Revealing Lithium Nitrate-Mediated Solid-Electrolyte Interphase of Lithium Metal Anode via Cryogenic Transmission Electron Microscopy.

The cycle stability of lithium metal anode (LMA) largely depends on solid-electrolyte interphase (SEI). Electrolyte engineering is a common strategy to adjust SEI properties, yet understanding its impact is challenging due to limited knowledge on ultrafine SEI structures. Herein, using cryogenic transmission electron microscopy, we reveal the atomic-level SEI structure of LMA in ether-based electrolytes, focusing on the role of LiNO3 additives in SEI modulation at different temperature (25 and 50 °C). Poor cycle stability of LMA in the baseline electrolyte without LiNO3 additives stems from the Li2CO3-rich mosaic-type SEI. Increased LiNO3 content and elevated operating temperature enhance cyclic performance by forming bilayer or multilayer SEI structures via preferential LiNO3 decomposition, but may thicken the SEI, leading to reduced initial Coulombic efficiency and increased overpotential. The optimal SEI features a multilayer structure with Li2O-rich inner layer and closely packed grains in the outer layer, minimizing electrolyte decomposition or corrosion.

An electrospun three-layer nanofibrous membrane-based in situ gel separator for efficient lithium-organic batteries.

An in situ gel separator based on an electrospun three-layer nanofibrous membrane (PSE11-Gel) is developed for high-performance lithium-organic batteries (LOBs). The highly efficient shuttle effect inhibition of organic cathode molecules or lithiated intermediates has been demonstrated for PSE11-Gel to realize high-capacity stable LOBs.

Evaluation of the anterior dentoalveolar relationship in skeletal Class III malocclusion patients with different vertical facial patterns using cone-beam computed tomography.

OBJECTIVES: To measure and compare labiolingual inclinations of the teeth and alveolar bone and the anterior dentoalveolar inclination in patients with skeletal Class III malocclusions with different vertical facial patterns using cone-beam computed tomography (CBCT). MATERIALS AND METHODS: Based on the inclusion and exclusion criteria, 84 CBCT images of patients with untreated skeletal Class III malocclusion were selected. There were 28 patients each in the hypo-, normo-, and hyperdivergent groups. The labiolingual inclinations of the teeth, the corresponding alveolar bone, and the anterior dentoalveolar inclinations were measured and analyzed statistically. RESULTS: The inclinations of the mandibular canine and corresponding alveolar bone were smaller in the hypodivergent group than in the hyperdivergent group. The inclination of the alveolar bone and the maxillary dentoalveolar inclination were smaller in the hyperdivergent group than in the hypodivergent group. CONCLUSIONS: There were differences in the inclination of the teeth, corresponding alveolar bone, and dentoalveolar inclinations at different positions among skeletal Class III patients with different vertical facial patterns. The roots were generally located on the labial side of the alveolar bone.

Visualization of the Active Sites of Zinc-Chromium Oxides and the CO/H2 Activation Mechanism in Direct Syngas Conversion.

Despite wide studies demonstrating the versatility of the metal oxide-zeolite (OXZEO) catalyst concept to tackle the selectivity challenge in syngas chemistry, the active sites of metal oxides and the mechanism of CO/H2 activation remain to be elucidated. Herein, we demonstrate experimentally the role of Cr in zinc-chromium oxides and unveil visually, for the first time, the active sites for CO activation employing scanning transmission electron microscopy-electron energy loss spectroscopy using the volumetric density of surface carbon species as a descriptor. The ZnCr2O4 spinel surface with atomic ZnOx overlayer is the most active site for C-O bond dissociation, particularly at the narrow ZnCr2O4(110) facets constrained between the (311) and (111) facets, followed by the Cr-doped wurtzite ZnO surface. In comparison, the surfaces of ZnCr2O4 with aggregated ZnOx overlayers, pure ZnO, and the stoichiometric ZnCr2O4 exhibit a significantly lower activity. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometric study on different temperature programmed surface reactions with isotopes of C18O, 13CO, and D2 validates direct CO dissociation over ZnCrn oxides in CO, forming CH2 and further to hydrocarbons if H2 is present and CH2CO intermediates in syngas. The activity of CO dissociation and hydrogenation over ZnCrn oxides correlates well with the syngas-to-light-olefins activity of ZnCrn-SAPO-18 composite catalysts as a function of the Cr/Zn ratio.

Switchable Broadband Terahertz Absorbers Based on Conducting Polymer-Cellulose Aerogels.

