Spatially Confined Microcells: A Path toward TMD Catalyst Design.

With the ability to maximize the exposure of nearly all active sites to reactions, two-dimensional transition metal dichalcogenide (TMD) has become a fascinating new class of materials for electrocatalysis. Recently, electrochemical microcells have been developed, and their unique spatial-confined capability enables understanding of catalytic behaviors at a single material level, significantly promoting this field. This Review provides an overview of the recent progress in microcell-based TMD electrocatalyst studies. We first introduced the structural characteristics of TMD materials and discussed their site engineering strategies for electrocatalysis. Later, we comprehensively described two distinct types of microcells: the window-confined on-chip electrochemical microcell (OCEM) and the droplet-confined scanning electrochemical cell microscopy (SECCM). Their setups, working principles, and instrumentation were elucidated in detail, respectively. Furthermore, we summarized recent advances of OCEM and SECCM obtained in TMD catalysts, such as active site identification and imaging, site monitoring, modulation of charge injection and transport, and electrostatic field gating. Finally, we discussed the current challenges and provided personal perspectives on electrochemical microcell research.

N-Doping-Induced Amorphization for Achieving Ultrastable Aqueous Zinc-Ion Batteries.

Vanadium-based oxides, known for their high capacity and low cost, have garnered significant attention as promising cathode candidates in aqueous zinc-ion batteries. Nonetheless, their poor rate performance and limited durability in aqueous electrolytes present a challenge to the realistic implementation of vanadium-based aqueous zinc-ion batteries. Here, we synthesized nitrogen-doped V2O3@C (N-V2O3@N-C) via ammonia treatment of V2O3@C derived from vanadium-based metal-organic framework (V-MOF), aiming to achieve outstanding rate and cycling performance. The N-V2O3@N-C electrode exhibits notable in situ self-transformation into an amorphous state. Density functional theory calculations reveal that the distorted N-V2O3 structure and uneven charge distribution result in the creation of an amorphous state. As expected, Zn/N-V2O3@N-C aqueous zinc-ion batteries can achieve remarkable specific capacity (349.0 mAh g-1 at 0.1 A g-1), along with impressive rate performance, showcasing a capacity of 253.5 mAh g-1 at 5 A g-1 and exceptional durability at 5 A g-1 (96.4% after 1350 cycles). The employed induced amorphization approach offers novel perspectives for designing high-performance cathodes that exhibit both sturdy structures and extended cycling lifespans.

Surface heterojunction based on n-type low-dimensional perovskite film for highly efficient perovskite tandem solar cells.

Enhancing the quality of junctions is crucial for optimizing carrier extraction and suppressing recombination in semiconductor devices. In recent years, metal halide perovskite has emerged as the most promising next-generation material for optoelectronic devices. However, the construction of high-quality perovskite junctions, as well as characterization and understanding of their carrier polarity and density, remains a challenge. In this study, using combined electrical and spectroscopic characterization techniques, we investigate the doping characteristics of perovskite films by remote molecules, which is corroborated by our theoretical simulations indicating Schottky defects consisting of double ions as effective charge dopants. Through a post-treatment process involving a combination of biammonium and monoammonium molecules, we create a surface layer of n-type low-dimensional perovskite. This surface layer forms a heterojunction with the underlying 3D perovskite film, resulting in a favorable doping profile that enhances carrier extraction. The fabricated device exhibits an outstanding open-circuit voltage (VOC) up to 1.34 V and achieves a certified efficiency of 19.31% for single-junction wide-bandgap (1.77 eV) perovskite solar cells, together with significantly enhanced operational stability, thanks to the improved separation of carriers. Furthermore, we demonstrate the potential of this wide-bandgap device by achieving a certified efficiency of 27.04% and a VOC of 2.12 V in a perovskite/perovskite tandem solar cell configuration.

On-device phase engineering.

