Excellent Water Stability Research Articles

Reconstructed wood with high water stability from bark cellulose and corncob lignin

Natural wood has been highly valued for thousands of years due to its excellent strength, low density, and ease of processing. However, its poor water stability, which leads to swelling and deformation, limits its competitiveness. In response, we designed a reconstructed wood through a process involving pretreatment, TEMPO oxidation, lignin self-assembly, lignin melting, and densification. In this material, cellulose serves as the skeleton, while lignin with a phenylpropyl structure acts as both a filler and binder. The resulting wood exhibits outstanding water stability, with no changes after 60 days of water immersion and a water absorption rate as low as 8.32 %. This stability is achieved through the densification of lignin, which is enhanced by lignin melting and pressure during self-assembly. The reconstructed wood not only offers excellent water stability but also boasts superior UV resistance and thermal stability. Additionally, it can be hot-pressed into straws within a mold, providing better water stability and tensile strength compared to paper straws. This reconstructed wood, made from natural wood and corncob, is biodegradable and environmentally friendly, offering a new approach to wood water stability strategies.

Dual metal centers within a water-stable Co/Ni bimetallic metal-triazolate framework contribute to durable photocatalysis for water treatment.

Bimetallic metal-organic frameworks (MOFs) have been studied extensively in various fields, including photocatalytic and electrocatalytic applications. The enhanced catalytic activity is typically attributed to the synergistic effect of the two metals, often without further explanation. Here, we demonstrate a CoNi-bimetallic triazolate MOF with fixed metal occupancy within the MOF's secondary building unit. Due to the difference in electronegativity and so on, the charge redistribution between the two metal centers could be responsible for the enhanced photocatalytic activity. In addition, the metal(II)-triazolate MOFs we synthesized exhibit unique metal-N coordination and a strong bond between the metal center and triazole ring. Therefore, their crystal structure and high porosity are highly retained even after exposure to humid environments for several months or stirring in water for several days. Overall, the CoNi-bimetallic triazolate MOF combines the excellent water stability and high surface area of its two monometallic counterparts. It can be further tailored to yield the highest colloidal stability during photocatalytic water treatment. As a result, the dual metal centers within the bimetallic MOF, combined with boosted colloidal stability, demonstrate the highest reactive oxygen species generation and promising antibacterial performance compared to their Ni- or Co-based counterparts. These findings shed light on the future design of robust MOF-based photocatalysts, particularly bimetallic ones.

Structural reconstruction synthesis of highly luminous water-stable CsPbBr3@CsPb2Br5@DSPE core-shell perovskite nanocrystals for bioimaging, pattering, and LEDs

Lead halide perovskite (LHP) nanocrystals (NCs) suffer from poor stability against environmental factors (heat, moisture, oxygen, etc.), which seriously hinders their practical application. Constructing a core-shell structure could be an effective approach to improve the stability and optical properties of the LHP NCs. Herein, a novel strategy of water-triggered phase transformation and phospholipid (DSPE) micelle encapsulation is proposed, generating highly luminescent water-dispersed CsPbBr3@CsPb2Br5@DSPE core-shell-shell nanocrystals. The epitaxial growth of the CsPb2Br5 shell is induced by the in-situ reconstruction of the CsPbBr3 surface by water erosion, and the lattice mismatch with the CsPbBr3 core is small (3.8%). The further amphipathic phospholipid encapsulation guarantees their excellent water dispersity and stability. Revealed by the femtosecond transient absorption spectroscopy, the dense CsPb2Br5@DSPE shell effectively passivates the surface of the CsPbBr3 core, thus improving its stability and luminescence performance. The resulting CsPbBr3@CsPb2Br5@DSPE nanoparticles exhibit excellent performance as fluorescent probes for bioimaging, aqueous inks for high-resolution pattering, and light conversion layers for LEDs, demonstrating their promising potential in multiple applications.

