Synthesis of Graphdiyne Hollow Spheres and Multiwalled Nanotubes and Applications in Water Purification and Raman Sensing.

Controlling the structure of graphdiyne (GDY) is crucial for the discovery of new properties and the development of new applications. Herein, the microemulsion synthesis of GDY hollow spheres (HSs) and multiwalled nanotubes composed of ultrathin nanosheets is reported for the first time. The formation of an oil-in-water (O/W) microemulsion is found to be a key factor controlling the growth of GDY. These GDY HSs have fully exposed surfaces because of the avoidance of overlapping between nanosheets, thereby showing an ultrahigh specific surface area of 1246 m2 g-1 and potential applications in the fields of water purification and Raman sensing.

Exploring the Fate of Copper Ions in the Synthesis of Graphdiyne.

Copper is a crucial catalyst in the synthesis of graphdiyne (GDY). However, as catalysts, the final fate of the copper ions has hardly been concerned, which are usually treated as impurities. Here, it is observed that after simple washing with water and ethanol, GDY still contains a certain amount of copper ions, and demonstrated that the copper ions are adsorbed at the atomic layers of GDY. Furthermore, we transformed in situ the copper ions into ultrathin Cu nanocrystals, and the obtained Cu/GDY hybrids can be generally converted into a series of metal/GDY hybrid materials, such as Ag/GDY, Au/GDY, Pt/GDY, Pd/GDY, and Rh/GDY. The Cu/GDY hybrids exhibit extraordinary surface enhanced Raman scattering effect and can be applied in pollutant efficient enrichment and detection.

Tailoring Li Deposition by Regulating Structural Connectivity of Electrochemical Li Reservoir in Li-metal Batteries.

Irregular Li deposition is the major reason for poor reversibility and cycle instability in Li metal batteries, even leading to safety hazards, the causes of which have been extensively explored. The structural disconnection induced by completely dissolving Li in the traditional testing protocol is a key factor accounting for irregular Li growth during the subsequent deposition process. Herein, the critical role played by the structural connectivity of electrochemical Li reservoir in subsequent Li deposition behaviors is elucidated and a morphology-performance correlation is established. The structural connection and resultant well-distributed morphology of the in situ electrochemical Li reservoir ensure efficient electron transfer and Li+ diffusion pathway, finally leading to homogenized Li nucleation and growth. Tailoring the geometry of Li reservoir can improve the coulombic efficiency and cyclability of anode-free Li metal batteries by optimizing Li deposition behavior.

Efficient formaldehyde sensor based on PtPd nanoparticles-loaded nafion-modified electrodes.

The noble metal-based electrochemical sensor design for efficient and stable formaldehyde(FA) detection is important ongoing research. In this paper, PtPd/Nafion/GCE is prepared by electrochemical cyclic voltammetry deposition method based on electrodepositing nanostructured platinum (Pt)-palladium (Pd) nanoparticles in Nafion film-coated glassy carbon electrode (GCE). The influence of deposition parameters and chemical composition (atomic ratio of Pt and Pd) on the electrochemical behaviour of PtPd/Nafion/GCE has been investigated. PtPd/Nafion/GCE displays a remarked electrocatalytic activity for the oxidation of FA and exhibits a linear relationship in the range of 10-5000µM, with a detection limit of 3.3µM in 0.1 M H2SO4solution. It is proved that the detection performance of PtPd/Nafion/GCE electrode is valuable for further application with low detection limit, wide linear range, favourable selectivity and high response.

Directly Convert Carbonaceous Microspheres to Three-Dimensional Porous Carbon Microspheres with a Robust Self-Supporting Structure as a Metal-Free SERS Substrate for Online High-Throughput Analysis.

