Effect of Carboxyl Group Position on Assembly Behavior and Structure of Hydrocarbon Oil-Carboxylic Acid Compound Collector on Low-Rank Coal Surface: Sum-Frequency Vibration Spectroscopy and Coarse-Grained Molecular Dynamics Simulation Study.

In this work, the assembly behavior and structure of a compound collector with different carboxyl group positions at the low-rank coal (LRC)-water interface were investigated through coarse-grained molecular dynamics simulation (CGMD) combined with sum-frequency vibration spectroscopy (SFG). The choice of compound collector was dodecane +decanoic acid (D-DA) and dodecane +2-butyl octanoic acid (D-BA). CGMD results showed that the carboxyl group at the carbon chain's middle can better control the assembly process between carboxylic acid and D molecules. SFG research found that the carboxyl group at the carbon chain's termination had a greater impact on the displacement of the methyl/methylene symmetric stretching vibration peak, while the carboxyl group at the carbon chain's middle had a greater impact on the displacement of the methyl/methylene asymmetric stretching vibration peak. The spatial angle calculation results revealed that the methyl group's orientation angle in the D-BA molecule was smaller and the carboxyl group's orientation angle in the BA molecule was bigger, indicating that D-BA spread more flatly on the LRC surface than D-DA. This meant that the assembled structure had a larger effective adsorption area on the LRC surface. The flotation studies also verified that the assembly behavior and structure of D-BA with the carboxyl group at the carbon chain's middle at the LRC-water interface were more conducive to the improvement of flotation efficiency. The study of interface assembly behavior and structure by CGMD combined with SFG is crucial for the creation of effective compound collectors.

Structured Emulgels by Interfacial Assembly of Terpenes and Nanochitin.

Interfacial assemblies formed by colloidal complexation are effective in multiphase stabilization, as shown in structured liquids and Pickering emulgels. Herein, we demonstrate a type of biobased colloidal system that spontaneously stabilizes an organic phase in a continuous hydrogel phase. Specifically, a triterpene extracted from bark (betulin, BE) is added to an organic phase containing a coniferous resin (rosin acid, a diterpene). BE is shown to take part in strong noncovalent interactions with the nanochitin dispersed in the aqueous (hydrogel) phase, leading to a complex of high interfacial activity. The viscoelastic response of the system is rationalized by the presence of a superstable structured dual network. When used as a templating material, the emulgel develops into structured liquids and cryogels. The herein introduced all-biobased type of nanoparticle surfactant system forms a gel ("emulsion-filled" with "aggregated droplets") that features the functional benefits of both betulin and nanochitin.

Small molecules interfacial assembly regulate the crystallization transition process for nobiletin stabilization.

Many bioactive nutraceuticals naturally occurring in food materials possess beneficial biological activities, while their use as functional supplements is subjected to hydrophobicity and crystallinity. Currently, inhibiting crystallization for such nutrients is of immense scientific interest. Here, we exploited diverse structural polyphenols as potential inhibitors for restraining Nobiletin crystallization. Specifically, the crystallization transition process could be influenced by the polyphenol gallol density, Nobiletin supersaturation (1, 1.5, 2, 2.5 mM), temperature (4, 10, 15, 25 and 37 ℃), and pH (3.5, 4, 4.5, 5), important factors for regulating the binding attachment and interactions. The optimized samples could be guided by NT100 lied in 4 ℃ at pH 4. Besides, the main assembly driving force was hydrogen-bonding cooperated with π-π stacking and electrostatic interaction, leading to a Nobiletin/TA combination ratio of âˆ¼ 3:1. Our findings proposed an innovative synergistic strategy for inhibiting crystallization and broaden potential applications of polyphenol-based materials in advanced biological fields.

Micellar Nanoreactors Enabled Site-Selective Decoration of Pt Nanoparticles Functionalized Mesoporous SiO2 /WO3-x Composites for Improved CO Sensing.