Stabilized/solidified chlorine saline soils with ground granulated blast furnace slag and calcium carbide residue

To optimize the use of chlorine saline soils commonly found in many coastal areas, ground granulated blast furnace slag (GGBS) and calcium carbide residue (CCR) were used in this study to stabilize/solidify these soils. This study aims at evaluating the suitability of GGBS-CCR as industrial by-products in improving the mechanical behaviors of chlorine saline soil in comparison with the use of Portland cement (PC) as a traditional binder. The optimal proportion of the binder was determined by the unconfined compressive strength, conductivity, and leaching characteristics. Moreover, the water stability coefficients, collapse coefficients and microscopic characteristics of the solidified soil were evaluated. The results reveal that when the ratio of GGBS to CCR in the binder is 4:1, the 28-day unconfined compressive strength reaches 4.53 MPa, and the leaching of chloride ions is reduced by 94.1 %. The excellent water stability and reduced collapsibility further indicate that GGBS-CCR is a preferable binder for solidifying saline soil compared to PC. Furthermore, microscopic analysis revealed that chloride ions in the saline soil were involved in the hydration reaction to form Friedel's salt.

Water-Stable and Sensitive X-ray Detectors by Supramolecular Interaction-Enhanced Polyoxometalates.

Polyoxometalates (POMs) have shown prominence in the field of semiconductive materials in recent years. However, electronic applications based on these emerging materials are still in their early stages. Here, a sensitive and water-stable F-PEA-ZnW12 X-ray detector has been designed and constructed for hard X-ray detection and imaging. Supramolecular interactions of H···O bonding, electrostatic, and anion-π interactions not only enable FPEA-ZnW12 excellent water stability but also shorten the distance between [ZnW12O40]6- clusters, which reduces ion migration and dark current simultaneously, resulting in the conductivity of 3.2 × 10-11 S cm-1. Furthermore, the heteropoly blue formed on the surface of the O-FPEA-ZnW12 wafer device promotes the effective separation and extraction of X-ray-induced carriers, enhancing the sensitivity for X-ray detection. The R/O-FEPA-ZnW12 wafer device yields a high sensitivity of 3.1 × 104 μC Gyair-1 cm-2 with the lowest detectable dose rate of 69 nGyair s-1 under 120 kV hard X-ray irradiation. In addition, the O-FPEA-ZnW12 wafer detector exhibits the potential for X-ray detection in water with a sensitivity of 1.0 × 104 μC Gyair-1 cm-2. Moreover, the fabricated POM X-ray detector shows excellent X-ray imaging capability and long-term operational stability without any attenuation of 1 year exposure to air without any encapsulation.

CsPbBr3 perovskite quantum dots by mesoporous silica encapsulated for enhancing water and thermal stability via high temperature solid state method

All inorganic perovskite quantum dots (PQDs) have great application prospects in the lighting and display fields due to their excellent photoelectric properties. However, their instabilities in water and high temperature lead to photoluminescence (PL) quenching, and colloidal synthesis methods usually use a mass of organic solvents, limiting their practical application. Herein, we successfully synthesized mesoporous silica (m-SiO2) and employed a confinement effect to successfully synthesize CsPbBr3@m-SiO2 powders using a simple high-temperature solid-phase synthesis method in an air atmosphere. When the m-SiO2 content is 0.2 g, optimal green luminous intensity is achieved with a peak wavelength of 522 nm and a full width at half maximum (FWHM) of 23 nm. CsPbBr3@m-SiO2 powders have excellent thermal stability, the PL spectral shapes do not change and the PL intensity can maintain 88.1 % of the original level after 10 heating cycles (200 °C). In addition, CsPbBr3@m-SiO2 powders exhibit excellent water stability, which can still be well dispersed after 30 days exposure to water, and the PL strength remain basically unchanged. This study presents a novel approach for the advancement of stable perovskite luminescent materials.

Nanoarchitectonics of Methyl and Aldehyde Group-Decorated SOD-Type Metal-Azolate Framework for SF6 Capture and Recovery.

