Thermally induced atomic reconstruction into fully commensurate structures of transition metal dichalcogenide layers.

Twist angle between two-dimensional layers is a critical parameter that determines their interfacial properties, such as moiré excitons and interfacial ferro-electricity. To achieve better control over these properties for fundamental studies and various applications, considerable efforts have been made to manipulate twist angle. However, due to mechanical limitations and the inevitable formation of incommensurate regions, there remains a challenge in attaining perfect alignment of crystalline orientation. Here we report a thermally induced atomic reconstruction of randomly stacked transition metal dichalcogenide multilayers into fully commensurate heterostructures with zero twist angle by encapsulation annealing, regardless of twist angles of as-stacked samples and lattice mismatches. We also demonstrate the selective formation of R- and H-type fully commensurate phases with a seamless lateral junction using chemical vapour-deposited transition metal dichalcogenides. The resulting fully commensurate phases exhibit strong photoluminescence enhancement of the interlayer excitons, even at room temperature, due to their commensurate structure with aligned momentum coordinates. Our work not only demonstrates a way to fabricate zero-twisted, two-dimensional bilayers with R- and H-type configurations, but also provides a platform for studying their unexplored properties.

Low-Temperature Direct Growth of Amorphous Boron Nitride Films for High-Performance Nanoelectronic Device Applications.

We successfully demonstrated the improvement and stabilization of the electrical properties of a graphene field effect transistor by fabricating a sandwiched amorphous boron nitride (a-BN)/graphene (Gr)/a-BN using a directly grown a-BN film. The a-BN film was grown via low-pressure chemical vapor deposition (LPCVD) at a low growth temperature of 250 °C and applied as a protection layer in the sandwiched structure. Both structural and chemical states of the as-grown a-BN were verified by various spectroscopic and microscopic analyses. We analyzed the Raman spectra of Gr/SiO2 and a-BN/Gr/a-BN structures to determine the stability of the device under exposure to ambient air. Following exposure, the intensity of the 2D/G-peak ratio of Gr/SiO2 decreased and the position of the G and 2D peaks red-shifted due to the degradation of graphene. In contrast, the peak position of encapsulated graphene is almost unchanged. We also confirmed that the mobility of a-BN/Gr/a-BN structure is 17,941 cm2/Vs. This synthetic strategy could provide a facile way to synthesize uniform a-BN film for encapsulating various van der Waals materials, which is beneficial for future applications in nanoelectronics.

Atomic Reconstruction and Oxygen Evolution Reaction of Mn3O4 Nanoparticles.

Understanding the chemical states of individual surface atoms and their arrangements is essential for addressing several current issues such as catalysis, energy stroage/conversion, and environmental protection. Here, we exploit a profile imaging technique to understand the correlation between surface atomic structures and the oxygen evolution reaction (OER) in Mn3O4 nanoparticles. We image surface structures of Mn3O4 nanoparticles and observe surface reconstructions in the (110) and (101) planes. Mn3+ ions at the surface, which are commonly considered as the active sites in OER, disappear from the reconstructed planes, whereas Mn3+ ions are still exposed at the edges of nanoparticles. Our observations suggest that surface reconstructions can deactivate low-index surfaces of Mn oxides in OER. These structural and chemical observations are further validated by density functional theory calculations. This work shows why atomic-scale characterization of surface structures is crucial for a molecular-level understanding of a chemical reaction in oxide nanoparticles.

Comparison of Postoperative Pain and Adverse Effects between Variable-Rate Feedback Infusion and Conventional Fixed-Rate Basal Infusion Modes of Patient-Controlled Epidural Analgesia following Open Gastrectomy: A Randomized Controlled Trial.