Terahertz (THz) technologies provide opportunities ranging from calibration targets for satellites and telescopes to communication devices and biomedical imaging systems. A main component will be broadband THz absorbers with switchability. However, optically switchable materials in THz are scarce and their modulation is mostly available at narrow bandwidths. Realizing materials with large and broadband modulation in absorption or transmission forms a critical challenge. This study demonstrates that conducting polymer-cellulose aerogels can provide modulation of broadband THz light with large modulation range from ≈ 13% to 91% absolute transmission, while maintaining specular reflection loss < -30 dB. The exceptional THz modulation is associated with the anomalous optical conductivity peak of conducting polymers, which enhances the absorption in its oxidized state. The study also demonstrates the possibility to reduce the surface hydrophilicity by simple chemical modifications, and shows that broadband absorption of the aerogels at optical frequencies enables de-frosting by solar-induced heating. These low-cost, aqueous solution-processable, sustainable, and bio-friendly aerogels may find use in next-generation intelligent THz devices.

Dehiscence and fenestration of skeletal Class III malocclusions with different vertical growth patterns in the anterior region: A cone-beam computed tomography study.

INTRODUCTION: This study aimed to evaluate the incidence and distribution of alveolar bone dehiscence and fenestration in skeletal Class III malocclusions with different vertical growth patterns in the anterior region using cone-beam computed tomography (CBCT). METHODS: In this retrospective study, 84 patients with skeletal Class III malocclusions who underwent CBCT were selected. This study included 28 patients with hypodivergence (mean age, 22.9 ± 3.9 years), 28 with normodivergence (mean age, 21.0 ± 3.0 years), and 28 with hyperdivergence (mean age, 21.0 ± 3.7 years). Teeth in the anterior region were examined using CBCT to detect dehiscence and fenestration. The incidences of dehiscence and fenestration in the anterior teeth region were recorded, and statistical analysis was conducted using SPSS software (version 25.0, IBM, Armonk, NY). RESULTS: Among the patients with skeletal Class III malocclusions, dehiscence and fenestration were prone to occur in the mandible. Dehiscence and fenestration were more prevalent in patients with hyperdivergence compared with in patients with hypodivergence and normodivergence. CONCLUSIONS: Dehiscence and fenestration are prevalent among patients with skeletal Class III malocclusion. Furthermore, the occurrence of alveolar bone defects is higher in patients with hyperdivergence.

Slowly Removing Surface Ligand by Aging Enhances the Stability of Pd Nanosheets toward Electron Beam Irradiation and Electrocatalysis.

Surface ligands play an important role in shape-controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well-preserved morphology, together with significantly enhanced stability toward both e-beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re-exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect-rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand.

Fabrication of a PdCu@SiO2@Cu core-shell-satellite catalyst for the selective hydrogenation of acetylene.

Pd25Cu75@SiO2 core-shell and PdCu@SiO2@Cu core-shell-satellite architectures were fabricated by silica-coating of Pd25Cu75 colloids in a reverse microemulsion. Hydrolysis of tetraethylorthosilicate in the reverse microemulsion containing hydrazine and ammonia yielded a core-shell structure, while the use of ammonia only, instead of a mixture of hydrazine and ammonia, formed a core-shell-satellite structure. The ammonia-leached copper species migrated onto the developing silica shell and formed smaller Cu clusters. Air-calcination at 673 K followed by H2-reduction at 773 K of the as-synthesized samples removed the organic surfactants and generated the permeable porous silica shells. The core-shell catalyst consisted of a metal core (8.5 nm) and a silica shell (7.8 nm), while the core-shell-satellite catalyst was composed by a metal core (7.0 nm), a silica shell (8.0 nm), and satellite Cu clusters (1.4 nm) on the silica shell. When used to catalyze the selective hydrogenation of acetylene to ethylene, the core-shell-satellite catalyst showed substantially enhanced activity and stability because of the synergetic catalysis between the metal core and the surrounding Cu clusters.

Atomic Structure of the Fe3O4/Fe2O3 Interface During Phase Transition from Hematite to Magnetite.