Site-selective and partial decoration of supported metal nanoparticles (NPs) with transition metal oxides (e.g., FeOx ) can remarkably improve its catalytic performance and maintain the functions of the carrier. However, it is challenging to selectively deposit transition metal oxides on the metal NPs embedded in the mesopores of supporting matrix through conventional deposition method. Herein, a restricted in situ site-selective modification strategy utilizing poly(ethylene oxide)-block-polystyrene (PEO-b-PS) micellar nanoreactors is proposed to overcome such an obstacle. The PEO shell of PEO-b-PS micelles interacts with the hydrolyzed tungsten salts and silica precursors, while the hydrophobic organoplatinum complex and ferrocene are confined in the hydrophobic PS core. The thermal treatment leads to mesoporous SiO2 /WO3-x framework, and meanwhile FeOx nanolayers are in situ partially deposited on the supported Pt NPs due to the strong metal-support interaction between FeOx and Pt. The selective modification of Pt NPs with FeOx makes the Pt NPs present an electron-deficient state, which promotes the mobility of CO and activates the oxidation of CO. Therefore, mesoporous SiO2 /WO3-x -FeOx /Pt based gas sensors show a high sensitivity (31 ± 2 in 50 ppm of CO), excellent selectivity, and fast response time (3.6 s to 25 ppm) to CO gas at low operating temperature (66 °C, 74% relative humidity).

Secondary bond interface assembly of polyethyleneimine on zein microparticles for rapid adsorption of Reactive Black 5.

Textile dye wastewater has the characteristics of high concentration, complex composition and changeable color degree and pH, which is difficult to be effectively and completely treated, and easy to cause environmental pollution. Here, a strategy of secondary bond interface assembly of polyethyleneimine on zein microparticles (PEI) (PEI@zein) was constructed to achieve rapid and efficient removal of Reactive Black 5 (RB5), which is one of the most widely used reactive dyes in the textile industry. Structural analysis indicated that the as-prepared PEI layer immobilized on zein microparticles was constructed based on the interface assembly dominated by hydrophobic interactions and electrostatic attraction between PEI molecules and zein chains. The novel interface showed excellent absorption performance for RB5 with an absorption capacity of 631.0 mg·g-1, rapid adsorption in 2 min, wide pH range of 4-10. Mechanism analysis suggested the effective adsorption of RB5 by PEI@zein microparticles was mainly attributed to secondary bond interface such as electrostatic interaction and hydrogen bond between RB5 and PEI immobilized on the surface of zein microparticles. Moreover, due to the presence of secondary bond interface, RB5 adsorbed on microparticles can be easily desorbed by using 0.01 M NaOH. Therefore, the strategy of secondary bond interface assembly with polyethyleneimine on zein microparticles has high potential for practical application in the treatment of dye-containing wastewater.

Interface Microstructure and Properties of Vacuum-Hot-Rolled 55#/316L Clad Rebars.

The existing process for the preparation of cladded rebars is too complicated for large-scale industrial production. Therefore, this paper proposes a 55#/316L rebar preparation method based on vacuum hot rolling. The microstructure and mechanical properties of the composite interface of the rebar, along with the connecting technique, were studied using transmission electron microscopy, X-ray diffraction, and Vickers hardness testing. The obtained results showed that the minimum thickness of the 55#/316L rebar cladding was 0.25 mm, which was twice that of the M 329M/M 329-11 design standard used in the United States of America. Due to the diffusion of carbon, large numbers of second-phase particles were precipitated on the stainless-steel side, which resulted in intergranular chromium depletion. After multi-pass hot rolling, the minimum bonding strength of the composite interface reached 316.58 MPa, which was considerably higher than the specified value of 210 MPa. In addition, we designed three different types of rebar connection joints: sleeve, groove-welded, and bar-welded. According to the tensile test, the bar-welded joint had higher yield strength (385 MPa) and tensile strength (665 MPa) than the base rebar (376.6 MPa and 655 MPa), as well as a very high corrosion resistance.

K-Functionalized Carbon Quantum Dots-Induced Interface Assembly of Carbon Nanocages for Ultrastable Potassium Storage Performance.

