Lewis Acid Site Assisted Bifunctional Activity of Tin Doped Gallium Oxide and Its Application in Rechargeable Zn-Air Batteries.

The enhanced safety, superior energy, and power density of rechargeable metal-air batteries make them ideal energy storage systems for application in energy grids and electric vehicles. However, the absence of a cost-effective and stable bifunctional catalyst that can replace expensive platinum (Pt)-based catalyst to promote oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the air cathode hinders their broader adaptation. Here, it is demonstrated that Tin (Sn) doped ß-gallium oxide (ß-Ga2 O3 ) in the bulk form can efficiently catalyze ORR and OER and, hence, be applied as the cathode in Zn-air batteries. The Sn-doped ß-Ga2 O3 sample with 15% Sn (Snx =0.15 -Ga2 O3 ) displayed exceptional catalytic activity for a bulk, non-noble metal-based catalyst. When used as a cathode, the excellent electrocatalytic bifunctional activity of Snx =0.15 -Ga2 O3 leads to a prototype Zn-air battery with a high-power density of 138 mW cm-2 and improved cycling stability compared to devices with benchmark Pt-based cathode. The combined experimental and theoretical exploration revealed that the Lewis acid sites in ß-Ga2 O3 aid in regulating the electron density distribution on the Sn-doped sites, optimize the adsorption energies of reaction intermediates, and facilitate the formation of critical reaction intermediate (O*), leading to enhanced electrocatalytic activity.

Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics.

This work for the first time unfurls the fundamental mechanisms and sets the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band-gap oxide material. Specifically, we report on the tunable optical properties, in terms of wide spectral selectivity and red-shifted band gap, and electrocatalytic behavior of iron (Fe)-doped gallium oxide (ß-Ga2O3) model system. X-ray diffraction (XRD) studies of sintered Ga2-x Fe x O3 (GFO) (0.0 ≤ x ≤ 0.3) compounds provide evidence for the Fe3+ substitution at Ga3+ site without any secondary phase formation. Rietveld refinement of XRD patterns reveals that the GFO compounds crystallize in monoclinic crystal symmetry with a C2/m space group. The electronic structure of the GFO compounds probed using X-ray photoelectron spectroscopy data reveals that at lower concentrations, Fe exhibits mixed chemical valence states (Fe3+, Fe2+), whereas single chemical valence state (Fe3+) is evident for higher Fe content (x = 0.20-0.30). The optical absorption spectra reveal a significant red shift in the optical band gap with Fe doping. The origin of the significant red shift even at low concentrations of Fe (x = 0.05) is attributed to the strong sp-d exchange interaction originated from the 3d5 electrons of Fe3+. The optical absorption edge observed at ≈450 nm with lower intensity is the characteristic of Fe-doped compounds associated with Fe3+-Fe3+ double-excitation process. Coupled with an optical band-gap red shift, electrocatalytic studies of GFO compounds reveal that, interestingly, Fe-doped Ga2O3 compound exhibits electrocatalytic activity in contrast to intrinsic Ga2O3. Fe-doped samples (GFO) demonstrated appreciable electrocatalytic activity toward the generation of H2 through electrocatalytic water splitting. An onset potential and Tafel slope of GFO compounds include ∼900 mV, ∼210 mV dec-1 (x = 0.15) and ∼1036 mV, ∼290 mV dec-1 (x = 0.30), respectively. The electrocatalytic activity of Fe-doped Ga-oxide compounds is attributed to the cumulative effect of different mechanisms such as doping resulting in new catalytic centers, enhanced conductivity, and electron mobility. Hence, in this report, for the first time, we explored a new pathway; the electrocatalytic behavior of Fe-doped Ga2O3 resulted due to Fe chemical states and red shift in the optical band gap. The implications derived from this work may be applicable to a large class of compounds, and further options may be available to design functional materials for electrocatalytic energy production.