Phase transition between iron oxides practically defines their functionalities in both physical and chemical applications. Direct observation of the atomic rearrangement and a quantitative description of the dynamic behavior of the phase transition, however, are rare. Here, we monitored the structure evolution from a rod-shaped hematite nanoparticle to magnetite during H2 reduction at elevated temperatures. Environmental transmission electron microscopy observations, along with selected area electron diffraction experiments, identified that the reduction preferentially commenced with Fe3O4 nucleation on the surface defective sites, followed by laterally growing into a Fe3O4 film until fully covering the particle surface. The Fe3O4 phase then propagated toward the bulk particle via a Fe3O4/α-Fe2O3 interface with the relationship α-Fe2O3(0001)//Fe3O4(111) in an aligned orientation of [112]Fe3O4||[112̅0]α-Fe2O3. Upon this Fe3O4/α-Fe2O3 interface, the Fe-O octahedra in Fe3O4(111) (as layer A) matches that of α-Fe2O3(0001) at a rotation angle of 30°, and the reduction proceeds in such a pattern that two-thirds of the FeOh in the adjacent layer (layer B) is transformed into FeTe.

Soft Electromagnetic Vibrotactile Actuators with Integrated Vibration Amplitude Sensing.

Soft vibrotactile devices have the potential to expand the functionality of emerging electronic skin technologies. However, those devices often lack the necessary overall performance, sensing-actuation feedback and control, and mechanical compliance for seamless integration on the skin. Here, we present soft haptic electromagnetic actuators that consist of intrinsically stretchable conductors, pressure-sensitive conductive foams, and soft magnetic composites. To minimize joule heating, high-performance stretchable composite conductors are developed based on in situ-grown silver nanoparticles formed within the silver flake framework. The conductors are laser-patterned to form soft and densely packed coils to further minimize heating. Soft pressure-sensitive conducting polymer-cellulose foams are developed and integrated to tune the resonance frequency and to provide internal resonator amplitude sensing in the resonators. The above components together with a soft magnet are assembled into soft vibrotactile devices providing high-performance actuation combined with amplitude sensing. We believe that soft haptic devices will be an essential component in future developments of multifunctional electronic skin for future human-computer and human-robotic interfaces.

Ambient noise-based weakly supervised manhole localization methods over deployed fiber networks.

We present a manhole localization method based on distributed fiber optic sensing and weakly supervised machine learning techniques. For the first time to our knowledge, ambient environment data is used for underground cable mapping with the promise of enhancing operational efficiency and reducing field work. To effectively accommodate the weak informativeness of ambient data, a selective data sampling scheme and an attention-based deep multiple instance classification model are adopted, which only requires weakly annotated data. The proposed approach is validated on field data collected by a fiber sensing system over multiple existing fiber networks.

Chemical doping of unsubstituted perylene diimide to create radical anions with enhanced stability and tunable photothermal conversion efficiency.

N-doping of perylene diimides (PDIs) to create stable radical anions is significant for harvesting photothermal energy due to their intensive absorption in the near-infrared (NIR) region and non-fluorescence. In this work, a facile and straightforward method has been developed to control the doping of perylene diimide to create radical anions using organic polymer polyethyleneimine (PEI) as a dopant. It was demonstrated that PEI is an effective polymer-reducing agent for the n-doping of PDI toward the controllable generation of radical anions. In addition to the doping process, PEI could suppress the self-assembly aggregation and improve the stability of PDI radical anions. Tunable NIR photothermal conversion efficiency (maximum 47.9%) was also obtained from the radical-anion-rich PDI-PEI composites. This research provides a new strategy to tune the doping level of unsubstituted semiconductor molecules for varying yields of radical anions, suppressing aggregation, improving stability, and obtaining the highest radical anion-based performance.

Atomic-Scale Engineering of CuOx-Au Interfaces over AuCu Single-Nanoparticles.

A face-centered tetragonal (fct) AuCu particle with a size of 7.1 nm and an Au/Cu molar ratio of 1/1 was coated by a silica shell of 6 nm thickness. Segregation of Cu atoms from the metal particle under an oxidative atmosphere precisely mediated the CuOx-Au interfacial structure by simply varying the temperature. As raising the temperature from 473 to 773 K, more Cu atoms emigrated from the AuCu particle and were oxidized into CuOx layers that grew up to 0.8 nm in thickness. Simultaneously, the size of the Au-rich particle lowered moderately while the crystalline structure transformed from the fct phase into the face-centered cubic (fcc) phase. The CuOx-Au interface shifted from the CuOx monolayer bound to Au single-atoms to Au@CuOx core-shell geometry, while the catalytic activity for CO oxidation at 433 K decreased dramatically. Moreover, a sharp loss in activity was observed as the crystal-phase transition occurred. This change in catalytic performance was ascribed to the geometrical configuration at the interfacial sites: the synergetic effect between the fct-AuCu particle and CuOx monolayer contributed to the much higher activity, whereas the fcc-AuCu/Au particle weakened its interaction with the thicker CuOx layer and thus decreased the activity.