Carbon nanocages (CNCs), with unique merits of morphology and structure, have attracted increasing attention for energy storage and conversion. However, the synthesis of CNCs reported so far suffers from relatively harsh conditions and expensive raw materials. Herein, porous CNCs are intelligently designed using low-cost glucose as the carbon precursor via a facile K-functionalized carbon quantum dots (K-CQDs)-induced assembly route under hydrothermal process. The resulting CNCs have a unique cage-like structure, large surface area, and rich carboxyl groups. With these elegant structural merits, the as-made CNCs anode shows a high reversible capacity of 270 mAh g-1 at 100 mA g-1 after 200 cycles and a long-term cycling stability of 206 mAh g-1 at 2000 mA g-1 after 4000 cycles. An intercalation reaction mechanism with the K+ intercalation compound is further identified through an in-situ Raman technique. Density functional theory simulations reveal that abundant carboxyl groups inherited from K-CQDs can significantly promote the potassium storage capacities of the CNCs electrode.

Interface assembly of specific recognition gripper wrapping on activated collagen fiber for synergistic capture effect of iodine.

Efficient capture of radioactive iodine (129I, 131I) is of great significance in spent fuel treatment. In this paper, a new adsorbent named Catechin@ACF was successfully prepared through interface assembly of specific recognition gripper with plant polyphenols (catechin) on activated collagen fiber (ACF), and the catechin membrane with specific grip on iodine was successfully constructed on the surface of ACF. The results showed that the adsorbent assembled catechin membrane was rich in aromatic rings, hydroxyl groups and imine adsorption sites, and possessed specific recognition and capture characteristics of iodine. Moreover, the as-prepared Catechin@ACF showed excellent capture capacity for iodine vapor and iodine in organic solution with the maximum capture capacity of 2122.68 mg/g and 258.29 mg/g, respectively. In iodine-cyclohexane solution, the adsorption process was in according with the Pseudo first order kinetic and Langmuir isothermal model. In addition, the specific recognition and capture mechanism analysis indicated that the aromatic rings, phenolic hydroxyl groups and imine groups in the catechin membrane were the specific and effective grippers for iodine, and finally iodine formed a stable conjugated system with the adsorbent in the form of I- and I3-. Therefore, the as-prepared specific iodine capturer Catechin@ACF was expected to play a vital role in the capture of radioactive iodine in spent fuel off-gas because of its specific recognition, high capture capacity, large-scale preparation, and environment-friendly.

A review of clay based photocatalysts: Role of phyllosilicate mineral in interfacial assembly, microstructure control and performance regulation.

Over the past decades, inspired by the outstanding properties of clay minerals such as abundance, low-cost, environmental benignity, high stability, and regularly arranged silica-alumina framework, researchers put much efforts on the interface assembly and surface modification of natural minerals with bare photocatalysts, i.e. TiO2, g-C3N4, ZnO, MoS2, etc. The clay-based hybrid photocatalysts have resulted in a rich database for their tailor-designed microstructures, characterizations, and environmental-related applications. Therefore, in this study, we took a brief introduction of three representative minerals, i.e. kaolinite, montmorillonite and rectorite, and discussed their basic merits in photocatalysis applications. After that, we summarized the recent advances in construction of stable visible-light driven photocatalysts based on these minerals. The structure-activity relationships between the properties of clay types, pore structure, distribution/dispersion and light absorption, carrier separation efficiency as well as redox performance were illustrated in detail. Such representative information would provide theoretical basis and scientific support for the application of clay based photocatalysts. Finally, we pointed out the major challenges and future directions at the end of this review. Undoubtedly, control and preparation of novel photocatalysts based on clays will continue to witness many breakthroughs in the arena of solar-driven technologies.

A Versatile Interfacial Coassembly Method for Fabrication of Tunable Silica Shells with Radially Aligned Dual Mesopores on Diverse Magnetic Core Nanoparticles.

Anisotropic magnetic nanoparticles with a mesoporous silica shell have the combined merits of a magnetic core and a robust shell. Preparation of magnetically guidable core-shell nanostructures with a robust silica shell that contains well-defined, large, radially aligned silica pores is challenging, and hence this has rarely been described in detail. Herein, a dynamic soft-templating strategy is developed to controllably synthesize hierarchical, dual-mesoporous silica shells on diverse core nanoparticles, in terms of nanoparticle shape (i.e., spherical, chainlike, and disclike), magnetic properties (i.e., hard magnetic and superparamagnetic), and dimensions (i.e., from 3 nm to submicrometers). The developed interfacial coassembly method allows easy design of applicable silica shells containing tunable pore geometries with pore sizes ranging from below 5 nm to above 40 nm, with a specific surface area of 577 m2 g-1 and pore volume of 1.817 cm3 g-1. These are the highest values reported for magnetically guidable anisotropic nanoparticles. The versatility of the method is shown by transfer of the coating procedure to core particles as diverse as spherical superparamagnetic nanoparticles and their clusters as well as by ferromagnetic 3 nm thick hexaferrite nanoplatelets. This method can serve as a general approach for the fabrication of well-designed mesoporous silica coatings on a wide variety of core nanoparticles.

