In Situ Phase Separation-Induced Self-Healing Catalyst for Efficient Direct Seawater Electrolysis.

Direct seawater electrolysis technology for sustainable hydrogen production has garnered significant attention, owing to its abundant resource supply and economic potential. However, the complex composition and high chloride concentration of seawater have hindered its practical implementation. In this study, we report an in situ-synthesized dual-phase electrocatalyst (HPS-NiMo), comprising an amorphous phosphide protective outer phase and a crystalline alloy inner phase with supplementary sulfur active sites, to improve the kinetics of direct seawater electrolysis. The HPS-NiMo exhibits long-term stability, remaining stable for periods exceeding 120 h at 200 mA cm-2; moreover, it lowers the required operating voltage to ∼1.8 V in natural seawater. The chlorine chemistry, corrosion during direct natural seawater electrolysis, and mechanism behind the high-performing catalysts are discussed. We also investigated the possibility of recovering the anode precipitates, which inevitably occurs during seawater electrolysis.

Valgus Arthritic Knee Responds Better to Conservative Treatment than the Varus Arthritic Knee.

Background and Objectives: Clinically, it is beneficial to determine the knee osteoarthritis (OA) subtype that responds well to conservative treatments. Therefore, this study aimed to determine the differences between varus and valgus arthritic knees in the response to conservative treatment. We hypothesized that valgus arthritic knees would respond better to conservative treatment than varus arthritic knees. Materials and Methods: Medical records of 834 patients who received knee OA treatment were retrospectively reviewed. Patients with Kellgren-Lawrence grades III and IV were divided into two groups according to knee alignment (varus arthritic knee, hip-knee-ankle angle [HKA] > 0° or valgus arthritic knee, HKA < 0°). The Kaplan-Meier curve with total knee arthroplasty (TKA) as an endpoint was used to compare the survival probability between varus and valgus arthritic knees at one, two, three, four, and five years after the first visit. A receiver operating characteristic (ROC) curve was used to compare the HKA thresholds for TKA between varus and valgus arthritic knees. Results: Valgus arthritic knees responded better to conservative treatment than varus arthritic knees. With TKA as an endpoint, the survival probabilities for varus and valgus arthritic knees were 24.2% and 61.4%, respectively, at the 5-year follow-up (p < 0.001). The thresholds of HKA for varus and valgus arthritic knees for TKA were 4.9° and -8.1°, respectively (varus: area under the ROC curve [AUC] = 0.704, 95% confidence interval [CI] 0.666-0.741, p < 0.001, sensitivity = 0.870, specificity = 0.524; valgus: AUC = 0.753, 95% CI 0.693-0.807, p < 0.001, sensitivity = 0.753, specificity = 0.786). Conclusions: Conservative treatment is more effective for valgus than for varus arthritic knees. This should be considered when explaining the prognosis of conservative treatment for knees with varus and valgus arthritis.

Highly Efficient Self-Encapsulated Flexible Semitransparent Perovskite Solar Cells via Bifacial Cation Exchange.

Flexible semitransparent perovskite solar cells (ST-PSCs) have great potential for use in high-density energy systems, such as building or vehicle integrated photovoltaics, considering the great features of PSC devices, including high performance, light weight, thin-film processability, and high near-infrared transmittance. Despite numerous efforts toward achieving efficiency and flexibility in ST-PSCs, the realization of high-performance and operational stability in ST-PSCs still require further development. Herein, we demonstrated the development of highly efficient, stable, and flexible ST-PSCs using polyimide-integrated graphene electrodes via a lamination-assisted bifacial cation exchange strategy. A high-quality perovskite layer was obtained through the cation exchange reaction using the lamination process, and ST-PSCs with 15.1% efficiency were developed. The proposed ST-PSC device also demonstrated excellent operational stability, mechanical durability, and moisture stability owing to the chemically inert and mechanically robust graphene electrodes. This study provides an effective strategy for developing highly functional ST-perovskite optoelectronic devices with high-performance and long-term operational stability.

