Simultaneously Improved Surface and Bulk Participation of Evolved Perovskite Oxide for Boosting Oxygen Evolution Reaction Activity Using a Dynamic Cation Exchange Strategy.

Perovskite oxides are intriguing electrocatalysts for the oxygen evolution reaction, but both surface (e.g., composition) and bulk (e.g., lattice oxygen) properties should be optimized to maximize their participation in offering favorable activity and durability. In this work, it is demonstrated that through introducing exogenous Fe3+ ( Fe exo 3 + ${\rm{Fe}}_{{\rm{exo}}}^{3 + }$ ) into the liquid electrolyte, not only is the reconstructed surface stabilized and optimized, but the lattice oxygen diffusion is also accelerated. As a result, compared to that in Fe-free 0.1 m KOH, PrBa0.5 Sr0.5 Co2 O5+δ in 0.1 m KOH + 0.1 mm Fe3+ demonstrates a tenfold increment in activity, an extremely low Tafel slope of ≈50 mV dec-1 , and outstanding stability at 10.0 mA cm-2  for 10 h. The superior activity and stability are further demonstrated in Zn-air batteries by presenting high open-circuit voltage, narrow potential gap, high power output, and long-term cycle stability (500 cycles). Based on experimental and theoretical calculations, it is discovered that the dynamical interaction between the Co hydr(oxy)oxide from surface reconstruction and intentional Fe3+ from the electrolyte plays an important role in the enhanced activity and durability, while the generation of a perovskite-hydr(oxy)oxide heterostructure improves the lattice oxygen diffusion to facilitate lattice oxygen participation and enhances the stability.

Electrochemical properties and facile preparation of hollow porous V2O5 microspheres for lithium-ion batteries.

Vanadium pentoxide (V2O5) has shown great potential to be used in lithium-ion batteries (LIBs), but it has limited applications because it has cycle instability and poor rate capability, and its lithiation mechanism is not well understood. In this work, hollow porous V2O5 microspheres (HPVOM) were obtained by a facile poly(vinylpyrrolidone) and ethylene glycol-assisted soft-template solvothermal method. Half cells with HPVOM exhibited good capacity, rate capability, and stability, delivering 407.9 mAh g-1 at 1.0 A g-1 after 700 cycles. Furthermore, a LiFePO4/HPVOM full cell had a discharge capacity of 109.9 mAh g-1 after 150 cycles at 0.1 A g-1. Using an equivalent circuit model (ECM) and distribution of relaxation times (DRT), we found that the charge-transfer (including the solid-state interface resistance) and bulk resistances varied regularly with the charge/discharge state, while the electrolyte resistance was largely maintained. The bulk resistance finally vanished, indicative of dynamic activation. The method used to prepare the hollow microspheres, as well as the display of electrode kinetics via ECM and DRT, could be broadly applied in developing efficient electrodes for LIBs.

Fluorescence resonance energy transfer aptasensor between nanoceria and graphene quantum dots for the determination of ochratoxin A.

In the present work, colloidal cerium oxide nanoparticles (nanoceria) and graphene quantum dots (GQDs) were firstly synthesized by sol-gel method and pyrolysis respectively, which all have a uniform nano-size and significant fluorescence emission. Due to the fluorescence emission spectrum of nanoceria overlapped the absorption spectrum of GQDs, fluorescence resonance energy transfer (FRET) between nanoceria and GQDs could occur effectively by the electrostatic interaction. Based on it, a sensitive ratiometric fluorescence aptasensor for the determination of ochratoxin A (OTA), a small molecular mycotoxin produced by Aspergillus and Penicillium strains, has been successfully constructed. In which, probe DNA1@nanoceria and DNA2@GQD were designed to complementary with OTA aptamer, both could adsorb each other, leading to the occur of FRET. After adding of OTA aptamer and then introducing of OTA, the FRET would be interrupted/recovered due to the specific affinity of OTA and its aptamer, the fluorescence recovery value would increase with the addition of OTA. Under the optimal experimental conditions (pH 7, mGQD/nanoceria 2, captamer 100 nM, incubation time 30 min), the constructed ratiometric fluorescence aptasensor exhibited a satisfying linear range (0.01-20 ng mL-1), low limit of detection (2.5 pg mL-1) and good selectivity towards OTA, and has been successfully applied for the analysis of real sample peanuts with good accuracy of the recoveries ranged from 90 to 110%.

Decorated and reconstructed perovskite-oxide electrodes for oxygen electrocatalysis and Zn-air batteries.

Although decorated nanoparticles offer a great potential to generate extra active sites, their preparation usually requires time- and energy-consuming approaches. We report the remarkable activity and durability augmentation for the oxygen evolution reaction (OER) via effective and facile on-site electrochemical manipulation, using LaNiO3 as a model catalyst. When compared to the pristine LaNiO3, the electrochemically manipulated LaNiO3 cycled in Fe3+-containing 0.1 M KOH (i.e., E-LNO+Fe) exhibits an almost three-fold improvement in current density at 1.65 V. It is experimentally and theoretically shown that the electrochemical manipulation leads to the creation of defective LaNiO3-δ and NiO on the surfaces, which accelerate phase transformation to (oxy)hydroxides and hence the OER. Furthermore, a Zn-air battery assembled with E-LNO+Fe has demonstrated superior activity by presenting 171 mW cm-2. Thus, our work demonstrates that substantial performance increases may be achieved by decorating and reconstructing perovskite-oxide electrodes via on-site electrochemical modification.