Trimethoxy Silane Research Articles

Modified SiO2 microspheres/polyacrylate resin composites for the enhancement of oil-absorbing performance

Inserting inorganic materials into the skeleton of oil-absorbing resin (OAR) would weaken the interchain winding of polymer, regulate the pore channel structure, and thus enhance the oil-absorbing performance. However, the effects of surface modifiers on the oil-absorbing ability have been rarely explored. Herein, SiO2 microspheres coated with three kinds of silane coupling agents (3-aminopropyltriethoxysilane (APTES), γ-(methacryloxypropyl) trimethoxy silane (MEMO) and chlorotrimethylsilane (TMCS)) were composited with P(SMA-co-BA-co-ST) (octadecyl methacrylate (SMA), butyl acrylate (BA) and styrene (ST)). The as-prepared composite resin microspheres (OAR-APTES-SiO2, OAR-MEMO-SiO2 and OAR-TMCS-SiO2) were fully characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), optical microscopy (OM) and thermal gravimetric analysis (TGA). The results showed that the average particle sizes of the as-prepared SiO2 microspheres were nearly 300 nm and the silane coupling agent of APTES exhibited the best surface modification for SiO2 microspheres (grafting rate reached 16.78%). While, the average particle sizes of composite resins (OAR-APTES-SiO2, OAR-MEMO-SiO2 and OAR-TMCS-SiO2) were nearly 1.5 mm, 2 mm and 2.5 mm, respectively. Meanwhile, composite resin OAR-APTES-SiO2 showed the highest saturated oil-absorbing capacities, which were calculated to be 44.97, 38.12, 27.29 and 22.86 g/g for CCl4, CHCl3, CH2Cl2 and gasoline, respectively, under the optimal adding amount of SiO2 (ω(SiO2) = 0.8%), reaching more than 90% of the saturated oil-absorbing capacity in 30 min. Meanwhile, the oil-absorbing capacity of composite resin is 1.34 times higher than that of bare acrylic resin. It can be recycled 7 times without the obvious decrease in oil absorption ability. This study provides a novel method for the preparation of composite materials with high stability, high oil-absorbing capacity and low-saturation oil-absorbing time by regulating the resin pore structure.

Application of Alumina Nanofibers as Adsorbents for the Removal of Mercury (II) and Lead (II) from Aqueous Solutions

This study aims to design novel amine-functionalized alumina nanofibers for the removal of lead (II) and mercury (II) ions from aqueous solutions. The γ-Al2O3 nanofibers were prepared by calcination of boehmite, and then functionalization with 3-(2-aminoethylamino) propyl trimethoxy silane. The characterization of the nanofibers was carried out using TEM, EDS, elemental mapping, XRD, and XPS. The effects of initial concentration, pH, contact time, and selectivity were studied. The results revealed that the nanofibers can remove 98% of Hg2+ ions and 90% of Pb2+ ions from aqueous solution at concentrations of 40 mg/L and 35 mg/L, respectively. Additionally, the optimal pH conditions for mercury and lead ion adsorption were established to be 6. It was also observed that for concentrations of 100 mg/L and 250 mg/L, the majority of ion contaminants were removed by the nanofibers within the first hour. The adsorption capacities were found to be 129 mg/g and 165 mg/g for Hg2+ and 72.3 mg/g and 111 mg/g for Pb2+ at 100 mg/L and 250 mg/L concentrations, respectively. The ion-adsorption kinetic data was best fitted to a pseudo-second-order model. High sorption capacities were also demonstrated when employed to selectively adsorb mercury (II) and lead (II) ions from aqueous solutions containing Zn2+, Mg2+, Cu4+, Sn4+, and Ni4+. Desorption tests were performed to explore the stability of the heavy metals on the nanofiber.

Development of biomaterial-based oxygen transportation vehicles for circulation within blood

BackgroundSeveral blood replacements have been developed because of issues with blood collection and storage, increased expenditures, and a global lack of reserves. Studies on artificial blood primarily concentrate on the research and synthesis of molecules that transport oxygen. The primary objective of the current work was to create a supporting, oxygen-carrying biological material that can replace blood and be used to save lives when blood is not available. MethodsThe work started with the synthesis of superparamagnetic iron oxide nanoparticles (SPIONS), and two distinct procedures were applied to ensure binding to hemoglobin (Hb) molecules. The surface modifications of the particles were carried out gradually by 3-amino propyl trimethoxy silane (3APGASPIONS) and tartaric acid (TASPIONS). Analysis methods used to characterize the particles include Fourier transform infrared spectrophotometer (FT-IR), elemental analysis (EDX), scanning electron microscope (SEM), X-ray diffractometry (XRD), and high contrast transmission electron microscopy (C-TEM). The characterization studies of SPIONS which bind Hb molecules to the surface were repeated and their effects on endothelial cell culture were examined to determine their toxic effects in vitro. Cell proliferation, superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) activity changes were assessed in the evaluation of the possible toxic effects of the cells against the treated particles in the prepared cell lines. Blood substitute solutions synthesized by two different methods were stored on the shelf for about 1 month and the results were compared with fresh Hb solutions. Results and ConclusionThe CV and UV analysis results obtained from artificial Hb substitutes revealed that the structural integrity of Hb molecules did not change, the oxygen transport capabilities of biomolecules were preserved, and this state remained stable for a long time. Furthermore, it was determined that nanocomplexes synthesized by the two methods caused different cellular proliferation and there was a more limited increase in cellular enzyme activities (SOD, CAT, GPx) of Hb-bound particle solutions when compared to pure SPIONS.