Patient-controlled epidural analgesia is widely used to control postoperative pain following major intra-abdominal surgeries. However, determining the optimal infusion dose that can produce effective analgesia while reducing side effects remains a task to be solved. Postoperative pain and adverse effects between variable-rate feedback infusion (VFIM group, n = 36) and conventional fixed-rate basal infusion (CFIM group, n = 36) of fentanyl/ropivacaine-based patient-controlled epidural analgesia were evaluated. In the CFIM group, the basal infusion rate was fixed (5 mL/h), whereas, in the VFIM group, the basal infusion rate was increased by 0.5 mL/h each time a bolus dose was administered and decreased by 0.3 mL/h when a bolus dose was not administered for 2 h. Patients in the VFIM group experienced significantly less pain at one to six hours after surgery than those in the CFIM group. Further, the number of patients who suffered from postoperative nausea was significantly lower in the VFIM group than in the CFIM group until six hours after surgery. The variable-rate feedback infusion mode of patient-controlled epidural analgesia may provide better analgesia accompanied with significantly less nausea in the early postoperative period than the conventional fixed-rate basal infusion mode following open gastrectomy.

Quasi-graphitic carbon shell-induced Cu confinement promotes electrocatalytic CO2 reduction toward C2+ products.

For steady electroconversion to value-added chemical products with high efficiency, electrocatalyst reconstruction during electrochemical reactions is a critical issue in catalyst design strategies. Here, we report a reconstruction-immunized catalyst system in which Cu nanoparticles are protected by a quasi-graphitic C shell. This C shell epitaxially grew on Cu with quasi-graphitic bonding via a gas-solid reaction governed by the CO (g) - CO2 (g) - C (s) equilibrium. The quasi-graphitic C shell-coated Cu was stable during the CO2 reduction reaction and provided a platform for rational material design. C2+ product selectivity could be additionally improved by doping p-block elements. These elements modulated the electronic structure of the Cu surface and its binding properties, which can affect the intermediate binding and CO dimerization barrier. B-modified Cu attained a 68.1% Faradaic efficiency for C2H4 at -0.55 V (vs RHE) and a C2H4 cathodic power conversion efficiency of 44.0%. In the case of N-modified Cu, an improved C2+ selectivity of 82.3% at a partial current density of 329.2 mA/cm2 was acquired. Quasi-graphitic C shells, which enable surface stabilization and inner element doping, can realize stable CO2-to-C2H4 conversion over 180 h and allow practical application of electrocatalysts for renewable energy conversion.

Thermodynamically driven self-formation of Ag nanoparticles in Zn-embedded carbon nanofibers for efficient electrochemical CO2 reduction.

The electrochemical CO2 reduction reaction (CO2RR), which converts CO2 into value-added feedstocks and renewable fuels, has been increasingly studied as a next-generation energy and environmental solution. Here, we report that single-atom metal sites distributed around active materials can enhance the CO2RR performance by controlling the Lewis acidity-based local CO2 concentration. By utilizing the oxidation Gibbs free energy difference between silver (Ag), zinc (Zn), and carbon (C), we can produce Ag nanoparticle-embedded carbon nanofibers (CNFs) where Zn is atomically dispersed by a one-pot, self-forming thermal calcination process. The CO2RR performance of AgZn-CNF was investigated by a flow cell with a gas diffusion electrode (GDE). Compared to Ag-CNFs without Zn species (53% at -0.85 V vs. RHE), the faradaic efficiency (FE) of carbon monoxide (CO) was approximately 20% higher in AgZn-CNF (75% at -0.82 V vs. RHE) with 1 M KOH electrolyte.

Electrochemical oxidation of boron-doped nickel-iron layered double hydroxide for facile charge transfer in oxygen evolution electrocatalysts.

The oxygen evolution reaction (OER) is the key reaction in water splitting systems, but compared with the hydrogen evolution reaction (HER), the OER exhibits slow reaction kinetics. In this work, boron doping into nickel-iron layered double hydroxide (NiFe LDH) was evaluated for the enhancement of OER electrocatalytic activity. To fabricate boron-doped NiFe LDH (B:NiFe LDH), gaseous boronization, a gas-solid reaction between boron gas and NiFe LDH, was conducted at a relatively low temperature. Subsequently, catalyst activation was performed through electrochemical oxidation for maximization of boron doping and improved OER performance. As a result, it was possible to obtain a remarkably reduced overpotential of 229 mV at 10 mA cm-2 compared to that of pristine NiFe LDH (315 mV) due to the effect of facile charge-transfer resistance by boron doping and improved active sites by electrochemical oxidation.