General and Efficient Synthesis of Two-Dimensional Monolayer Mesoporous Materials with Diverse Framework Compositions.

Two-dimensional (2D) mesoporous materials have received substantial research interest due to their highly exposed active sites and unusual nanoconfinement effect. However, controllable and efficient synthesis of 2D mesoporous materials and investigation of their intrinsic properties have remained quite rare. Herein, a general and effective surface-limited cooperative assembly (SLCA) method enabled by leveling precursor solutions on KCl crystals via centrifugation is employed to conveniently synthesize two-dimensional (2D) monolayer mesoporous materials with different compositions. This novel strategy is performed in a manner similar to spin coating, not only enabling generation of ultrathin mesostructured composite film on KCl particles and recycling excessive precursor solution but also providing favorable solvent annealing environment for the film to form ordered mesostructures. Taking monolayer mesoporous Ce0.8Zr0.2O2 solid solutions as a sample, they display ultrathin nanosheet morphology with a thickness of ∼20 nm, highly open porous structure, and easily accessible active sites of surface superoxide species. Upon decoration of 2D mesoporous Ce0.8Zr0.2O2 nanosheets with Pt nanoparticles, the obtained catalyst exhibits superior catalytic activity and stability toward CO oxidation with a low onset temperature of 30 °C and a 100% conversion temperature of 95 °C, which are 35-70 °C lower than those for their counterpart materials, namely, three-dimensional (3D) mesoporous Pt/Ce0.8Zr0.2O2. Moreover, their TOFPt value is ∼11.3 times higher than that of 3D mesoporous Pt/Ce0.8Zr0.2O2. Characterizations based on various techniques indicate that such an outstanding catalytic performance is due to the ultrashort distance (20 nm) of mass diffusion, highly exposed active sites, rich surface-chemisorbed oxygen, and the synergistic effect between the Ce0.8Zr0.2O2 matrix and Pt species.

Synthesis of Podlike Magnetic Mesoporous Silica Nanochains for Use as Enzyme Support and Nanostirrer in Biocatalysis.

Magnetic mesoporous materials have attracted great interest due to their combined property of magnetic nanomaterials and mesoporous materials as well as their potential applications in catalysis, bioenrichment, drug delivery, nanoreactors, etc. In this study, one-dimensional (1D) podlike magnetic mesoporous silica nanochains with tunable hollow space (Fe3O4@nSiO2@void@mSiO2 nanochain named as podlike 1D magnetic mesoporous silica (PL-MMS) nanochain) are rationally synthesized for the first time through a controlled magnetic-induced interface coassembly approach. The obtained PL-MMS possesses a tunable diameter (300-500 nm), large and perpendicular mesopores (8.2 nm) in the outer shell, a silica-protected magnetic-responsive core, and a high surface area (325 m2/g). Benefiting from the large voids and unique mesopores, these mesoporous nanochains exhibit superior performance in enzyme (lipase with a size of 4.0 nm) immobilization with a high loading capacity of 223 µg/mg, and the immobilized lipase demonstrates enhanced catalytic activity in different pH values and temperatures as well as excellent tolerance of organic solvent.

Ammonium Polyphosphate with High Specific Surface Area by Assembling Zeolite Imidazole Framework in EVA Resin: Significant Mechanical Properties, Migration Resistance, and Flame Retardancy.

