Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)
DOI: https://doi.org/10.29363/nanoge.matsusfall.2024.257
Publication date: 28th August 2024
Forming complex structures of functional materials in a controlled and reproducible fashion is a well-known challenge. [1,2] Specifically, bimetallic phosphides are of interest for energy-related applications; however, a satisfactory structure-function relationship has not been fully deciphered yet. In this work, we show that a colloidal chemistry approach produces bimetallic phosphides electrocatalysts of Co and Cu, size range 40-100 nm, where segregation and phase transformation induce significant changes in morphology compared to solid solutions. Their complexity permits the tuning of the catalytic sites to the hydrogen and oxygen evolution reactions (HER and OER), allowing the bimetallic phosphides to catalyze the full water splitting reaction. The experimental results show that in alkaline medium water cleavage is particularly favorable on CuxCoyP catalysts (and especially when x = 50%), enhancing their HER performance with an overpotential of 184 mV @ 10 mA/cm2. As for the OER enhancement, the results show that the bimetallic phosphides undergo a surface transformation during the OER, whereby (oxy)hydroxides form at anodic potentials in alkaline solution and serve as the actual electrocatalysts. The best OER performance was displayed by Cu25Co75P having an overpotential of 283 mV @ 10 mA/cm2. [3] Additionally, these CuxCoyP catalysts offer promising functionality towards methanol oxidation reaction (MOR) without fully oxidizing it to CO2 and rather producing beneficial product formate (HCOO-), displaying a lower overpotential by up to 180 mV as compared to OER and a higher mass activity. At 1.52 V and on passing 300 C charge the Faradaic efficiency for formate production is 100% in case of both the bimetallic and monometallic phosphides. This kind of selective oxidation of methanol is highly desired in direct alcohol fuel cell applications. [4]
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