Removal and Reoccurrence of LLZTO Surface Contaminants under Glovebox Conditions.

The reactivity of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolytes to form lithio-phobic species such as Li2CO3 on their surface when exposed to trace amounts of H2O and CO2 limits the progress of LLZTO-based solid-state batteries. Various treatments, such as annealing LLZTO within a glovebox or acid etching, aim at removing the surface contaminants, but a comprehensive understanding of the evolving LLZTO surface chemistry during and after these treatments is lacking. Here, glovebox-like H2O and CO2 conditions were recreated in a near ambient pressure X-ray photoelectron spectroscopy chamber to analyze the LLZTO surface under realistic conditions. We find that annealing LLZTO at 600 °C in this atmosphere effectively removes the surface contaminants, but a significant level of contamination reappears upon cooling down. In contrast, HCl(aq) acid etching demonstrates superior Li2CO3 removal and stable surface chemistry post treatment. To avoid air exposure during the acid treatment, an anhydrous HCl solution in diethyl ether was used directly within the glovebox. This novel acid etching strategy delivers the lowest lithium/LLZTO interfacial resistance and the highest critical current density.

Understanding the Surface Regeneration and Reactivity of Garnet Solid-State Electrolytes.

Garnet solid-electrolyte-based Li-metal batteries can be used in energy storage devices with high energy densities and thermal stability. However, the tendency of garnets to form lithium hydroxide and carbonate on the surface in an ambient atmosphere poses significant processing challenges. In this work, the decomposition of surface layers under various gas environments is studied by using two surface-sensitive techniques, near-ambient-pressure X-ray photoelectron spectroscopy and grazing incidence X-ray diffraction. It is found that heating to 500 °C under an oxygen atmosphere (of 1 mbar and above) leads to a clean garnet surface, whereas low oxygen partial pressures (i.e., in argon or vacuum) lead to additional graphitic carbon deposits. The clean surface of garnets reacts directly with moisture and carbon dioxide below 400 and 500 °C, respectively. This suggests that additional CO2 concentration controls are needed for the handling of garnets. By heating under O2 along with avoiding H2O and CO2, symmetric cells with less than 10 Ωcm2 interface resistance are prepared without the use of any interlayers; plating currents of >1 mA cm-2 without dendrite initiation are demonstrated.

Water Formation Reaction under Interfacial Confinement: Al0.25Si0.75O2 on O-Ru(0001).

Confined nanosized spaces at the interface between a metal and a seemingly inert material, such as a silicate, have recently been shown to influence the chemistry at the metal surface. In prior work, we observed that a bilayer (BL) silica on Ru(0001) can change the reaction pathway of the water formation reaction (WFR) near room temperature when compared to the bare metal. In this work, we looked at the effect of doping the silicate with Al, resulting in a stoichiometry of Al0.25Si0.75O2. We investigated the kinetics of WFR at elevated H2 pressures and various temperatures under interfacial confinement using ambient pressure X-ray photoelectron spectroscopy. The apparent activation energy was lower than that on bare Ru(0001) but higher than that on the BL-silica/Ru(0001). The apparent reaction order with respect to H2 was also determined. The increased residence time of water at the surface, resulting from the presence of the BL-aluminosilicate (and its subsequent electrostatic stabilization), favors the so-called disproportionation reaction pathway (*H2O + *O ↔ 2 *OH), but with a higher energy barrier than for pure BL-silica.

Xenon Trapping in Metal-Supported Silica Nanocages.

Xenon (Xe) is a valuable and scarce noble gas used in various applications, including lighting, electronics, and anesthetics, among many others. It is also a volatile byproduct of the nuclear fission of uranium. A novel material architecture consisting of silicate nanocages in contact with a metal surface and an approach for trapping single Xe atoms in these cages is presented. The trapping is done at low Xe pressures and temperatures between 400 and 600 K, and the process is monitored in situ using synchrotron-based ambient pressure X-ray photoelectron spectroscopy. Release of the Xe from the cages occurs only when heating to temperatures above 750 K. A model that explains the experimental trapping kinetics is proposed and tested using Monte Carlo methods. Density functional theory calculations show activation energies for Xe exiting the cages consistent with experiments. This work can have significant implications in various fields, including Xe production, nuclear power, nuclear waste remediation, and nonproliferation of nuclear weapons. The results are also expected to apply to argon, krypton, and radon, opening an even more comprehensive range of applications.

