B-site Doping Boosts the OER and ORR Performance of Double Perovskite Oxide as Air Cathode for Zinc-Air Batteries.

Double perovskite oxides are key players as electrocatalytic oxygen catalysts in alkaline media. In this study, we synthesized B-site doped NdBaCoaFe2-aO5+δ (a= 1.0, 1.4, 1.6, 1.8) electrocatalysts, systematically to probe their bifunctionality and assess their performance in zinc-air batteries as air cathodes. X-ray photoelectron spectroscopy analysis reveals a correlation between iron reduction and increased oxygen vacancy content, influencing electrocatalyst bifunctionality by lowering the work function. The electrocatalyst with highest cobalt content, NdBaCo1.8Fe0.2O5+δ exhibited a bifunctional index of 0.95 V, outperforming other synthesized electrocatalysts. Remarkably, NdBaCo1.8Fe0.2O5+δ, demonstrated facilitated charge transfer rate in oxygen evolution reaction with four-electron oxygen reduction reaction process. As an air cathode in a zinc-air battery, NdBaCo1.8Fe0.2O5+δ demonstrated superior performance characteristics, including maximum capacity of 428.27 mA h at 10 mA cm-2 discharge current density, highest peak power density of 64 mW cm-2, with an outstanding durability and stability. It exhibits lowest voltage gap change between charge and discharge even after 350 hours of cyclic operation with a rate capability of 87.14%.

Multi-Foulant-Resistant Material Design by Matching Coating-Fluid Optical Properties.

The buildup of corrosion deposits, known as fouling, seriously hinders large-scale energy production. From nuclear power plants to geothermal reservoirs, fouling increases system pressure drops, impedes heat transfer, and accelerates corrosion, leading to derating and early failure. Here, we investigate the collodial interactions between multiple foulants and coated surfaces, with the aim of discovering principles for minimizing the adhesion of foulants to them. We hypothesize that matching the full refractive index spectrum of a coating to its surrounding fluid minimizes the adhesion of all foulants entrained within and that the Lifshitz theory is sufficient to predict which materials will be multi-foulant-resistant. First-principle calculations of Hamaker constants and refractive indices of six foulants on six coatings in water correlate well to direct measurements of adhesion by atomic force microscopy (AFM)-based force spectroscopy. Amorphous 2% fluorine-doped tin oxide, crystalline SiO2, CaF2, and Na3AlF6, which all nearly match the refractive index spectrum of water, successfully resisted adhesion of six diverse foulant materials in aqueous AFM measurements. The validation of this design principle may be expanded to design multi-fouling-resistant coatings for any system in which van der Waals forces are the dominant adhesion mechanism.

What is the trigger for the hydrogen evolution reaction? - towards electrocatalysis beyond the Sabatier principle.

The mechanism of the hydrogen evolution reaction, although intensively studied for more than a century, remains a fundamental scientific challenge. Many important questions are still open, making it elusive to establish rational principles for electrocatalyst design. In this work, a comprehensive investigation was conducted to identify which dynamic phenomena at the electrified interface are prerequisite for the formation of molecular hydrogen. In fact, what we observe as an onset of the macroscopic faradaic current originates from dynamic structural changes in the double layer, which are entropic in nature. Based on careful analysis of the activation process, an electrocatalytic descriptor is introduced, evaluated and experimentally confirmed. The catalytic activity descriptor is named as the potential of minimum entropy. The experimentally verified catalytic descriptor reveals significant potential to yield innovative insights for the design of catalytically active materials and interfaces.

Alkaline manganese electrochemistry studied by in situ and operando spectroscopic methods - metal dissolution, oxide formation and oxygen evolution.

Manganese-based systems are considered as candidate electrocatalysts for the electrochemical oxygen evolution reaction (OER), because of their abundance in biochemical oxygen producing catalyst systems. In this work, the surface of metallic manganese was investigated in situ and operando in potentiodynamic cyclic voltammetry (CV) experiments and potentiostatic chronoamperometry (CA) experiments in NaOH. In both cases, the surfaces were initially reduced. At corresponding potentials, no oxide species can be detected by Raman spectroscopy, though electrochemical data and the absence of dissolution above the reversible potential for reactions of type Mn → MnII indicate that the material is passive. The CV shows anodic peaks at potentials in line with expectations on the basis of thermodynamic data for the oxidation to Mn3O4 and Mn2O3; the thickness of the surface layer increases by a few nm during these peaks, as evidenced by spectroscopic ellipsometry. Dissolution of Mn as evidenced by downstream electrolyte analysis by inductively coupled plasma mass spectrometry in a scanning flow cell (SFC-ICP-MS) of the electrolyte is negligible in the range of electrode potential vs. Ag|AgCl|3 M KCl, EAg|AgCl, up to 0.3 V. Remarkably, Raman spectra already show the occurrence of α-MnO2 at EAg|AgCl > -0.25 V, which is ca. 0.5 V below the potential at which oxidation to MnO2 is expected. This observation is attributed to disproportionation above a certain level of MnIII. For EAg|AgCl > 0.4 V, dissolution sets in, at a constant layer thickness. Above the onset potential of the OER, at EAg|AgCl≈ 0.6 V, SFC-ICP-MS analysis shows fast dissolution, and the oxide layer thickness is constant or increases. CA experiments during the OER show strong dissolution, and the re-formation of a strongly disordered, ß-MnO2-like oxide, which exists in a quasi-stationary state at the interface. Several CV cycles increase the dissolution per cycle and the fraction of α-MnO2 on the surface which cannot be reduced. The high dissolution currents show that metallic Mn is hardly suitable as an OER catalyst, however, at least the MnIV oxides remain stationarily present in the system.