It is of great significance for practical applications to directly convert readily available biomass carbon into three-dimensional (3D) porous carbon microspheres with a self-supporting structure. Herein, we report the convenient conversion of biomass carbon microspheres to hierarchical porous carbon microspheres (HP-CMSs) with a robust self-supporting framework structure. A general SiO2-induced etching mechanism is proposed for the formation of the HP-CMSs. Benefiting from this robust 3D self-supporting frame structure, these HP-CMSs have outstanding mechanical, chemical, and thermal stability. As a metal-free surface-enhanced Raman scattering (SERS) substrate with an ultrahigh specific surface area (4216 m2 g-1) and a high density of active sites, the HP-CMSs exhibit high sensitivity with a detection limit of 10-10 M and a Raman enhancement factor of 3.5 × 106. By integrating the enrichment and sensing functions of the HP-CMSs in a microfluidic channel, online high-throughput SERS detection of 20 samples within 5 min is achieved in a single channel, and the relative standard deviation of the signals between samples is only 5.1%. The current work develops a convenient preparation method that converts sustainable biomass carbon to 3D hierarchical porous carbon and provides a potential material for sensing, energy, catalysis, and other fields.

Recent advances in photodegradation of antibiotic residues in water.

Antibiotics are widely present in the environment due to their extensive and long-term use in modern medicine. The presence and dispersal of these compounds in the environment lead to the dissemination of antibiotic residues, thereby seriously threatening human and ecosystem health. Thus, the effective management of antibiotic residues in water and the practical applications of the management methods are long-term matters of contention among academics. Particularly, photocatalysis has attracted extensive interest as it enables the treatment of antibiotic residues in an eco-friendly manner. Considerable progress has been achieved in the implementation of photocatalytic treatment of antibiotic residues in the past few years. Therefore, this review provides a comprehensive overview of the recent developments on this important topic. This review primarily focuses on the application of photocatalysis as a promising solution for the efficient decomposition of antibiotic residues in water. Particular emphasis was laid on improvement and modification strategies, such as augmented light harvesting, improved charge separation, and strengthened interface interaction, all of which enable the design of powerful photocatalysts to enhance the photocatalytic removal of antibiotics.

Research progress of metal biomaterials with potential applications as cardiovascular stents and their surface treatment methods to improve biocompatibility.

Facing the growing issue of cardiovascular diseases, metallic materials with higher tensile strength and fatigue resistance play an important role in treating diseases. This review lists the advantages and drawbacks of commonly used medical metallic materials for vascular stents. To avoid post-procedural threats such as thrombosis and in-stent restenosis, surface treatments, and coating methods have been used to further improve the biocompatibility of these materials. Surface treatments including laser, plasma treatment, polishing, oxidization, and fluorination can improve biocompatibility by modifying the surface charges, surface morphology, and surface properties of the material. Coating methods based on polymer coatings, carbon-based coatings, and drug-functional coatings can regulate the surface properties, and also serve as an effective barrier to the interaction of metallic biomaterial surfaces with biomolecules, which can be used to improve corrosion resistance and stability, as well as improve their biocompatibility. Biocompatibility serves as the most fundamental property of cardiovascular stents, and maintaining the excellent and stable biocompatibility of cardiovascular stent surfaces is a current research bottleneck. Few reviews have been published on metallic biomaterials as cardiovascular stents and their surface treatments. For the purpose of advancing research on cardiovascular stents, common metal biomaterials, surface treatment methods, and coating methods to improve biocompatibility and comprehensive properties of the materials are described in this review. Finally, we suggest future directions for stent development, including continuously improving the durability and stability of permanent stents, accelerating the development of biodegradable stents, and strengthening feedback to improve the safety and reliability of cardiovascular stents.

Preparation of novel Au-Nb3O7F nanosheets for the photodegradation of tetracycline hydrochloride.

Water pollution caused by antibiotics is a growing problem and photodegradation by efficient catalysts is an environmentally friendly technology that can effectively degrade organic pollutants in water. Here, a novel method was innovatively used to synthesize niobium oxyfluoride (Nb3O7F) nanosheets decorated with Au nanoparticles, which is the first report for the composites of Au and Nb3O7F. We prepared the Nb3O7F nanosheets via hydrothermal synthesis followed by deposition of Au nanoparticles on their surface using HAuCl4. The prepared samples were characterized by XRD, HRTEM, XPS, and UV-Vis. The diameters of most Au NPs are ranging from 5 to 25 nm with an average size of about 16.9 nm, as well as the Nb3O7F nanosheets in size ranging from 200 nm to 700 nm. The chemical composition of the Au-Nb3O7F showed a Au/Nb atomic ratio of 1/10, as well as a Nb/O/F ratio of 3/7/1. UV-Vis spectrum reveals a largest absorption peak at 520 nm for the Au-Nb3O7F nanosheets. The prepared Au-Nb3O7F nanomaterials were applied to the visible-light photodegradation of tetracycline hydrochloride, with the photocatalytic degradation rate reached more than 50% under the optimal conditions within 1 h. Capture experiments indicated that h+ and •O2 - are the main active substances involved during the course of the photodegradation. Furthermore, the proposed mechanism for the photodegradation of the novel Au-Nb3O7F nanosheets was given.