A Most Enantioselective Chiral Surface: Tartaric Acid on All Surfaces Vicinal to Cu(110).

Enantioselective chemistry on intrinsically chiral surfaces is the quintessential form of structure-sensitive surface chemistry, arising purely from the dissymmetry of the surface structure. Identification or design of chiral surface structures that maximize enantioselectivity for a given processes is extremely challenging because of the limited magnitude of the enantiospecific interaction energetics of chiral molecules with chiral surfaces. Using spherical Cu single crystals exposing surfaces with a continuous two-dimensional distribution of crystallographic orientations, we mapped the enantiospecific surface reaction kinetics of tartaric acid decomposition across the surface orientation space. These measurements reveal both the mechanistic origin of enantioselectivity and identify the structural features of the most enantiospecific surface orientation.

Kinetics and Mechanism of Aspartic Acid Adsorption and Its Explosive Decomposition on Cu(100).

The mechanism and kinetics of aspartic acid (Asp, HO2CCH(NH2)CH2CO2H) decomposition on Cu(100) have been studied using X-ray photoemission spectroscopy and temperature-programmed reaction spectroscopy. We investigate the Asp decomposition mechanism in detail using unlabeled d-Asp and isotopically labeled l-Asp-4-13C (HO2CCH(NH2)CH213CO2H), l-Asp- d7 (DO2CCD(ND2)CD2CO2D), l-Asp-2,3,3- d3 (HO2CCD(NH2)CD2CO2H), and l-Asp-15N-2,3,3- d3 (HO2CCD(15NH2)CD2CO2H). The monolayer of Asp adsorbed on the Cu(100) surface is in a doubly deprotonated bi-aspartate form (-O2CCH(NH2)CH2CO2-). During heating, Asp decomposes on Cu(100) with kinetics consistent with a vacancy-mediated explosion mechanism. The mechanistic steps yield CO2 by sequential cleavage of the C3-C4 and C1-C2 bonds, and N≡CCH3 and H2 via decomposition of the remaining CH(NH2)CH2 intermediate. Deuterium labeling has been used to demonstrate that scrambling of H(D) occurs during the decomposition to acetonitrile of the CD(NH2)CD2 intermediate formed by decarboxylation of l-Asp-2,3,3- d3 and l-Asp-15N-2,3,3- d3.

An ex vivo comparative study of occlusal and proximal caries using terahertz and X-ray imaging.

OBJECTIVES:: To examine the effectiveness of terahertz (THz) pulsed imaging (TPI) in comparison to intraoral photostimulable phosphor late (PSP) and cone beam CT (CBCT) for the detection of dental caries ex vivo. METHODS:: Newly extracted 32 human permanent teeth surfaces (16 with caries and 16 without caries) were serially sectioned mesiodistally and imaged by using four image sets as follows: (1) CBCT; (2) PSP; (3) THz movie video; and (4) THz static images. All images were evaluated twice separately by two calibrated observers for the presence/absence of caries using a 5-grade rating/confidence scale. Weighted κ coefficients were calculated. Different image sets were compared with the histological gold-standard using the receiver operating characteristic and area under curves for each image set were compared using χ2 tests, with a significance level of α = 0.05. RESULTS:: Intra- and interobserverκ-values for all image sets were almost excellent ranging between 0.777 and 0.988. Mean Az values of observers and readings were 0.898 for CBCT, 0.888 for PSP images, 0.853 for THz static images and 0.781 for THz video movie. No statistically significant differences (p > 0.05) were found between Az values for the different image sets. When observer scores were evaluated according to caries location again no statistically significant differences (p > 0.05) were found between Az values for the occlusal and proximal caries for the four image sets. CONCLUSIONS:: Terahertz pulsed imaging was found to be successful for the detection of dental caries ex vivo.