A zeolite imidazole framework (ZIF-67) was assembled onto the surface of ammonium polyphosphate (APP) for preparing a series multifunctional flame-retardant APP-ZIFs. The assembly mechanism, chemical structure, chemical compositions, morphology, and specific surface area of APP-ZIFs were characterized. The typical APPZ1 and APPZ4 were selected as intumescent flame retardants with dipentaerythritol (DPER) because of their superior unit catalytic efficiency of cobalt by thermogravimetric analysis. APPZ1 and APPZ4 possessed 6.8 and 92.1 times the specific surface area of untreated APP, which could significantly enhance the interfacial interaction, mechanical properties, and migration resistance when using in ethylene-vinyl acetate (EVA). With 25% loading, 25% APPZ4/DPER achieved a limiting oxygen index value of 29.4% and a UL 94 V-0 rating, whereas 25% APP/DPER achieved a limiting oxygen index value of only 26.2% and a V-2 rating, respectively. The peak of the heat release rate, smoke production rate, and CO production rate respectively decreased by 34.7%, 39.0%, and 40.1%, while the char residue increased by 91.7%. These significant improvements were attributed to the catalytic graphitization by nano cobalt phosphate and the formation of a more protective char barrier comprised of graphite-like carbon.

Robust Nacrelike Graphene Oxide-Calcium Carbonate Hybrid Mesh with Underwater Superoleophobic Property for Highly Efficient Oil/Water Separation.

Inspired by the mastoid structure of the lotus leaf and the robust layered structure of the nacre, a novel nacrelike graphene oxide-calcium carbonate (GO-CaCO3) hybrid mesh with superhydrophilic and underwater superoleophobic property was prepared for the first time, via a facile, economical, and environmentally friendly layer-by-layer (LBL) self-assembly method using commercially available stainless steel mesh (SSM) as a ready-made mask. Interestingly, GO nanosheets played a threefold role, regulating the growth of CaCO3 nanocrystals between the GO interlamination for constructing a "brick-and-mortar" structure, improving the interface stability via coordination assembly onto SSM, and creating strong hydration derived from rich oxygen-containing functional groups. The surface hydrophilicity and hierarchically micro/nanoscale structure of GO-CaCO3 artificial pearls imbed on the SSM, contributing to outstanding superhydrophilicity and underwater superoleophobicity. The biomimetic hybrid mesh exhibited a strong mechanical property with a Young's modulus of 25.4 ± 2.6 GPa. The optimized hybrid mesh showed a high separation efficiency of more than 99% toward a series of oil/water mixtures with high flux. The low oil-adhesion force, high fatigue-resistance, chemical stability (acid/alkali/salt resistance), and excellent recycling performance enlighten the great prospects of GO-based nacrelike material for application in oily wastewater treatment.

Fabrication of Novel Hierarchical Multicompartment Highly Stable Triple Emulsions for the Segregation and Protection of Multiple Cargos by Spatial Co-encapsulation.

High-order multiple emulsions are of great interest in both fundamental research and industrial applications as vehicles for their encapsulation capability of actives. In this work, we report a hierarchically multicompartmental highly stable triple emulsion by emulsifying and assembling of natural Quillaja saponin. Water-in-oil-in-(oil-in-water) (W2/O2/(O1/W1)) triple emulsion indicates that the compartmented system consisted of surfaced saponin-coated nanodroplets (SNDs) and dispersed oil globules, which in turn contained smaller aqueous droplets. The effects of formulation parameters, including lipophilic emulsifier content, oil fraction, and SND concentration, on the formation of multiple emulsions were systematically investigated. The assembly into fibrillar network of SNDs at the outer oil-water interface effectively protected the triple emulsion droplets against flocculation and coalescence, and strongly prevented the osmotic-driven water diffusion between the internal water droplets and the external water phase, thus contributing to superior stability during 180 days storage. All of these characteristics make the multicompartmentalized emulsions suitable to co-encapsulate a hydrophilic bioactive (gardenia blue) and two hydrophobic bioactives (eapsanthin and curcumin) in a single emulsion droplet hierarchically for the segregation and protection of multiple cargos. This approach offers a promising route toward accessing the next generation of functional deliveries and encapsulation strategies.

Stabilizing Liquids Using Interfacial Supramolecular Polymerization.