Determination of multi-residue pesticides in dairy products using single-step emulsification/demulsification clean-up strategy combined with low-pressure gas chromatography-tandem mass spectrometry.

In this study, a simple, sensitive, and rapid method was developed for the simultaneous determination of 99 kinds of pesticides in fatty milk samples. This novel emulsification-demulsification clean-up approach, coupled with an automatic demulsification-dehydration cartridge, allowed rapid single-step clean-up operation and high throughput. It also achieved effective and selective removal of lipids. The analysis was performed using low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS). Based on the optimal conditions, the targeted pesticides showed good linearity in the range of 5-250 µg/kg, with recoveries of 70-120% at spiking levels of 5, 10, and 20 µg/kg in cow milk, goat milk, and almond milk, respectively. The limit of quantification for most pesticides was 5 µg/kg, and the RSDs were lower than 20%. Analysis of real dairy products obtained from local markets revealed a potential risk in plant-derived almond milk, but no significant risks were found for cow and goat milk.

Surfactant-free interfacial growth of graphdiyne hollow microspheres and the mechanistic origin of their SERS activity.

As a two-dimensional carbon allotrope, graphdiyne possesses a direct band gap, excellent charge carrier mobility, and uniformly distributed pores. Here, a surfactant-free growth method is developed to efficiently synthesize graphdiyne hollow microspheres at liquid‒liquid interfaces with a self-supporting structure, which avoids the influence of surfactants on product properties. We demonstrate that pristine graphdiyne hollow microspheres, without any additional functionalization, show a strong surface-enhanced Raman scattering effect with an enhancement factor of 3.7 × 107 and a detection limit of 1 × 10-12 M for rhodamine 6 G, which is approximately 1000 times that of graphene. Experimental measurements and first-principles density functional theory simulations confirm the hypothesis that the surface-enhanced Raman scattering activity can be attributed to an efficiency interfacial charge transfer within the graphdiyne-molecule system.

Durable underwater super-oleophobic/super-hydrophilic conductive polymer membrane for oil-water separation.

Oily sewage has made serious impact on environment and people's life, and its treatment has become a global problem to be urgently solved. Oil-water separation has been considered to be an effective method to treat oily sewage at present. In this work, an underwater super-oleophobic/super-hydrophilic membrane with oil-water separation and self-cleaning properties was fabricated by electrochemical oxidation of sodium lignosulfonate doped polypyrrole. The membrane showed super-hydrophilicity for water-removal in air and super-hydrophilicity for oil-removal underwater in both oxidation and reduction states. The oil-water separation efficiency of the membranes for different organics exceeded 98.44%, no matter in oxidation or reduction state. Moreover, the membrane still exhibited excellent performance in terms of the oil-water separation efficiency and flux after 70 cycles, which were greater than 97.18% and 70.14 L·m-2·h-1, respectively. Simultaneously, through exploration of the mechanism, it was found that the larger anion kept intact in the membrane during the redox process, which made the stability of composition and performance. Thus, the membrane with advantageous properties, including underwater super-oleophobic/super-hydrophilicity, high oil-water separation efficiency, high circulating rate and stability, has significant potential in separation and collection of oily sewage.

A corrosion inhibiting layer to tackle the irreversible lithium loss in lithium metal batteries.

