrodeposition, providing an example of how polyaminocarboxylate ligands can be further implemented into efforts towards improving the energy efficiency of aqueous redox flow batteries.
The aerobic photochemical oxidation of benzylamine was carried out on the ternary oxides CuWO and BiVO as a test proton-coupled-electron-transfer reaction in acetonitrile. Both oxides give the coupled imine product, N-benzylidenebenzylamine, in near quantitative (98-99%) yield, with rate constants of 0.34 h g and 0.70 h g for CuWO and BiVO, respectively.
Depositing the earth-abundant water oxidation electrocatalyst FeOOH onto WO 3 has been shown to increase the Faradaic efficiency of the tandem WO 3 |FeOOH photoanode to near 100% for the photoelectrocatalytic oxidation of water to oxygen. Here we begin to explore how this gain in Faradaic efficiency is imparted through hydroxyl radical trap and Tafel experiments. It was found that increasing the FeOOH deposition time of the WO 3 | FeOOH caused a decrease in the quantity of hydroxyl radical trapped during photoelectrocatalytic water oxidation. These results, along with the disparate Tafel slopes of bare WO 3 and WO 3 |FeOOH, suggest a change in the water oxidation mechanism between the two materials.
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