Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid.

We demonstrate electric power generation via the electrooxidation of ethylene glycol (EG) on a series of Fe-group nanoalloy (NA) catalysts in alkaline media. A series of Fe-group binary NA catalysts supported on carbon (FeCo/C, FeNi/C, and CoNi/C) and monometallic analogues (Fe/C, Co/C, and Ni/C) were synthesized. Catalytic activities and product distributions on the prepared Fe-group NA catalysts in the EG electrooxidation were investigated by cyclic voltammetry and chronoamperometry, and compared with those of the previously reported FeCoNi/C, which clarified the contributory factors of the metal components for the EG electrooxidation activity, C2 product selectivity, and catalyst durability. The Co-containing catalysts, such as Co/C, FeCo/C, and FeCoNi/C, exhibit relatively high catalytic activities for EG electrooxidation, whereas the catalytic performances of Ni-containing catalysts are relatively low. However, we found that the inclusion of Ni is a requisite for the prevention of rapid degradation due to surface modification of the catalyst. Notably, FeCoNi/C shows the highest selectivity for oxalic acid production without CO2 generation at 0.4 V vs. the reversible hydrogen electrode (RHE), resulting from the synergetic contribution of all of the component elements. Finally, we performed power generation using the direct EG alkaline fuel cell in the presence of the Fe-group catalysts. The power density obtained on each catalyst directly reflected the catalytic performances elucidated in the electrochemical experiments for the corresponding catalyst. The catalytic roles and alloying effects disclosed herein provide information on the design of highly efficient electrocatalysts containing Fe-group metals.

CO2-free power generation on an iron group nanoalloy catalyst via selective oxidation of ethylene glycol to oxalic acid in alkaline media.

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.