In situ tailoring of two-dimensional materials' phases under external stimulus facilitates the manipulation of their properties for electronic, quantum and energy applications. However, current methods are mainly limited to the transitions among phases with unchanged chemical stoichiometry. Here we propose on-device phase engineering that allows us to realize various lattice phases with distinct chemical stoichiometries. Using palladium and selenide as a model system, we show that a PdSe2 channel with prepatterned Pd electrodes can be transformed into Pd17Se15 and Pd4Se by thermally tailoring the chemical composition ratio of the channel. Different phase configurations can be obtained by precisely controlling the thickness and spacing of the electrodes. The device can be thus engineered to implement versatile functions in situ, such as exhibiting superconducting behaviour and achieving ultralow-contact resistance, as well as customizing the synthesis of electrocatalysts. The proposed on-device phase engineering approach exhibits a universal mechanism and can be expanded to 29 element combinations between a metal and chalcogen. Our work highlights on-device phase engineering as a promising research approach through which to exploit fundamental properties as well as their applications.

CPA4 as a biomarker promotes the proliferation, migration and metastasis of clear cell renal cell carcinoma cells.

Clear cell renal cell carcinoma (ccRCC) is a commonly occurring and highly aggressive urological malignancy characterized by a significant mortality rate. Current therapeutic options for advanced ccRCC are limited, necessitating the discovery of novel biomarkers and therapeutic targets. Carboxypeptidase A4 (CPA4) is a zinc-containing metallocarboxypeptidase with implications in various cancer types, but its role in ccRCC remains unexplored. The Cancer Genome Atlas (TCGA) and Gene Expression Omnibus (GEO) databases were utilized in order to investigate the differential expression patterns of CPA4. The expression of CPA4 in ccRCC patients was further verified using immunohistochemical (IHC) examination of 24 clinical specimens. A network of protein-protein interactions (PPI) was established, incorporating CPA4 and its genes that were expressed differentially. Functional enrichment analyses were conducted to anticipate the contribution of CPA4 in the development of ccRCC. To validate our earlier study, we conducted real-time PCR and cell functional tests on ccRCC cell lines. Our findings revealed that CPA4 is overexpressed in ccRCC, and the higher the expression of CPA4, the worse the clinical outcomes such as TNM stage, pathological stage, histological grade, etc. Moreover, patients with high CPA4 expression had worse overall survival, disease-specific survival and progress-free interval than patients with low expression. The PPI network analysis highlighted potential interactions contributing to ccRCC progression. Functional enrichment analysis indicated the involvement of CPA4 in the regulation of key pathways associated with ccRCC development. Additionally, immune infiltration analysis suggested a potential link between CPA4 expression and immune response in the tumour microenvironment. Finally, cell functional studies in ccRCC cell lines shed light on the molecular mechanisms underlying the role of CPA4 in promoting ccRCC formation. Overall, our study unveils CPA4 as a promising biomarker with prognostic potential in ccRCC. The identified interactions and pathways provide valuable insights into its implications in ccRCC development and offer a foundation for future research on targeted therapies. Further investigation of CPA4's involvement in immune responses may contribute to the development of immunotherapeutic strategies for ccRCC treatment.

MXenes as emerging adsorbents for removal of environmental pollutants.

MXenes are a recently emerging class of two-dimensional nanomaterials that have gained considerable interest in the field of environmental protection. Owing to their high surface area, abundant terminal groups, and unique two-dimensional layered structures, MXenes have demonstrated high efficacy as adsorbents for various pollutants. Here we focused on the latest developments in the field of MXene-based adsorbents, including the structure and properties of MXenes, their synthesis and modification methods, and their adsorption performance and mechanisms for various pollutants. Among the pollutants that have been reported to be adsorbed by MXenes are radionuclides (U(VI), Sr(II), Cs(I), Eu(III), Ba(II), Th(IV), and Tc(VII)/Re(VII)), heavy metals (Hg(II), Cu(II), Cr(VI), and Pb(II)), dyes, per- and polyfluoroalkyl substances (PFAS), antibiotics (tetracycline, ciprofloxacin, and sulfonamides), antibiotic resistance genes (ARGs), and other contaminates. Moreover, future directions in MXene research are also suggested in this review.