Tuning crystal-phase of bimetallic single-nanoparticle for catalytic hydrogenation.

Bimetallic nanoparticles afford geometric variation and electron redistribution via strong metal-metal interactions that substantially promote the activity and selectivity in catalysis. Quantitatively describing the atomic configuration of the catalytically active sites, however, is experimentally challenged by the averaging ensemble effect that is caused by the interplay between particle size and crystal-phase at elevated temperatures and under reactive gases. Here, we report that the intrinsic activity of the body-centered cubic PdCu nanoparticle, for acetylene hydrogenation, is one order of magnitude greater than that of the face-centered cubic one. This finding is based on precisely identifying the atomic structures of the active sites over the same-sized but crystal-phase-varied single-particles. The densely-populated Pd-Cu bond on the chemically ordered nanoparticle possesses isolated Pd site with a lower coordination number and a high-lying valence d-band center, and thus greatly expedites the dissociation of H2 over Pd atom and efficiently accommodates the activated H atoms on the particle top/subsurfaces.

Fabrication of monodisperse gold-copper nanocubes and AuCu-cuprous sulfide heterodimers by a step-wise polyol reduction.

Monodisperse gold-copper nanocubes and AuCu-cuprous sulfide (Cu1.96S) heterodimers were fabricated by a step-wise polyol reduction with the aid of oleylamine and 1-dodecanethiol. The geometric configuration was mediated by simply varying the Cu/Au atomic ratio: Au-Cu cubes with sizes of 6.4 and 4.3 nm were yielded at Cu/Au atomic ratios of 1/3 and 1/1, respectively; while AuCu-Cu1.96S heterodimer, consisting of a AuCu cube of 4.6 nm and a Cu1.96S sphere of 6.3 nm was obtained at Cu/Au atomic ratio of 3/1. Detailed structural analysis on the intermediate products, collected at different intervals during the synthesis, revealed that small-sized Au seeds formed at 423 K, followed by the growth of Cu and Cu1.96S crystals at 473 K. Oleylamine coordinated to Au3+ and Cu2+ and thus mediated the particle size; while 1-dodecanethiol bonded to Au3+ and directed the cubic morphology. Excessive Cu2+, at the Cu/Au atomic ratio of 3/1, interacted with 1-dodecanethiol and formed Cu1.96S spherical particle that epitaxially grew over the AuCu cube, resulting in a heterodimer structure. Due to the enriched surficial Cu atoms and their electronic interactions with Au atoms, Au-Cu nanocubes and AuCu-Cu1.96S heterodimers showed pronounced activities for the catalytic reduction of 4-nitrophenol to 4-aminophenol with NaBH4 at 298 K.

Ultrahigh oxygen evolution reaction activity in Au doped co-based nanosheets.

Oxygen evolution reaction (OER) has attracted enormous interest as a key process for water electrolysis over the past years. The advance of this process relies on an effective catalyst. Herein, we employed single-atom Au doped Co-based nanosheets (NSs) to theoretically and experimentally evaluate the OER activity and also the interaction between Co and Au. We reveal that Au-Co(OH)2 NSs achieved a low overpotential of 0.26 V at 10 mA cm-2. This extraordinary phenomenon presents an overall superior performance greater than state-of-the-art Co-based catalysts in a sequence of α-Co(OH)2 < Co3O4 < CoOOH < Au-Co(OH)2. With ab initio calculations and analysis in the specific Au-Co(OH)2 configuration, we reveal that OER on highly active Au-Co(OH)2 originates from lattice oxygen, which is different from the conventional adsorbate evolution scheme. Explicitly, the configuration of Au-Co(OH)2 gives rise to oxygen non-bonding (ONB) states and oxygen holes, allowing direct O-O bond formation by a couple of oxidized oxygen with oxygen holes, offering a high OER activity. This study provides new insights for elucidating the origins of activity and synthesizing efficient OER electrocatalysts.

Environmentally Friendly, Durably Waterproof, and Highly Breathable Fibrous Fabrics Prepared by One-Step Fluorine-Free Waterborne Coating.