A new look at oxide formation at the copper/electrolyte interface by in situ spectroscopies.

The widely used engineering material copper is a prototype of an electrochemically passive metal. In this work, the passive films on evaporated copper in 0.1 M NaOH are investigated in situ and operando by spectroscopic ellipsometry and Raman spectroscopy, both conducted during oxidation in potentiostatic step experiments. Oxide growth is initiated by jumping from a potential at which the surface is oxide-free to -0.1 V vs. Ag|AgCl|3 M KCl (+0.11 V vs. standard hydrogen electrode, SHE). At subsequent electrode potential jumps, no corresponding jumps in the thickness are observed; instead, oxide growth proceeds steadily. Above +0.3 V vs. Ag|AgCl|3 M KCl (+0.51 V vs. SHE), the oxide layer thickness remains constant at ≈7 nm. Raman spectra show a peak at 530 cm(-1), which agrees with the dominant peak in spectra of copper mixed oxide, Cu4O3 (Cu2(I)Cu2(II)O3). Crystalline Cu4O3 nucleates from a precursor state showing strong photoluminescence (PL), which hints at the involvement of Cu2O. Overall, the PL spectra of the growing oxide and absorption spectra indicate the presence of Cu2O in the thin films. Absorption spectra cannot be understood as a superposition of the spectra from different well-described copper oxides, which points to defect-rich oxides that show rather different spectra. Raman spectra also point to an involvement of both crystalline and amorphous oxides that coexist. The results show that the passive layers on copper are more complex than the duplex layers described in the literature; they do contain an oxide with a mixed valency of copper.

Synthesis of N-Doped Graphene Photo-Catalyst for Photo-Assisted Charging of Li-Ion Oxygen Battery.

In this work, nitrogen (N)-doped graphene film is synthesized, as a photo-catalyst, on one side of the copper foam by chemical vapor deposition and the copper foam is directly used as an electrode after porous Pd@rGO cathode loading to the other side of the foam for the photo-assisted charging of the Li-ion oxygen battery. The amount of urea (CO(NH2)2), which is used as N atom source, is optimized to get maximum photo-anodic currents from the n-type graphene films. The optical band gap and the valance band edge potential of the optimized N-doped graphene film are determined as 2.00 eV and 3.71 VLi+/Li, respectively. X-ray photoelectron spectra provided that the atomic percent of N atoms in the graphene film is 1.34% and the graphitic, pyrrolic and pyridinic N atom percentages are 54.01%, 42.20% and 3.79%, respectively. The photo-assisted charging tests indicated that the N-doped graphene film photo-catalyst reduced the charging potential significantly even at 1000 mA g-1 (0.1 mA cm-2) current density and improved the cyclic discharge-charge performance of the Li-ion oxygen battery considerably.

Engineering Oxygen Vacancies in (FeCrCoMnZn)3O4-δ High Entropy Spinel Oxides Through Altering Fabrication Atmosphere for High-Performance Rechargeable Zinc-Air Batteries.

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.

Facile Synthesis and Origin of Enhanced Electrochemical Oxygen Evolution Reaction Performance of 2H-Hexagonal Ba2CoMnO6-δ as a New Member in Double Perovskite Oxides.

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.

Electrochemical Performance of (MgCoNiZn)1-xLixO High-Entropy Oxides in Lithium-Ion Batteries.

High-entropy oxides (HEOs), which are a new class of single-phase solid solution materials, have recently attracted significant attention as an anode material for lithium-ion batteries (LIBs). In this study, (MgCoNiZn)1-xLixO (x = 0.05, 0.15, 0.25, and 0.35) HEOs were synthesized and their electrochemical performances as the anode material were observed in LIBs. X-ray photoelectron spectroscopy (XPS) analysis showed that the increase in the lithium cation concentration causes generation of more oxygen vacancies, which greatly affected the electrochemical performance of (MgCoNiZn)1-xLixO HEO anodes, in the structure. The more the oxygen vacancy concentration in the anode, the higher the discharge capacity in the LIB. The (MgCoNiZn)0.65Li0.35O anode had 1930 mA h g-1 initial and 610 mA h g-1 stable (after 130 cycles) discharge capacities at a current density of 1000 mA g-1. This work clearly indicated that designing a HEO with abundant oxygen vacancies in the structure was a very efficient strategy to improve the electrochemical performance of the HEO electrode for LIBs.

Cyclodextrin inhibits zinc corrosion by destabilizing point defect formation in the oxide layer.

Corrosion inhibitors are added in low concentrations to corrosive solutions for reducing the corrosion rate of a metallic material. Their mechanism of action is typically the blocking of free metal surface by adsorption, thus slowing down dissolution. This work uses electrochemical impedance spectroscopy to show the cyclic oligosaccharide ß-cyclodextrin (ß-CD) to inhibit corrosion of zinc in 0.1M chloride with an inhibition efficiency of up to 85%. Only a monomolecular adsorption layer of ß-CD is present on the surface of the oxide covered metal, with Raman spectra of the interface proving the adsorption of the intact ß-CD. Angular dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to extract a band-like diagram of the ß-CD/ZnO interface, showing a large energy level shift at the interface, closely resembling the energy level alignment in an n-p junction. The energy level shift is too large to permit further electron transfer through the layer, inhibiting corrosion. Adsorption hence changes the defect density in the protecting ZnO layer. This mechanism of corrosion inhibition shows that affecting the defect chemistry of passivating films by molecular inhibitors maybe a viable strategy to control corrosion of metals.