Sulfur hexafluoride (SF6) is widely used as an insulating gas, being an etchant and contrast agent in the electrical, semiconductor, and medical industries. However, due to its long lifetime and high global warming potential in the atmosphere, SF6 must be carefully handled to prevent leakage during production and usage. Herein, we report a sod-net metal-azolate framework (MAF) named MAF-stu-111, which decorates methyl and aldehyde groups in the porous windows, showing high adsorption affinity for SF6 at low pressure. Stability tests, gas adsorption, and breakthrough experiments demonstrated that MAF-stu-111 possesses excellent water and chemical stability, fully reversible SF6 uptake, high SF6/N2 separation selectivity (10:90, 285.2), good reusability, and high SF6 recovery purity (99.03%). Theoretical calculations revealed that hydrogen atoms of methyl and aldehyde groups can form multiple hydrogen bonds with SF6 molecules, which ensure that SF6 molecules are firmly held within the MAF-stu-111 framework, playing a key role in the selective separation of SF6/N2.

A terbium coordination polymer based on mixed rigid and flexible organic ligands as a luminescent sensor for the convenient visual detection of ascorbic acid

Ascorbic acid (AA) is an essential antioxidant in the human body, whose detection is of significance in many fields. In this study, a two-dimensional terbium coordination polymer [Tb (dlba) (phen)]n (Tb-CP) based on a rigid 1,10-phenanthroline (phen) and a flexible 2-(3,5-dicarboxybenzyloxy) benzoic acid unit (H3dlba) was prepared under the hydrothermal conditions and characterized by Powder X-ray diffraction, elemental analysis, thermogravimetric analysis, infrared spectroscopy and single crystal X-ray diffraction. The Tb-CP synthesized via the mixed ligand strategy exhibits excellent water stability and acid-alkali resistance. As a luminescent sensor, the Tb-CP showed bright green luminescence characteristics of Tb3+, which was quenched after the addition of AA, with a quenching efficiency of 95.3 %. Additionally, the sensor shows high sensitivity and a rapid response time of 30 s. The detection limit is as low as 55.4 nM. In the actual sample test, the recovery rate of AA was 95–105 % (RSD< 1 %), indicating that the sensor has the potential for practical application. Furthermore, an integrated system based on Tb-CP and a smartphone can be employed for the visual detection of AA.

Development of laboratory-cooked, water-resistant, and high-performance Cu-MOF: an economic analysis of Cu-MOF for PFOS pollution management and remediation

Water pollution is a pressing global concern, with per- and polyfluoroalkyl substances (PFAS) being considered as “forever contaminants.” Among them, perfluorooctanesulfonic acid (PFOS) has received significant attention for its adverse effects on human health and aquatic ecosystems. This study aimed to design an innovative adsorbent for effective PFOS removal with exceptional water stability, improving its cost-performance trade-off. The current work simultaneously improved the stability of water of Cu-based metal–organic framework (CMOF) and increased its PFOS removal capacity by modifying it with amine-functionalized SiO2 nanoparticles (AF-CMOF). AF-CMOF presented a lower specific surface area of 999 m2 g−1 compared to CMOF with a surface area of 1098 m2 g−1. AF-CMOF showed remarkable PFOS uptake performance of 670 mg/g compared to the performance of the Cu-based MOF which exhibited a PFOS uptake capacity of only 22 mg/g. The most suitable pH for PFOS removal using both adsorbents was determined to be 3. In addition, AF-CMOF demonstrated excellent water stability, retaining its structural integrity even after seven days of water contact, while CMOF structure collapsed rapidly after four days of water exposure. Moreover, the study identified the significant pH influence on the PFOS uptake process, with electrostatic interactions between protonated amine functionalities and PFOS molecules identified as the dominant mechanism. The study’s findings present the potential of synthesized adsorbent as a superior candidate for PFOS uptake and contribute to the development of effective water treatment technologies.