Core-shell design of UiO66-Fe3O4 configured with EDTA-assisted washing for rapid adsorption and simple recovery of heavy metal pollutants from soil.

The coupling of washing with adsorption process can be adopted for the treatment of soils contaminated with heavy metals pollution. However, the complex environment of soil and the competitive behavior of leaching chemicals considerably restrain adsorption capacity of adsorbent material during washing process, which demands a higher resistance of the adsorbents to interference. In this study, we synthesized strongly magnetic, high specific surface area (573.49 m2/g) UiO66 composites (i.e., UiO66-Fe3O4) using hydrothermal process. The UiO66-Fe3O4 was applied as an adsorbent during the ethylene diamine tetraacetic acid (EDTA)-assisted washing process of contaminated soil. The incorporation of UiO66-Fe3O4 results in rapid heavy metal removal and recovery from the soil under low concentrations of washing agent (0.001 mol/L) with reduced residual heavy metal mobility of soil after remediation. Furthermore, UiO66-Fe3O4 can quickly recollect by an external magnet, which offers a simple and inexpensive recovery method for heavy metals from contaminated soil. Overall, UiO66-Fe3O4 configuration with EDTA-assisted washing process showed opportunities for heavy metals contaminated sites.

High-Pressure Synthesis of Single-Crystalline SnS Nanoribbons.

Two-dimensional tin monosulfide (SnS) is attractive for the development of electronic and optoelectronic devices with anisotropic characteristics. However, its shape-controlled synthesis with an atomic thickness and high quality remains challenging. Here, we show that highly crystalline SnS nanoribbons can be produced via high-pressure (0.5 GPa) and thermal treatment (400 °C). These SnS nanoribbons have a length of several tens of micrometers and a thickness down to 5.8 nm, giving an average aspect ratio of ∼30.6. The crystal orientation along the zigzag direction and the in-plane structural anisotropy of the SnS nanoribbons are identified by transmission electron microscopy and polarized Raman spectroscopy, respectively. An ionic liquid-gated field-effect transistor fabricated using the SnS nanoribbon exhibits an on/off current ratio of >103 and a field-effect mobility of ∼0.7 cm2 V-1 s-1. This work provides a unique way to achieve one-dimensional growth of SnS.

Naturally occurring beneficial bacteria Vibrio alginolyticus X-2 protects seaweed from bleaching disease.

Microbiome manipulation is gaining fresh attention as a way to mitigate diseases in aquaculture. The commercially farmed seaweed Saccharina japonica suffers from a bacterial-induced bleaching disease, which has major implications for the reliable supply of healthy sporelings. Here, we identify a beneficial bacterium, Vibrio alginolyticus X-2 that significantly reduces the risk of bleaching disease. By combining infection assays and multi-omic analyses, we provide evidence to suggest that the underlying protective mechanisms of V. alginolyticus X-2 involve maintaining epibacterial communities, increasing the gene expression of S. japonica related to immune and stress protection pathways, and stimulating betaine concentrations in S. japonica holobionts. Thus, V. alginolyticus X-2 can elicit a suite of microbial and host responses to mitigate the bleaching disease. Our study provides insights into disease control in farmed S. japonica through the application of beneficial bacteria. IMPORTANCE Beneficial bacteria can elicit a suite of microbial and host responses to enhance the resistance to bleaching disease.

A Morphing Point-to-Point Displacement Control Based on Long Short-Term Memory for a Coplanar XXY Stage.

