Revealing synergetic structural activation of a CuAu surface during water-gas shift reaction.

Bimetallic alloy catalysts show strong structural and compositional dependence on their activity, selectivity, and stability. Often referred to as the "synergetic effect" of two metal elements in the alloys, their detailed dynamic information, structurally and chemically, of catalyst surface under reaction conditions remains largely elusive. Here, using aberration-corrected environmental transmission electron microscopy, we visualize the atomic-scale synergetic surface activation of CuAu under a water­gas shift reaction condition. The unique "periodic" structural activation largely determines the dominating reaction pathway, which is related to a possible "carboxyl" reaction route corroborated by density functional theory­based calculation and ab initio molecular dynamics simulation. These results demonstrate how the alloy surface is activated and catalyzes the chemical reaction, which provides insights into catalyst design with atom precision.

Catalytically Stable Potassium Single-Atom Solid Superbases.

Solid superbases can catalyze diverse reactions under mild conditions, while they suffer from aggregation of basic sites and poor stability during recycling. Here we report a new generation of solid superbases derived from K single atoms (SAs) prepared by a tandem redox strategy. The initial redox reaction takes place between base precursor KNO3 and graphene support, producing K2 O at 400 °C. Further increasing the temperature to 800 °C, the graphene reduces K2 O to K anchored by its vacancies, leading to the generation of K SAs (denoted as K1 /G). The source of basicity in the K1 /G is K SAs, and neighboring single atoms (NSAs) possess superbasicity, which is different from conventional basicity originated from oxygen and nitrogen atoms. Due to the superbasicity as well as high dispersion and anchoring of basic sites, the K1 /G shows excellent catalytic activity and stability in transesterification reaction, which is much superior to the reported catalysts.

Atomic-Scale Dynamic Interaction of H_{2}O Molecules with Cu Surface.

Atomic-scale interaction of water vapor with metal surfaces beyond surface adsorption under technologically relevant conditions remains mostly unexplored. Using aberration-corrected environmental transmission electron microscopy, we reveal the dynamic surface activation of Cu by H_{2}O at elevated temperature and pressure. We find a structural transition from flat to corrugated surface for the Cu(011) under low water-vapor pressure. Increasing the water-vapor pressure leads to the surface reaction of Cu with dissociated H_{2}O, resulting in the formation of a metastable "bilayer" Cu─O─H phase. Corroborated by density functional theory and ab initio molecular dynamics calculations, the cooperative O and OH interaction with Cu is responsible for the formation and subsurface propagation of this phase.

Real-Time Atomic-Scale Visualization of Reversible Copper Surface Activation during the CO Oxidation Reaction.

By using in situ aberration-corrected environmental transmission electron microscopy, for the first time at atomic level, the dynamic evolution of the Cu surface is captured during CO oxidation. Under reaction conditions, the Cu surface is activated, typically involving 2-3 atomic layers with the formation of a reversible metastable phase that only exists during catalytic reactions. The distinctive role of CO and O2 in the surface activation is revealed, which features CO exposure to lead to surface roughening and consequently formation of low-coordinated Cu atoms, while O2 exposure induces a quasi-crystalline CuOx phase. Supported by DFT calculations, it is shown that crystalline CuOx reversibly transforms into the amorphous phase, acting as an active species to facilitate the interaction of gas reactants and catalyzing CO oxidation.

Molecular design of ionic liquids as novel non-metal catalysts for the acetylene hydrochlorination reaction.

Theoretical prediction of catalytic performance is crucial for the rational design of novel catalysts. In this study, density functional theory (DFT) simulations were carried out to predict the catalytic performance of four ionic liquids (ILs) used as novel non-metal catalysts in the acetylene hydrochlorination reaction, and the obtained catalytic performances were verified via our experimental tests; moreover, both the theoretical and experimental results showed that the catalytic performance of the four IL catalysts followed the order tetraphenylphosphonium bromide (TPPB) > tetraphenylphosphonium chloride (TPPC) > butyltriphenylphosphonium bromide (BuTPPB) ≫ tetraphenylphosphonium tetrafluoroborate (TPPT), and the 15%TPPB/SAC catalyst exhibited efficient catalytic performance when compared with the recently reported non-metal catalysts for the acetylene hydrochlorination reaction. Furthermore, the catalytic mechanisms of the four ILs with different cations and anions were revealed via theoretical Mulliken, partial density of states (PDOS) and electron density difference (EDD) analyses combined with the experimental XPS and XRD characterizations. The results showed that the effects of the anions on the catalytic activity were much significant than those of the cations. A good IL non-metal catalyst for acetylene hydrochlorination would mainly donate electrons to Cl to activate the H-Cl bond, and then, the electrons would be donated back to the IL catalyst in the transition state. This study provides new insights into the design of efficient nonmercuric catalysts for the acetylene hydrochlorination reaction.