Cell-Based Meat Scaffold Based on a 3D-Printed Starch-Based Gel.

Starch was mixed with a gel to produce a starch-based gel ink, which exhibited favorable printing characteristics. Through the optimization of infill density, 3D-printed scaffolds with 50% infill density and a highly ordered microstructure were successfully fabricated. The addition of calcium carbonate nanoparticles-glucono delta lactone (CaCO3 NPs-GDL) had notable effects on the swelling degree, in vitro digestion, water stability, and pore distribution of the scaffolds. When the amount of CaCO3 NPs in the starch-based gel was 0.075 g, the resulting 3D-printed gel scaffold with a 50% infill density proved to be the most suitable for cultivating cell-based meat. It featured pore sizes ranging from 80 to 120 μm and a compression modulus of 246.76 Pa. After 7 days of proliferation, the C2C12 mouse skeletal myoblasts exhibited an approximately 2.81-fold increase in cell numbers. The fusion index and maturation index of C2C12 cells on the scaffolds were 57.00 ± 0.45% and 34.56 ± 0.56%, respectively. The starch-based gel scaffolds demonstrated excellent water stability and in vitro degradability. Moreover, C2C12 cells exhibited successful proliferation and differentiation on the starch-based scaffolds, ultimately leading to the production of cell-based meat. This study developed a starch-based composite gel scaffold for the manufacture of cell-based meat.

Water-Stable Ln-MOF as a multi-emitting luminescent sensor for the detection of metal ions and pharmaceuticals

The development of innovative multi-emission sensors for the rapid and accurate detection of contaminants is both vital and challenging. In this study, utilizing two rigid ligands (H3ICA and H4BTEC), a series of water-stable bimetallic organic frameworks (EuTb-MOFs) were synthesized. Luminescent investigations have revealed that EuTb-MOF-1 exhibits prominent multiple emission peaks, attributed to the distinctive fluorescence characteristics of Eu(III) and Tb(III) ions. Therefore, EuTb-MOF-1 efficiently recognized various metal ions and pharmaceutical compounds through 2D decoded maps. Fe3+ and Pb2+ exhibited significant quenching effects on the luminescence of EuTb-MOF-1, which were attributed to the internal filtering effect and the interaction between Lewis basic sites within EuTb-MOF-1 and Pb2+ ions, respectively. Furthermore, EuTb-MOF-1 demonstrated high sensitivity to sulfonamide antibiotics, with detection limits of 0.037 μM for SMZ and 0.041 μM for SDZ, respectively. In addition, EuTb-MOF-1 was immobilized to prepare MOF-based test strips, enabling direct visual detection of sulfonamides as a portable sensor. With excellent water stability, multi-responsive recognition capabilities, and high sensitivity to specific analytes, EuTb-MOF-1 is a promising candidate for environmental contaminant detection in aquatic systems.

Construction of chiral crown ethers in robust covalent organic frameworks for electrochromatographic enantioseparation

ABSTRACT Capillary electrochromatography (CEC) is a rapidly emerging separation technique that merges the high separation efficiency of capillary electrophoresis with the exceptional selectivity of liquid chromatography. However, it remains a synthetic challenge to design functional chiral stationary phases (CSPs) with high chemical stability against acid and base in CEC enantioseparation. Here we demonstrate that incorporating chiral crown ethers into stable covalent organic frameworks (COFs) enables efficient and stable separations of racemates by CEC. This facilitates the crafting of two three-dimensional (3D) chiral COFs by polycondensation of a chiral 1,1'-binaphyl-20-crown-6-derived dialdehyde and tetraamines with diisopropyl substituents. Both feature an 11-fold interpenetrated diamond framework, characterized by tubular open channels decorated with chiral crown ethers serving as enantioselective recognition and binding sites. These frameworks demonstrate excellent stability in water, acid and base, thanks to the presence of bulky isopropyl groups that shield the dynamic imine linkages. Moreover, the precisely defined COF channels enhanced the accessibility of the enclosed crown ethers to the analytes while providing strong protection against harsh environments, rendering them suitable for CSPs in CEC separations. They can effectively separate some important enantiomers, including ketones, epoxides and alkaline substances, when utilized as coatings on chiral columns, particularly facilitating the chiral separation of drugs. This study advances the application of COFs in electrochromatographic separations, expanding the scope of porous materials design and engineering to create COFs with targeted enantioselective properties.