In this study, visual recognition with a charge-coupled device (CCD) image feedback control system was used to record the movement of a coplanar XXY stage. The position of the stage is fedback through the image positioning method, and the positioning compensation of the stage is performed by the image compensation control parameter. The image resolution was constrained and resulted in an average positioning error of the optimized control parameter of 6.712 µm, with the root mean square error being 2.802 µm, and the settling time being approximately 7 s. The merit of a long short-term memory (LSTM) deep learning model is that it can identify long-term dependencies and sequential state data to determine the next control signal. As for improving the positioning performance, LSTM was used to develop a training model for stage motion with an additional dial indicator with an accuracy of 1 µm being used to record the XXY position information. After removing the assisting dial indicator, a new LSTM-based XXY feedback control system was subsequently constructed to reduce the positioning error. In other words, the morphing control signals are dependent not only on time, but also on the iterations of the LSTM learning process. Point-to-point commanded forward, backward and repeated back-and-forth repetitive motions were conducted. Experimental results revealed that the average positioning error achieved after using the LSTM model was 2.085 µm, with the root mean square error being 2.681 µm, and a settling time of 2.02 s. With the assistance of LSTM, the stage exhibited a higher control accuracy and less settling time than did the CCD imaging system according to three positioning indices.

Symmetry-Broken 2D Lead-Tin Mixed Chiral Perovskite for High Asymmetry Factor Circularly Polarized Light Detection.

Symmetry-broken-induced spin splitting plays a key role for selective circularly polarized light absorption and spin carrier transport. Asymmetrical chiral perovskite is rising as the most promising material for direct semiconductor-based circularly polarized light detection. However, the increase of asymmetry factor and extension of response region remain to be a challenge. Herein, we fabricated a two-dimensional tin-lead mixed chiral perovskite with tunable absorption in the visible region. Theoretical simulation indicates that the mixing of the tin and lead in chiral perovskite breaks the symmetry of the pure ones, resulting in pure spin splitting. We then fabricated a chiral circularly polarized light detector based on this tin-lead mixed perovskite. A high asymmetry factor for the photocurrent of 0.44 is achieved, which is 144% higher than pure lead 2D perovskite, and it is the highest value reported for the pure chiral 2D perovskite-based circularly polarized light detector using a simple device structure.

Recent Progress in Double-Layer Honeycomb Structure: A New Type of Two-Dimensional Material.

Two-dimensional (2D) materials are no doubt the most widely studied nanomaterials in the past decade. Most recently, a new type of 2D material named the double-layer honeycomb (DLHC) structure opened a door to achieving a series of 2D materials from traditional semiconductors. However, as a newly developed material, there still lacks a timely understanding of its structure, property, applications, and underlying mechanisms. In this review, we discuss the structural stability and experimental validation of this 2D material, and systematically summarize the properties and applications including the electronic structures, topological properties, optical properties, defect engineering, and heterojunctions. It was concluded that the DLHC can be a universal configuration applying to III-V, II-VI, and I-VII semiconductors. Moreover, these DLHC materials indeed have exotic properties such as being excitonic/topological insulators. The successful fabrication of DLHC materials further demonstrates it is a promising topic. Finally, we summarize several issues to be addressed in the future, including further experimental validation, defect engineering, heterojunction engineering, and strain engineering. We hope this review can help the community to better understand the DLHC materials timely and inspire their applications in the future.

Role of N in Transition-Metal-Nitrides for Anchoring Platinum-Group Metal Atoms toward Single-Atom Catalysis.

Single-atom catalysts (SACs) with a maximum atom utilization efficiency have received growing attention in heterogeneous catalysis. The supporting substrate that provides atomic-dispersed anchoring sites and the local electronic environment in these catalysts is crucial to their activity and stability. Here, inspired by N-doped graphene substrate, the role of N is explored in transition metal nitrides for anchoring single metal atoms toward single-atom catalysis. A pore-rich metallic vanadium nitride (VN) nanosheet is fabricated as one supporting-substrate example, whose surface features abundant unsaturated N sites with lower binding energy than that of widely used N-doped graphene. Impressively, it is found that this support can anchor nearly all platinum-group single atoms (e.g., platinum, palladium, iridium, and ruthenium), and even be extendable to multiple SACs, i.e., binary (Pt/Pd) and ternary (Pt/Pd/Ir). As a proof-of-concept application for hydrogen production, Pt-based SAC (Pt1 -VN) performs excellently, exhibiting a mass activity up to 22.55 A mg-1 Pt at 0.05 V and a high turnover frequency value close to 0.350 H2 s-1 , superior to commercial platinum/carbon catalyst. The catalyst's durability can be further improved by using binary (Pt1 Pd1 -VN) SAC. This work provides inexpensive and durable nitride-based support, giving a possible pathway for universally constructing platinum-group SACs.