Waterproof and breathable membranes (WBMs) have drawn broad attention due to their widespread applications in various scientific and industry fields. However, creating WBMs with environment-friendliness and high performance is still a critical and challenging task. Herein, an environmentally friendly fluorine-free WBM with high performance was prepared through electrospinning and one-step dip-coating technology. The fluorine-free waterborne hydroxyl acrylic resin (HAR) emulsion containing long hydrocarbon chains endowed the electrospun polyacrylonitrile/blocked isocyanate prepolymer (PAN/BIP) fibrous membranes with superior hydrophobicity; meanwhile, crosslinking agent BIP ensured strong chemical binding between hydrocarbon segments and fiber substrate. The as-prepared PAN/BIP@HAR fibrous membranes achieve ideal properties with waterproofness of 112.5 kPa and moisture permeability of 12.7 kg m-2 d-1, which are comparable to the existing high-performance fluorinated WBMs. Besides, the PAN/BIP@HAR membranes also display impressive tensile strength and durability. Significantly, the proposed technology was also applicable to other hydrophilic fiber substrates, such as cellulose acetate and polyamide 6. The successful synthesis of environmentally friendly, durably waterproof, and highly breathable PAN/BIP@HAR membranes not only opens a new avenue to materials design, but also provides promising candidates with tremendous potential in various areas.

Strong Metal-Support Interaction Boosts Activity, Selectivity, and Stability in Electrosynthesis of H2O2.

Noble metals have an irreplaceable role in catalyzing electrochemical reactions. However, large overpotential and poor long-term stability still prohibit their usage in many reactions (e.g., oxygen evolution/reduction). With regard to the low natural abundance, the improvement of their overall electrocatalytic performance (activity, selectivity, and stability) was urgently necessary. Herein, strong metal-support interaction (SMSI) was modulated through an unprecedented time-dependent mechanical milling method on Pd-loaded oxygenated TiC electrocatalysts. The encapsulation of Pd surfaces with reduced TiO2-x overlayers is precisely controlled by the mechanical milling time. This encapsulation induced a valence band restructuring and lowered the d-band center of surface Pd atoms. For hydrogen peroxide electrosynthesis through the two-electron oxygen reduction reaction (ORR), these electronic and geometric modifications resulted in optimal adsorption energies of reaction intermediates. Thus, SMSI phenomena not only enhanced electrocatalytic activity and selectivity but also created an encapsulating oxide overlayer that protected the Pd species, increasing its long-term stability. This SMSI induced by mechanical milling was also extended to other noble metal systems, showing great promise for the large-scale production of highly stable and tunable electrocatalysts.

Single Iridium Atom Doped Ni2P Catalyst for Optimal Oxygen Evolution.

Single-atom catalysts (SACs) with 100% active sites have excellent prospects for application in the oxygen evolution reaction (OER). However, further enhancement of the catalytic activity for OER is quite challenging, particularly for the development of stable SACs with overpotentials <180 mV. Here, we report an iridium single atom on Ni2P catalyst (IrSA-Ni2P) with a record low overpotential of 149 mV at a current density of 10 mA·cm-2 in 1.0 M KOH. The IrSA-Ni2P catalyst delivers a current density up to ∼28-fold higher than that of the widely used IrO2 at 1.53 V vs RHE. Both the experimental results and computational simulations indicate that Ir single atoms preferentially occupy Ni sites on the top surface. The reconstructed Ir-O-P/Ni-O-P bonding environment plays a vital role for optimal adsorption and desorption of the OER intermediate species, which leads to marked enhancement of the OER activity. Additionally, the dynamic "top-down" evolution of the specific structure of the Ni@Ir particles is responsible for the robust single-atom structure and, thus, the stability property. This IrSA-Ni2P catalyst offers novel prospects for simplifying decoration strategies and further enhancing OER performance.

Carbon Monoxide Gas Induced 4H-to-fcc Phase Transformation of Gold As Revealed by In-Situ Transmission Electron Microscopy.

The hexagonal 4H phase gold nanostructures shows great potential for catalysis, optical, and biomedical fields. However, its phase stability remains largely unclear. Here, we report the 4H-to-face-centered cubic (fcc) phase transformation of gold induced by CO gas interactions and an electron beam observed through in-situ transmission electron microscopy (in-situ TEM). The atomic scale transformation mechanism is revealed experimentally and supported by first-principle calculations. Density functional theory calculations show that the 4H-to-fcc phase transformation processes via the transition of layer sliding with expanded layer spacing, which can be facilitated by both the adsorbed CO molecules and the extra electron provided by the electron beam. The transformation first takes place at the edges of the nanorods with the collective assistance of both CO and extra electrons, and then the inner portion of the bulk crystal follows with extra electrons as the lubricant. These results promote the understanding of the toxic effect of CO gas and shining light on the structural conversion and atomic migration of noble metal catalysts when they interact with CO molecules.