Ultrahigh proton conductivity of four ionic hydrogen-bonded organic frameworks based on functionalized terephthalates

Recently, the utilization of hydrogen-bonded organic frameworks (HOFs) with high crystallinity and inherent well-defined H-bonding networks in the field of proton conduction has received increasing attention, but obtaining HOFs with excellent water stability and prominent proton conductivity (σ) remains challenging. Herein, by employing functionalized terephthalic acids, 2,5-dihydroxyterephthalic acid, 2-hydroxyterephthalic acid, 2-nitro terephthalic acid, and terephthalic acid, respectively, four highly water-stable ionic HOFs (iHOFs), [(C8H5O6)(Me2NH2)]∙2H2O (iHOF 1), [(C8H5O5)(Me2NH2)] (iHOF 2), [(C8H4NO6)(Me2NH2)] (iHOF 3) and [(C8H5O4)(Me2NH2)] (iHOF 4) were efficiently prepared by a straightforward synthesis approach in DMF and H2O solutions. The alternating-current (AC) impedance testing in humid conditions revealed that all four iHOFs were temperature- and humidity-dependent σ, with the greatest value reaching 10-2 S·cm−1. As expected, the high density of free carboxylic acid groups, crystallization water, and protonated [Me2NH2]+ units offer adequate protons and hydrophilic environments for effective proton transport. Furthermore, the σ values of these iHOFs with different functional groups were compared. It was discovered that it dropped in the following order under 100 °C and 98 % relative humidity (RH): σ iHOF 1 (1.72 × 10−2 S·cm−1) > σ iHOF 2 (4.03 × 10−3 S·cm−1) > σ iHOF 3 (1.46 × 10−3 S·cm−1) > σ iHOF 4 (4.86 × 10−4 S·cm−1). Finally, we investigated the causes of the above differences and the proton transport mechanism inside the framework using crystal structure data, water contact angle tests, and activation energy values. This study provides new motivation to develop highly proton-conductive materials.

Photocatalytic degradation of tetracycline hydrochloride and oxytetracycline using novel zinc-based coordination polymers constructed with mixed linkers

In the present work, a new zinc-based coordination polymer was successfully synthesized by mixed-ligand method with the molecular formula of {[Zn(ipa)(Hpap)]·2H2O}n, (abbreviated as Zn-CP), where ipa = isophthalic acid, Hpap = 4-(1H-pyrazol-4-yl)pyridine. Furthermore, reasonable characterization of Zn-CP was carried out by single crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and other spectra. During the characterization process, it was found that Zn-CP can have excellent acid-base stability, water stability and thermal stability. In addition, the complex was able to effectively degrade tetracycline hydrochloride (TCH) and oxytetracycline (OTC) within 60 min under visible light irradiation (with degradation efficiencies of 80.2 % and 83.5 %, respectively), and the cycling experiments showed that Zn-CP could still effectively degrade TCH and OTC after three cycles. Finally, in order to propose a rational photocatalytic degradation mechanism, free radical trapping experiments and energy band structure analysis were also carried out.

A Dual-Function AgNW@COF SERS Membrane for Organic Pollutant Removal and Simultaneous Concentration Determination.