Intrinsic Photosensitivity of the Vulnerable Seagrass Phyllospadix iwatensis: Photosystem II Oxygen-Evolving Complex Is Prone to Photoinactivation.

Phyllospadix iwatensis, a foundation species of the angiosperm-dominated marine blue carbon ecosystems, has been recognized to be a vulnerable seagrass. Its degradation has previously been reported to be associated with environmental changes and human activities, while there has been a limited number of studies on its inherent characteristics. In this study, both the physiological and molecular biological data indicated that the oxygen-evolving complex (OEC) of P. iwatensis is prone to photoinactivation, which exhibits the light-dependent trait. When exposed to laboratory light intensities similar to typical midday conditions, <10% of the OEC was photoinactivated, and the remaining active OEC was sufficient to maintain normal photosynthetic activity. Moreover, the photoinactivated OEC could fully recover within the same day. However, under harsh light conditions, e.g., light intensities that simulate cloudless sunny neap tide days and continual sunny days, the OEC suffered irreversible photoinactivation, which subsequently resulted in damage to the photosystem II reaction centers and a reduction in the rate of O2 evolution. Furthermore, in situ measurements on a cloudless sunny neap tide day revealed both poor resilience and irreversible photoinactivation of the OEC. Based on these findings, we postulated that the OEC dysfunction induced by ambient harsh light conditions could be an important inherent reason for the degradation of P. iwatensis.

How the COVID-19 pandemic affects job sentiments of rural teachers.

This study investigates how the COVID-19 pandemic has affected teachers' job-specific stresses and their enthusiasm for the teaching occupation. We use unique data from China that cover the periods before and after the start of the pandemic and apply various estimation methods. We find that, among rural young teachers, the pandemic has caused higher teaching stress and career development stress and has reduced passion toward the teaching occupation. We investigate the working channels of the pandemic, including changes in job-related activities and social network. After controlling for possible working channels, the COVID-19 pandemic still shows a strong direct impact on job sentiments.

Electrolyte additives inhibit the surface reaction of aqueous sodium/zinc battery.

In aqueous zinc-based batteries, the reaction by-product Zn4SO4(OH)6·xH2O is commonly observed when cycling vanadium-based and manganese-based cathodes. This by-product obstructs ion transport paths, resulting in enhanced electrochemical impedance. In this work, we report a hybrid aqueous battery based on a Na0.44MnO2 cathode and a metallic zinc foil anode. The surfactant sodium lauryl sulfate is added to the electrolyte as a modifier, and the performance before and after modification is compared. The results show that sodium lauryl sulfate can generate an artificial passivation film on the electrode surface. This passivation film reduces the generation of Zn4SO4(OH)6·xH2O and inhibits the dissolution of Na0.44MnO2 in the electrolyte. Therefore, the reaction kinetics and cycle stability of the battery are significantly enhanced. A battery with this electrolyte additive delivers an initial discharge capacity of 235 mA h g-1 at a current density of 0.1 A g -1. At the same time, the battery has excellent rate performance. Under the high-rate condition of 1 A g-1, the battery still maintains a capacity retention rate of 93% after 1500 cycles. Finally, the functional mechanism of by-product inhibition by the electrolyte additive is discussed.

Extracellular Compounds from Pathogenic Bacterium Pseudoalteromonas piscicida X-8 Cause Bleaching Disease, Triggering Active Defense Responses in Commercially Farmed Saccharina japonica.