Atomic Defect Mediated Li-Ion Diffusion in a Lithium Lanthanum Titanate Solid-State Electrolyte.

Lithium lanthanum titanium oxide (LLTO) as a fast Li-ion conductor is a promising candidate for future all-solid-state Li batteries. Fundamental understanding of the microstructure of LLTO and its effect on the Li+ diffusion mechanism, especially across different length scales and interfaces, is a prerequisite to improving the material design and processing development of oxide-based solid electrolytes. Herein, through detailed structural analysis of LLTO ceramic pellets by aberration-corrected transmission electron microscopy, we discovered previously unreported intrinsic planar defects in LLTO single-crystal grains. These planar defects feature an antiphase boundary along specific crystal planes with a "rock-salt" structure enriched by Li within a few atomic layers. Corroborated by density-functional-theory-based calculations, we show an increased diffusion barrier across these planar defects inevitably lowers the bulk Li+ diffusivity of the oxide electrolyte.

A preliminary study comparing the sedative, cardiorespiratory, and histaminic-releasing effects of intramuscular and intravenous administration of pethidine (meperidine) with midazolam in healthy cats.

Pethidine is a synthetic opioid that is widely used in cats. However, the sedative, cardiorespiratory, and histaminic effects following administration of pethidine with midazolam in cats remain unclear. The objectives of this study were to evaluate and compare changes before and after intravenous (IV) and intramuscular (IM) administration of pethidine with midazolam in healthy cats. In this prospective randomized blind study, 12 cats were assigned equally to either the IV or IM treatment group. The IV group received pethidine 3 mg/kg and midazolam 0.1 mg/kg. The IM group received pethidine 6 mg/kg and midazolam 0.2 mg/kg. The sedative effects, heart rate, respiratory rate, non-invasive arterial blood pressures, and behavioral signs were recorded before and at 2, 5, 15, 30, 45, and 60 min after the injection. Blood samples were taken for an ELISA histamine assay at baseline and at 5 and 15 min after treatment. Cats that received IV treatment were rapidly induced a moderate degree of sedation but those received IM treatment were only mildly sedated. There was no significant difference in the cardiorespiratory values within and between the treatments over time. Plasma histamine concentrations increased by 3 and 5 times at 5 and 15 min after IV treatment, respectively, compared to baseline values. IM injections induced minimal changes in the plasma histamine concentration. In summary, intravenous pethidine with midazolam induced potentially superior sedative effects without serious side effects in clinically healthy cats. However, further studies with larger sample sizes are required to validate this finding.

Development of a heatable duck egg white translucent jelly: an evaluation of its physicochemical properties and thermal stability.

Though nutritional, the remaining separated duck egg white in duck egg processing plants presents challenges for its transportation and use, as it spoils easily and has a strong odor. Uses for the excess egg white are of paramount concern for agricultural resource reuse. The purpose of this study was to increase its value and use efficiency. Duck egg white was mixed with sodium hydroxide to produce translucent alkali-induced egg white jelly similar to that in preserved egg whites. To develop a heatable translucent egg white jelly, their physiochemical properties and thermal stabilities were investigated. A gel prepared with 150 mM sodium hydroxide at 25°C had optimal bloom strength and the densest microstructure. Storing the jelly at 5°C helped maintain its disulfide bonds and delayed liquefaction. Although heating decreased its bloom strength and total disulfide bond content as temperature increased (P < 0.05), scanning electron microscopy of the heated jelly revealed that the protein network structure was denser than that of unheated jelly. Heating caused parts of the structure to shrink and even dehydrate, leading to a wrinkled surface. However, no signs of liquefaction or collapse were observed, and the free alkali released during heating was lower than that from the white of existing preserved eggs. These results confirmed the thermal stability of the jelly and its potential to be served hot or used in food processing. Furthermore, in addition to disguising the odor and special flavor attributable to the alkaline treatment, adding ginger juice or turmeric to the preparation yielded higher bloom strength, resulted in lower free alkalinity, and delayed liquefaction, thus improving the jelly's thermal stability. Like preserved eggs on the market that can be served in hot congee, the proposed egg white jelly is rich in proteins and suitable for hot or instant serving. These findings may help address the problem of excessive remaining duck egg white created during food processing by diversifying duck egg processing and boosting its value.