Surface enhanced Raman spectroscopy (SERS) is a highly sensitive analytical detection method commonly employed in biochemical and environmental analysis. Nevertheless, the rapid movement of analytes and interfering components in flow systems can impact the real-time, online detection capability of Raman spectroscopy. To address this issue, we developed an innovative approach utilizing covalent organic framework (COF), a robust porous material with excellent water stability, to coat the surface of Ag nanowire (AgNW) for synthesizing AgNW@COF hybrid. The regular pores of the COF serve to effectively eliminate large interfering molecules while facilitating the efficient transport of specific analytes to SERS hot spots. Additionally, the fluid flow-induced scouring effect aids in excluding interfering molecules from the surface of AgNW. By incorporating AgNW@COF into a bifunctional filter membrane with simultaneous filtration and sensing capabilities, we had achieved efficient purification of organic pollutants as well as real-time identification of pollutant species and concentration.

Rapid eco-friendly selective dye removal using modified chitosan-based sponges: Synthesis, characterization, and application

The ongoing challenge of water scarcity persists alongside a concerning rise in water pollution driven by population expansion and industrial development. As a result, urgent measures are imperative to address the pressing need for a clean and sustainable water supply. In this study, a sustainable and green approach was utilized to prepare four chitosan-based sponges from a chemically modified chitosan with different alkyl chains in aqueous medium and at room temperature. The resulting sponges displayed excellent stability in water with outstanding dye removal efficiency. The adsorption capacity was associated with the alkyl chain length incorporated to the polymer backbone. All sponges displayed a high adsorption capacity of methyl orange (MO) ranges between 238 and 380 mg g−1, while a low capacity were obtained for methylene blue (MB) and Rhodamine B (RB). Competitive adsorption experiments were conducted on binary and ternary mixtures to assess the selective removal of MO from a mixture of dyes in which the separation factor was found to be ranging between 1.6 and 32. The adsorption kinetics isotherms of all sponges followed the pseudo-second-order, and the Langmuir model was found to be more suitable than the Freundlich for the adsorption of MO on the sponges. The chitosan-based sponges showed stable performance, robustness and reusability over 5 adsorption-desorption cycles, indicating their great potential for water treatment applications.

Preparation of cylindrical Chitosan/β-Cyclodextrin/MIL-68(Al) foam column for solid-phase extraction of sulfonamides in water, urine, and milk

This study describes the preparation of a cylindrical polymer foam column termed Chitosan/β-Cyclodextrin/MIL-68(Al) (CS/β-CD/MIL-68(Al)). An ice template-freeze drying technique was employed to prepare the CS/β-CD/MIL-68(Al) foam column by embedding MIL-68(Al) in a polymer matrix comprising cross-linked chitosan (CS) and β-cyclodextrin (β-CD). The cylindrical CS/β-CD/MIL-68(Al) foam was subsequently inserted into a syringe to develop a solid phase extraction (SPE) device. Without the requirement for an external force, the sample solution passed easily through the SPE column thanks to the porous structure of the CS/β-CD/MIL-68(Al) foam column. Moreover, the CS/β-CD/MIL-68(Al) foam column was thought to be a superior absorbent for SPE since it included the adsorptive benefits of CS, β-CD, and MIL-68(Al). The SPE was utilized in conjunction with high-performance liquid chromatography to analyze six sulfonamides found in milk, urine, and water. With matrix effects ranging from 80.49 % to 104.9 % with RSD values of 0.4–14.0 %, the method showed high recoveries ranging from 80.6 to 107.4 % for water samples, 93.4–105.2 % for urine, and 87.4–100.9 % for milk. It also demonstrated good linearity in the range of 10–258 ng·mL-1 with the limits of detection ranging from 1.88 to 2.58 ng·mL-1. The cylindrical CS/β-CD/MIL-68(Al) foam column prepared in this work offered several advantages, including its simple fabrication, excellent water stability, absence of pollutants, biodegradability, and reusability. It is particularly well-suited for SPE. Furthermore, the developed SPE method, employing CS/β-CD/MIL-68(Al) foam column, is straightforward and precise, and its benefits, including affordability, ease of preparation, lack of specialized equipment, and solvent economy, underline its broad applicability for the pretreatment of aqueous samples.