Pathogenic bacteria can trigger active defense responses in higher plants, leading to hypersensitive programmed cell death (PCD) to against those bacteria. However, related research on seaweeds is very limited. Pseudoalteromonas piscicida X-8 (PpX-8) has been identified as the pathogen that causes bleaching disease in commercially farmed Saccharina japonica. In this study, using an inoculation assay and microscopic observations, we found that the proportion of bleaching tissue pieces inoculated with PpX-8 extracellular compounds was significantly higher (p < 0.05) than that inoculated with heated extracellular compounds, indicating that the virulence factors of PpX-8 exist in extracellular compounds and they are heat-sensitive. Using TEM, we observed typical morphological characteristics of PCD after inoculation with extracellular compounds, including chloroplast shrinkage, cytoplasmic vacuolation, and intact mitochondrial structures. Moreover, we detected biochemical characteristics of PCD, such as 3'-OH ends resulting from DNA cleavage and caspase-3-like enzymatic activity, using a TUNEL assay and fluorescence staining. Therefore, PpX-8 extracellular compounds can induce PCD, thus triggering active defense responses in S. japonica. These results indicate that seaweeds and higher plants are conservative in their active defense responses against pathogenic bacteria. The results of this study lay the foundation for further investigation of the virulence mechanisms of PpX-8.

Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF3.

Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.

Double-Regiodetermining-Stages Mechanistic Model Explaining the Regioselectivity of Pd-Catalyzed Hydroaminocarbonylation of Alkenes with Carbon Monoxide and Ammonium Chloride.

Pd-catalyzed hydroaminocarbonylation (HAC) of alkenes with CO and NH4Cl enables atom-economic and regiodivergent synthesis of primary amides, but the origin of regioselectivity was incorrectly interpreted in previous computational studies. A density functional theory study was performed herein to investigate the mechanism. Different from the previous proposals, both alkene insertion and aminolysis were found to be potential regioselectivity-determining stages. In the alkene insertion stage, 2,1-insertion is generally faster than 1,2-insertion irrespective of neutral or cationic pathways for both P(tBu)3 and xantphos. Such selectivity results from the unconventional proton-like hydrogen of the Pd-H bond in alkene insertion transition states. For less bulky alkenes, aminolysis with P(tBu)3 shows low selectivity, while linear selectivity dominates in this stage with xantphos due to a stronger repulsion between xantphos and branched acyl ligands. It was further revealed that the less-mentioned CO concentration and solvents also influence the regioselectivity by adjusting the relative feasibilities of CO-involved steps and NH3 release from ammonium chloride, respectively. The presented double-regiodetermining-stages mechanistic model associated with the effects of ligands, CO concentration, and solvents well reproduced the experimental selectivity to prove its validity and illuminated new perspectives for the regioselectivity control of HAC reactions.

Photoinactivation of the oxygen-evolving complex regulates the photosynthetic strategy of the seagrass Zostera marina.

Zostera marina, a widespread seagrass, evolved from a freshwater ancestor of terrestrial monocots and successfully transitioned into a completely submerged seagrass. We found that its oxygen-evolving complex (OEC) was partially inactivated in response to light exposure, as evidenced by both the increment of the relative variable fluorescence at the K-step and the downregulation of the OEC genes and proteins. This photosynthetic regulation was further addressed at both proteome and physiology levels by an in vivo study. The unchanged content of the ΔpH sensor PsbS protein and the non-photochemical quenching induction dynamics, described by a single exponential function, verified the absence of the fast qE component. Contents and activities of chlororespiration, Mehler reaction, malic acid synthesis, and photorespiration key enzymes were not upregulated, suggesting that alternative electron flows remained unactivated. Furthermore, neither significant production of singlet oxygen nor increment of total antioxidative capacity indicated that reactive oxygen species were not produced during light exposure. In summary, these low electron consumptions may allow Z. marina to efficiently use the limited electrons caused by partial OEC photoinactivation to maintain a normal carbon assimilation level.