Metal-organic Framework-driven Porous Cobalt Disulfide Nanoparticles Fabricated by Gaseous Sulfurization as Bifunctional Electrocatalysts for Overall Water Splitting.

Both high activity and mass production potential are important for bifunctional electrocatalysts for overall water splitting. Catalytic activity enhancement was demonstrated through the formation of CoS2 nanoparticles with mono-phase and extremely porous structures. To fabricate porous structures at the nanometer scale, Co-based metal-organic frameworks (MOFs), namely a cobalt Prussian blue analogue (Co-PBA, Co3[Co(CN)6]2), was used as a porous template for the CoS2. Then, controlled sulfurization annealing converted the Co-PBA to mono-phase CoS2 nanoparticles with ~ 4 nm pores, resulting in a large surface area of 915.6 m2 g-1. The electrocatalysts had high activity for overall water splitting, and the overpotentials of the oxygen evolution reaction and hydrogen evolution reaction under the operating conditions were 298 mV and -196 mV, respectively, at 10 mA cm-2.

Anion Extraction-Induced Polymorph Control of Transition Metal Dichalcogenides.

Controlled phase conversion in polymorphic transition metal dichalcogenides (TMDs) provides a new synthetic route for realizing tunable nanomaterials. Most conversion methods from the stable 2H to metastable 1T phase are limited to kinetically slow cation insertion into atomically thin layered TMDs for charge transfer from intercalated ions. Here, we report that anion extraction by the selective reaction between carbon monoxide (CO) and chalcogen atoms enables predictive and scalable TMD polymorph control. Sulfur vacancy, induced by anion extraction, is a key factor in molybdenum disulfide (MoS2) polymorph conversion without cation insertion. Thermodynamic MoS2-CO-CO2 ternary phase diagram offers a processing window for efficient sulfur vacancy formation with precisely controlled MoS2 structures from single layer to multilayer. To utilize our efficient phase conversion, we synthesize vertically stacked 1T-MoS2 layers in carbon nanofibers, which exhibit highly efficient hydrogen evolution reaction catalytic activity. Anion extraction induces the polymorph conversion of tungsten disulfide (WS2) from 2H to 1T. This reveals that our method can be utilized as a general polymorph control platform. The versatility of the gas-solid reaction-based polymorphic control will enable the engineering of metastable phases in 2D TMDs for further applications.

Effects of recruitment manoeuvre on perioperative pulmonary complications in patients undergoing robotic assisted radical prostatectomy: A randomised single-blinded trial.

Robotic-assisted laparoscopic radical prostatectomy (RARP) needs a steep Trendelenburg position and a relatively high CO2 insufflation pressure, and patients undergoing RARP are usually elderly. These factors make intraoperative ventilatory care difficult and increase the risk of perioperative pulmonary complications. The aim was to determine the efficacy of recruitment manoeuvre (RM) on perioperative pulmonary complications in elderly patients undergoing RARP. A total of 60 elderly patients scheduled for elective RARP were randomly allocated to two groups after induction of anaesthesia; positive end expiratory pressure (PEEP) was applied during the operation without RM in the control group (group C) and after RM in the recruitment group (group R). The total number of patients who developed intraoperative desaturation or postoperative atelectasis was significantly higher in group C compared to group R (43.3% vs. 17.8%, P = 0.034). Intraoperative respiratory mechanics, perioperative blood gas analysis, and pulmonary function testing did not show differences between the groups. Adding RM to PEEP compared to PEEP alone significantly reduced perioperative pulmonary complications in elderly patients undergoing RARP.