ABSTRACT
High entropy oxides (HEOs) offer great potential as catalysts for oxygen electrocatalytic reactions in alkaline environments. Herein, a novel synthesis approach to prepare (FeCrCoMnZn)3O4-δ high entropy spinel oxide in a vacuum atmosphere, with the primary objective of introducing oxygen vacancies into the crystal structure, is presented. As compared to the air-synthesized counterpart, the (FeCrCoMnZn)3O4-δ with abundant oxygen vacancies demonstrates a low (better) bifunctional (BI) index of 0.89 V in alkaline media, indicating enhanced electrocatalytic oxygen catalytic activity. Importantly, (FeCrCoMnZn)3O4-δ demonstrates outstanding long-term electrochemical and structural stability. When utilized as electrocatalysts in the air cathode of Zn-air batteries, the vacuum atmosphere synthesized (FeCrCoMnZn)3O4-δ catalysts outperform the samples treated in an air atmosphere, displaying superior peak power density, specific capacity, and cycling stability. These findings provide compelling evidence that manipulating the synthesis atmosphere of multi-component oxides can serve as a novel approach to tailor their electrochemical performance.
ABSTRACT
Perovskite oxides have been considered promising oxygen evolution reaction (OER) electrocatalysts due to their high intrinsic activity. Yet, their poor long-term electrochemical and structural stability is still controversial. In this work, we apply an A-site management strategy to tune the activity and stability of a new hexagonal double perovskite oxide. We synthesized the previously inaccessible 2H-Ba2CoMnO6-δ (BCM) perovskite oxide via the universal sol-gel method followed by a novel air-quench method. The new 2H-BCM perovskite oxide exhibits outstanding OER activity with an overpotential of 288 mV at 10 mA cm-2 and excellent long-term stability without segregation or structural change. To understand the origin of outstanding OER performance of BCM, we substitute divalent Ba with trivalent La at the A-site and investigate crystal and electronic structure change. Fermi level and valence band analysis presents a decline in the work function with the Ba amount, suggesting a structure-oxygen vacancy-work function-activity relationship for Ba x La2-x CoMnO6-δ (x = 0, 0.5, 1, 1.5, 2) electrocatalysts. Our work suggests a novel production strategy to explore the single-phase new structures and develop enhanced OER catalysts.
ABSTRACT
Silver nanowire (Ag NW) networks have great potential to replace commercial transparent conducting oxides due to their superior properties in conjunction with their competitive cost, availability and mechanical flexibility. However, there are still challenges to overcome for the large scale utilization of Ag NWs in devices due to oxidation/sulfidation of NWs, which leads to performance loss. Here, we develop a solution-based strategy to deposit a thin platinum (Pt) shell layer (15 nm) onto Ag NWs to improve their chemical, environmental and electrochemical stabilities. Environmental and thermal stabilities of the core-shell NW networks were monitored under different relative humidity conditions (RH of 43, 75 and 85%) and temperature settings (75 °C for 120 hours and 150 °C for 40 hours) and compared to those of bare Ag NWs. Afterwards, stability of core-shell NW networks in hydrogen peroxide was investigated and compared to that of bare Ag NW networks. The potential window for electrochemical stability of the Ag NW networks was broadened to 0-1 V (vs. Ag/AgCl) upon Pt deposition, while bare Ag NWs were stable only in the 0-0.6 V range. Moreover, Ag-Pt core-shell NWs were used for the detection of hydrogen peroxide, where a high sensitivity of 0.04 µA µM-1 over a wide linear range of concentrations (16.6-990.1 µM) with a low detection limit (10.95 µM) was obtained for the fabricated sensors. All in all, this highly effective and simple strategy to improve the stability of Ag NWs will certainly open new avenues for their large-scale utilization in various electrochemical and sensing devices.