An Ice‐Dissolving‐Crosslinking Method for Efficient and Large‐Scale Preparation of Polyelectrolyte Monoliths with Ultra‐Stability in Aqueous Environments

AbstractIce‐templating is a versatile method for constructing macro‐porous hydrophilic polymer materials. However, the ice‐templating method is generally limited by high energy cost and low efficiency for large‐scale fabrication. Further, due to its hydrophilic nature, the constructed materials are vulnerable to water swelling and have poor structural stability. Here, an Ice‐Dissolving‐Crosslinking (IDCr) method is developed for efficient and large‐scale preparation of polyelectrolyte monoliths with ultra‐stability in aqueous environment. Specifically, Ice‐Dissolving in water‐miscible organic solvent is responsible for pore creation, while subsequent Crosslinking ensures pore structures stabilization. The macro‐porous architecture of materials, taking sodium carboxymethyl cellulose (CMC) as a polyelectrolyte example and trimesoyl chloride (TMC) as the crosslinker, CMC‐TMCIDCr is made much stabler as compared with the case of conventional Lyophilization‐Crosslinking technique (CMC‐TMCLC). The IDCr method is applicable to various hydrophilic polyelectrolytes and hybrids for long‐time use in water and brines, as exemplified by CMC‐TMC‐carbon nanotubes monolith, which exhibits high performance in solar thermal desalination process. This novel approach opens up new opportunities for the construction of porous monoliths with efficient preparation and excellent water stability.

Magnetic hybrid micelles with controllable structures via interfacial instability-induced confined Co-assembly

Co-assembly of amphiphilic block copolymers (BCPs) and nanoparticles (NPs) is an encouraging route to produce shape-tunable functional hybrid micelles, which can integrate the excellent water stability of BCPs and the versatile functionalities of NPs. In this paper, we present an facile method to prepare magnetic hybrid micelles through confined co-assembly of polystyrene grafted Fe3O4@PS NPs and PS-b-poly(ethylene oxide) (PS-b-PEO) induced by interfacial instability of emulsion droplets. The morphology of hybrid micelles can be regulated by varying the surfactant concentration, weight fraction of Fe3O4 NPs, and block ratio of PS-b-PEO. The distribution of NPs inside the micelles is determined by the ratio (d/L) of the NP diameter (d) to the thickness of PS domain of the micelles (L). When 0.49 ≤ d/L < 0.76, the NPs locate within the cylindrical micelles. When d/L ≥ 0.76, the NPs selectively locate in the spherical micelles. More interestingly, the size-selective loading of NPs in the micelles can be achieved, even mixture of NPs different in size is applied. Moreover, these magnetic hybrid micelles show good biocompatibility and morphology-dependent magnetic resonance responsiveness, which may find potential applications in magnetic resonance imaging.

Synthesis of High-Quality Bulk Single-Crystal Black Phosphorus by the Circulating Vapor Growth Approach.

Black phosphorus (BP), a promising two-dimensional (2D) layered semiconductor material, has gained enormous attention due to its impressive properties over the past several years. Although plenty of methods have been developed to synthesize high-quality BP, most of the currently available BP materials still suffer from unsatisfactory crystallization, purity, and stability in air, hindering their practical application. A facile approach to synthesizing ultrahigh-quality single-crystal BP is of significance to shed light on the nature of 2D semiconductor materials and their massive application. In this work, we present the facile and efficient circulating vapor growth approach to growing bulk single-crystal BP. The as-grown BP material features high crystallinity and ultrahigh purity (higher than 99.999 at %), exceeding those of all the previously reported and some commercially available BP crystals. It also maintains excellent stability in air and water after 15 consecutive days of test. Moreover, the as-synthesized BP material features good thermal stability, oxidation resistance, and excellent electrical properties, as well. This study provides a new approach for the fabrication of ultrahigh-quality BP material and thus promotes its application.