The strong electrostatic interactions at the oil-water interface between a small molecule, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin, H6 TPPS, dissolved in water, and an amine terminated hydrophobic polymer dissolved in oil are shown to produce a supramolecular polymer surfactant (SPS) of H6 TPPS at the interface with a binding energy that is sufficiently strong to allow an intermolecular aggregation of the supramolecular polymers. SPSs at the oil-water interface are confirmed by in situ real-space atomic force microcopy imaging. The assemblies of these aggregates can jam at the interface, opening a novel route to kinetically trap the liquids in non-equilibrium shapes. The elastic film, comprised of SPSs, wrinkles upon compression, providing a strategy to stabilize liquids in non-equilibrium shapes.

A Centimeter-Scale Inorganic Nanoparticle Superlattice Monolayer with Non-Close-Packing and its High Performance in Memory Devices.

Due to the near-field coupling effect, non-close-packed nanoparticle (NP) assemblies with tunable interparticle distance (d) attract great attention and show huge potential applications in various functional devices, e.g., organic nano-floating-gate memory (NFGM) devices. Unfortunately, the fabrication of device-scale non-close-packed 2D NPs material still remains a challenge, limiting its practical applications. Here, a facile yet robust "rapid liquid-liquid interface assembly" strategy is reported to generate a non-close-packed AuNP superlattice monolayer (SM) on a centimeter scale for high-performance pentacene-based NFGM. The d and hence the surface plasmon resonance spectra of SM can be tailored by adjusting the molecular weight of tethered polymers. Precise control over the d value allows the successful fabrication of photosensitive NFGM devices with highly tunable performances from short-term memory to nonvolatile data storage. The best performing nonvolatile memory device shows remarkable 8-level (3-bit) storage and a memory ratio over 105 even after 10 years compared with traditional devices with a AuNP amorphous monolayer. This work provides a new opportunity to obtain large area 2D NPs materials with non-close-packed structure, which is significantly meaningful to microelectronic, photovoltaics devices, and biochemical sensors.

Electrochemical Investigation of Adsorption of Single-Wall Carbon Nanotubes at a Liquid/Liquid Interface.

There is much interest in understanding the interfacial properties of carbon nanotubes, particularly at water/oil interfaces. Here, the adsorption of single-wall carbon nanotubes (SWCNTs) at the water/1,2-dichloroethane (DCE) interface, and the subsequent investigation of the influence of the adsorbed nanotube layer on interfacial ion transfer, is studied by using the voltammetric transfer of tetramethylammonium (TMA+) and hexafluorophosphate (PF6-) as probe ions. The presence of the interfacial SWCNT layer significantly suppresses the transfer of both ions across the interface, with a greater degree of selectivity towards the PF6- ion. This effect was attributed both to the partial blocking of the interface by the SWCNTs and to the potential dependant adsorption of background electrolyte ions on the surface of the SWCNTs, as confirmed by X-ray photoelectron spectroscopy, which is caused by an electrostatic interaction between the interfacial SWCNTs and the transferring ion.

Time-Controlled Colloidal Superstructures: Long-Range Plasmon Resonance Coupling in Particle Monolayers.

Particle interactions, from pronounced dipolar plasmon coupling to noncoupling in colloidal monolayers with interparticle distances of hundreds of nanometers, are demonstrated. Macroscopically sized, hexagonal monolayers with exceptionally high degrees of order are fabricated in one step. Time controls the interparticle spacing and no further processing is required.

Interface-mediated fabrication of bowl-like and deflated ballon-like hollow carbon nanospheres.

In our work, two kinds of hollow carbon nanospheres with controlled morphologies have been successfully prepared from low-cost and nontoxic glucose as the sole carbon precursor under neutral aqueous medium via a simple hydrothermal route. During the process, sodium dodecylbenzene sulfonate (SDBS) and triblock copolymer P123 ((EO)20(PO)70(EO)20) was skillfully selected as the structure-directing agent, respectively. SEM, TEM and AFM results revealed that the two products showed bowl-like and deflated-balloon-like morphology with uniform particle sizes, respectively. Based on the experimental observations, a possible formation mechanism was also discussed, in which the growth of the carbon nanospheres involved an interface-medicated assembly process. The present method was easy, green and mild. Apart from the unique nanostructure, the obtained bowl-like hollow carbon nanospheres exhibited excellent biocompatibility. In particular, it should be mentioned that the open window formed by the bowl-like morphology can facilitate ion transport, thus improving their performances.