Reactive negative electrodes like lithium (Li) suffer serious chemical and electrochemical corrosion by electrolytes during battery storage and operation, resulting in rapidly deteriorated cyclability and short lifespans of batteries. Li corrosion supposedly relates to the features of solid-electrolyte-interphase (SEI). Herein, we quantitatively monitor the Li corrosion and SEI progression (e.g., dissolution, reformation) in typical electrolytes through devised electrochemical tools and cryo-electron microscopy. The continuous Li corrosion is validated to be positively correlated with SEI dissolution. More importantly, an anti-corrosion and interface-stabilizing artificial passivation layer comprising low-solubility polymer and metal fluoride is designed. Prolonged operations of Li symmetric cells and Li | |LiFePO4 cells with reduced Li corrosion by ~74% are achieved (0.66 versus 2.5 µAh h-1). The success can further be extended to ampere-hour-scale pouch cells. This work uncovers the SEI dissolution and its correlation with Li corrosion, enabling the durable operation of Li metal batteries by reducing the Li loss.

Discrete Element Simulation of Fracture Evolution around a Borehole for Gas Extraction in Coal Seams.

The stability analysis of underground caverns, tunnels, and boreholes is of great significance to underground engineering. In order to study the stress change of the coal around a hole and the evolution law of fractures during the coal seam drilling process, the discrete element simulation of the coal seam drilling process was carried out by using the particle flow code (PFC2D). The results show that during the drilling process, under the influence of confining pressure and drilling disturbance, the coal stress field around the hole and the development of fractures around the hole have the characteristics of zoning and dynamic evolution. In the axial direction of the borehole, it is divided into front and rear areas, and in the vertical axial direction, it is divided into the drilling disturbance zone and the confining pressure main control zone. During the drilling process, the direction of the maximum principal stress in the front zone gradually changes from the vertical hole axis to the direction parallel to the hole axis, and tension fractures are mainly developed along the drilling direction. In the rear zone, the principal stress direction tends to be stable and the principal stress value undergoes dynamic changes, and a large number of vertical hole axis tension fractures are developed. The drilling disturbance zone appears near the hole wall and has an important influence on the stability of the hole wall, while the confining pressure main control zone determines the antireflection effect around the hole and the influence radius of the hole. This work helps the understanding of the damage range and failure characteristics of the surrounding rock during the drilling process and has great significance for the guidance of drilling design.

Analysis Method of the Occurrence Law of Coalbed Gas Based on Gas-Geology Units: A Case Study of the Guhanshan Mine Field, Jiaozuo Coalfield, China.

The correct understanding of the occurrence law of coalbed gas (CBG) is the premise of gas disaster prevention, outburst risk prediction, and gas exploitation. The factors affecting gas occurrence in different gas-geology units are different, so the correct division of gas-geology units is the foundation for studying the occurrence law of CBG. In view of this, this paper defined the division principle of gas-geology units. A gas-geology unit is an area with the same gas-geology characteristics. Based on the division of tectonic units, gas-geology units can be divided by integrating the differences of in situ stress, geological factors, and gas distribution of each tectonic unit. Then, taking the Guhanshan mine field in the Jiaozuo coalfield as an example, the analysis method of the occurrence law of CBG based on gas-geology units was expounded. Taking the EW section, NE section, and their extension lines of the Tuanxiang fault as the boundary, the Guhanshan mine field was divided into four tectonic units, and the factors affecting the gas occurrence of each tectonic unit were analyzed. Finally, according to the difference of the bedrock thickness and the CBG distribution in the four tectonic units, combined with the fracture development degree of the coal seam, surrounding rock, and the development degree of deformed coal, the Guhanshan mine field was divided into three gas-geology units, and their occurrence law of CBG was analyzed.

4-[(E)-(2,3-Dichloro-benzyl-idene)amino]-phenol.

In the title compound, C(13)H(9)Cl(2)NO, the dihedral angle between the benzene rings is 54.22 (10)°. In the crystal, mol-ecules are linked by O-H⋯N inter-molecular hydrogen bonds, forming a zigzag C(7) chain along the a axis.

4-[(E)-(4-Fluoro-benzyl-idene)amino]-phenol.

In the title compound, C(13)H(10)FNO, the dihedral angle between the aromatic rings is 55.60 (8)°. In the crystal, mol-ecules are linked by O-H-N hydrogen bonds, forming zigzag C(7) chains propagating in [101].