Rotator cuff retear after repair surgery: comparison between experienced and inexperienced surgeons.

BACKGROUND: We hypothesized in this study that the characteristics of retear cases vary according to surgeon volume and that surgical outcomes differ between primary and revision arthroscopic rotator cuff repair (revisional ARCR). METHODS: Surgeons performing more than 12 rotator cuff repairs (RCRs) per year were defined as high-volume surgeons, and those performing fewer than 12 RCRs were considered low-volume surgeons. Of the 47 patients who underwent revisional ARCR at our clinic enrolled in this study, 21 cases were treated by high-volume surgeons and 26 cases by low-volume surgeons. In all cases, the interval between primary surgery and revisional ARCR, degree of "acromial scuffing," number of anchors, RCR technique, retear pattern, fatty infiltration, retear size, operating time, and clinical outcome were recorded. RESULTS: During primary surgery, significantly more lateral anchors (p=0.004) were used, and the rate of use of the double-row repair technique was significantly higher (p<0.001) in the high- versus low-volume surgeon group. Moreover, the "cut-through pattern" was observed significantly more frequently among the cases treated by high- versus low-volume surgeons (p=0.008). The clinical outcomes after revisional ARCR were not different between the two groups. CONCLUSIONS: Double-row repair during primary surgery and the cut-through pattern during revisional ARCR were more frequent in the high- versus low-volume surgeon groups. However, no differences in retear site or size, fatty infiltration grade, or outcomes were observed between the groups.

Defect-Induced in Situ Atomic Doping in Transition Metal Dichalcogenides via Liquid-Phase Synthesis toward Efficient Electrochemical Activity.

Transition metal dichalcogenides (TMDs), due to their fascinating properties, have emerged as potential next-generation semiconducting nanomaterials across diverse fields of applications. When combined with other material systems, precise control of the intrinsic properties of the TMDs plays a vital role in maximizing their performance. Defect-induced atomic doping through introduction of a chalcogen vacancy into the TMDs lattices is known to be a promising strategy for modulating their characteristic properties. As a result, there is a need to develop tunable and scalable synthesis routes to achieve vacancy-modulated TMDs. Herein, we propose a facile liquid-phase ligand exchange approach for scalable, uniform, and vacancy-tunable synthesis of TMDs films. Varying the relative molar ratio of the chalcogen to transition metal precursors enabled the in situ modulation of the chalcogen vacancy concentrations without necessitating additional post-treatments. When employed as the electrocatalyst in the hydrogen evolution reaction (HER), the vacancy-modulated TMDs, exhibiting a synergetic effect on the energy level matching to the reduction potential of water and optimized free energy differences in the HER pathways, showed a significant enhancement in the hydrogen production via the improved charge transfer kinetics and increased active sites. The proposed approach for synthesizing tunable vacancy-modulated TMDs with wafer-scale synthesis capability is, therefore, promising for better practical applications of TMDs.

Suppressed Interdiffusion and Degradation in Flexible and Transparent Metal Electrode-Based Perovskite Solar Cells with a Graphene Interlayer.

Metal-based transparent conductive electrodes (TCEs) are attractive candidates for application in indium tin oxide (ITO)-free solar cells due to their excellent electrical conductivity and cost effectiveness. In perovskite solar cells (PSCs), metal-induced degradation with the perovskite layer leads to various detrimental effects, deteriorating the device performance and stability. Here, we introduce a novel flexible hybrid TCE consisting of a Cu grid-embedded polyimide film and a graphene capping layer, named GCEP, which exhibits excellent mechanical and chemical stability as well as desirable optoelectrical properties. We demonstrated the critical role of graphene as a protection layer to prevent metal-induced degradation and halide diffusion between the electrode and perovskite layer; the performance of the flexible PSCs fabricated with GCEP was comparable to that of their rigid ITO-based counterparts and also exhibited outstanding mechanical and chemical stability. This work provides an effective strategy to design mechanically and chemically robust ITO-free metal-assisted TCE platforms in PSCs.