Solvent-assisted crystallization of two-dimensional Ruddlesden-Popper perovskite.

Two dimensional (2D) perovskite materials, are more stable than 3D perovskite materials, which could solve the stability issue of perovskite solar cells (PSCs). However, the photovoltaic conversion efficiency (PCE) of PSCs based on 2D perovskite materials was low, due to the high dielectric and quantum confinement of 2D perovskite. In this work, we propose a solvent-assisted method to prepare 2D perovskite films, where the solvent was distributed in a gradient. Therefore, the top-down crystallization process of 2D perovskite can be accurately controlled. The PCE of PSCs fabricated by the solvent-assisted method was enhanced by 48%, compared with the control device. For the packaged devices, the stability test demonstrated that 94% of the initial PCE was still maintained after 1500 hours of storage (25 °C, RH 40%). After carefully analyzing the photophysical process of the carriers in the PSCs based on 2D perovskite, the enhanced carrier transfer mechanism of the solvent-assisted method has been proposed.

Recent progress in metal sulfide-based electron transport layers in perovskite solar cells.

High-quality electron transport layers (ETLs) are essential for stable and efficient perovskite solar cells (PSCs). Metal sulfides (MSs) are considered potential candidates for ETLs due to their high carrier mobility, low cost, and favorable chemical and physical stability. The quality of the MS films plays important role in the photovoltaic performance of PSCs. However, few reports focus on the relative preparation, characteristics, and corresponding mechanisms of MS-based ETLs. In this review, MS-based ETLs are summarized according to their preparation strategies and the mechanism. We hope that this review can help others understand the intrinsic phenomena of MS-based ETLs and motivate further investigations.

Study on the Quantitative Characterization and Seepage Evolution Characteristics of Pores of Loaded Coal Based on NMR.

Quantitative characterization of the pore structure and gas seepage characteristics of loaded coal is of great significance to the study of high-efficiency gas drainage in coal seams. Aiming at the problem of imperfect characterizations of coal seepage characteristics based on nuclear magnetic resonance (NMR), a calculation method for the pore permeability of coal with different pore diameters is proposed. The pore structure and seepage characteristics of coal have been quantitatively studied using a nuclear magnetic resonance (NMR) system. The results show that with increasing external load, the proportion of the pore volume of the coal sample in the range of 0.01-0.52 µm gradually decreases, while that in the range of 5.11-352.97 µm increases. In this process, the porosity increases from 0.9967 to 1.0103%, the connectivity increases from 0.1718 to 0.2391, and the permeability increases from 2.64 × 10-6 to 8.20 × 10-6 µm2. The calculation of the coal sample connectivity and permeability using the improved NMR permeability component proves that 94.37-352.97 µm pores are the main channel of fluid flow. When the axial pressure increases, the coal body permeability in the aperture range of 94.37-352.97 µm rapidly increases. The improved permeability component calculation model can better reflect the variation law of pore permeability of the loaded coal body.

Micro-Nano Fine Characterization of Coal Fracture Evolution During the Triaxial Compression Creep.

The production and evolution of fractures during coal creep will directly affect the occurrence, extraction and flow law of gas in a coal seam. The coal fracture evolution under creep conditions was studied by qualitative analysis and quantitative characterization. At a room temperature of 24 °C, triaxial compression creep tests of coal samples from the Zhaogu No. 2 coal mine in Jiaozuo were carried out under different loading conditions (0 MPa, 6 MPa, 9 MPa and 12 MPa), and low field nuclear magnetic resonance technique tests and industrial CT scanning experiments were performed. The obtained CT images were analyzed with the MATLAB software for equalization and binary image processing. The development and distribution of fractures in coal samples under different loading conditions were studied. The results show that the internal fractures are unevenly distributed and controlled by the main fracture, and the expansion direction of fractures is parallel to the direction of the maximum effective compressive stress. The number of fractures shows an increasing trend with the increase of axial stress, and the pace of growth of new fractures accelerates. The primary fractures in the coal body expand and generate new fractures, which improves the connectivity of the fractures in the coal body. The research results can provide a basis for studying the gas flow rule around the borehole and determining the influence range of the borehole.