Multifaceted Role of a Dibutylhydroxytoluene Processing Additive in Enhancing the Efficiency and Stability of Planar Perovskite Solar Cells.

Significant research efforts are currently being devoted to improving both the crystalline quality and stability of lead halide perovskite absorbers to advance the commercial prospects of perovskite-based solar cells. Herein, we report a simple one-step dibutylhydroxytoluene (BHT) additive-based approach for simultaneously improving the crystallinity and resistance of perovskite films under adverse degradation conditions. We found that BHT, commonly known for its antioxidant properties, can considerably improve the performance of methylammonium lead iodide perovskite solar cells by modulating the chemical environment within the precursor medium to form intermediate complexes, and it can also suppress photooxidation, which results in perovskite degradation under environmental operating conditions. Consequently, a device exhibited a significant power conversion efficiency improvement to 18.1% with the BHT-additive-based perovskite absorber, exceeding the 17.1% efficiency achieved for the control device. The BHT additive also improved the perovskite stability by quenching intermediate reactions resulting in perovskite degradation to an undesirable lead iodide phase, as evidenced by detailed analysis of absorption spectra, grazing-incidence wide-angle X-ray scattering, X-ray photoelectron spectra, and photoluminescence measurements.

In-situ local phase-transitioned MoSe2 in La0.5Sr0.5CoO3-δ heterostructure and stable overall water electrolysis over 1000 hours.

Developing efficient bifunctional catalysts for overall water splitting that are earth-abundant, cost-effective, and durable is of considerable importance from the practical perspective to mitigate the issues associated with precious metal-based catalysts. Herein, we introduce a heterostructure comprising perovskite oxides (La0.5Sr0.5CoO3-δ) and molybdenum diselenide (MoSe2) as an electrochemical catalyst for overall water electrolysis. Interestingly, formation of the heterostructure of La0.5Sr0.5CoO3-δ and MoSe2 induces a local phase transition in MoSe2, 2 H to 1 T phase, and more electrophilic La0.5Sr0.5CoO3-δ with partial oxidation of the Co cation owing to electron transfer from Co to Mo. Together with these synergistic effects, the electrochemical activities are significantly improved for both hydrogen and oxygen evolution reactions. In the overall water splitting operation, the heterostructure showed excellent stability at the high current density of 100 mA cm-2 over 1,000 h, which is exceptionally better than the stability of the state-of-the-art platinum and iridium oxide couple.

Development of Annealing-Free, Solution-Processable Inverted Organic Solar Cells with N-Doped Graphene Electrodes using Zinc Oxide Nanoparticles.

An annealing-free process is considered as a technological advancement for the development of flexible (or wearable) organic electronic devices, which can prevent the distortion of substrates and damage to the active components of the device and simplify the overall fabrication process to increase the industrial applications. Owing to its outstanding electrical, optical, and mechanical properties, graphene is seen as a promising material that could act as a transparent conductive electrode for flexible optoelectronic devices. Owing to their high transparency and electron mobility, zinc oxide nanoparticles (ZnO-NP) are attractive and promising for their application as charge transporting materials for low-temperature processes in organic solar cells (OSCs), particularly because most charge transporting materials require annealing treatments at elevated temperatures. In this study, graphene/annealing-free ZnO-NP hybrid materials were developed for inverted OSC by successfully integrating ZnO-NP on the hydrophobic surface of graphene, thus aiming to enhance the applicability of graphene as a transparent electrode in flexible OSC systems. Chemical, optical, electrical, and morphological analyses of ZnO-NPs showed that the annealing-free process generates similar results to those provided by the conventional annealing process. The approach was effectively applied to graphene-based inverted OSCs with notable power conversion efficiencies of 8.16% and 7.41% on the solid and flexible substrates, respectively, which promises the great feasibility of graphene for emerging optoelectronic device applications.