Condensation and hydrophobicity of the surface hydroxyl groups between organosilane modified water glass and microsilica

As one of the novel green foundry binders, the bonding strength of two-component inorganic binder system (water glass-microsilica) under wet conditions needs to be further improved. In this work, γ-(methacryloxypropyl) trimethoxy silane (MPS) was added to water glass. The effect of MPS on the storage stability of sand core was studied, based on which the mechanisms of condensation and hydrophobicity of water glass-microsilica were discussed. The results showed that the maximum bonding strength of 1.0 wt% MPS modified sand core was increased by 15.5% at 80–85% RH. MPS promoted the dehydration condensation between water glass and microsilica, which will make its three-dimensional network more complex. Moreover, it formed a hydrophobic organosilane layer on the surface of the bonding bridge, which can play a role in shielding hydrophilic Na+ and prevent the destruction of bonding film by forming Si–O–R bonds, preventing the external water from damaging.

Laser Writing of Block‐Copolymer Images into Mesopores Using SBDC‐Initiated Visible‐Light‐Induced Polymerization

AbstractFor miniaturization, as well as for improving artificial nanopore performance, precise local polymer functionalization and the combination of different functionalities are required. Imagining data driven nanopore design automated nanopore functionalization would be beneficial. Using direct laser writing as one option of automated nanopore polymer functionalization visible light induced polymerizations are beneficial. Here, we demonstrate the functionalization of mesoporous silicafilms with two different polymers using automated laser writing. For this we developed a visible light (400–700 nm and 405 nm) N,N(diethylamino)dithiocarbamoylbenzyl(trimethoxy)silane (SBDC) inifierter initiated polymerization. While transferring this visible light induced polymerization using SBDC to a commercially available microscope, direct, automated laser writing, as well as polymer re‐initiation was demonstrated. Thereby, polymer spots of 37 and 40 μm in diameter were achieved using 1–5 seconds for each irradiated spot.

Laser writing of block-copolymer images into mesopores using SBDC initiated visible light induced polymerization.

For miniaturization, as well as improving artificial nanopore performance, precise local polymer functionalization and the combination of different functionalities are required. Imagining data driven nanopore design automated nanopore functionalization would be beneficial. Using direct laser writing as one option of automated nanopore polymer functionalization visible light induced polymerizations are necessary. Here, we demonstrate the functionalization of mesoporous silicafilms with two different polymers using automated laser writing. For this we developed a visible light (400 - 700 nm and 405 nm) N,N(diethylamino)dithiocarbamoylbenzyl(trimethoxy)silane (SBDC) inifierter initiated polymerization. While transferring this visible light induced polymerization using SBDC to a commercially available microscope, direct, automated laser writing, as well as polymer re-initiation was demonstrated. Thereby, polymer spots of 37 and 40 µm in diameter were achieved using 1-5 seconds for each irradiated spot.

The effect of terminal group of hole injection self-assembled monolayers on the performance of optoelectronic devices on ITO anodes

We demonstrate the effect on the performance of conventional (Indium tin oxide (ITO)/N,Nj-Di (1- naphthyl)-N,Nj-diphenyl-(1,1-biphenyl)-4,4-diamine (NPB)/Tris-(8-hydroxyquinoline)aluminum (Alq3)/LiF/Al) optoelectronic devices when the ITO surface is modified with various types of self-assembled monolayer (SAM)s such as 3-(trimethoxysilyl)propylamine (NH2SAM), Trimethoxy (propyl)silane CH3SAM, and Trimethoxy (3,3,3-trifluoropropyl)silane (F3SAM). The head functional group and chain configuration are trimethoxysilylpropyl (-(CH3O)3Si(CH2)2) and the tail groups distinguished SAMs (-NH2, -CH3, and -CF3). The contact angles of NH2SAM, CH3SAM, and F3SAM deposited on ITO and ITO were 70.7°, 81.42°, 68.23°, and 30.85°, respectively. The SAM-modified ITO's surface morphology Rpv and Rq parameters were reduced from 31.02 nm to 2.0 nm and 1.18 nm–0.26 nm. The work functions values of ITO, ITO/NH2SAM, ITO/CH3SAM and ITO/F3SAM measured by UPS were 4.99eV, 4.39, 5.09 and 5.69eV, respectively. The maximum luminance of the SAM-modified device increased to 166-fold, and the current density 105-fold, compared to the unmodified device when the operating voltage is set to 11 V. Current and power efficiency increased by 1.9 and 2-fold, respectively. The hole injection conditions are enhanced and the hole injection barrier height between ITO/NPB is reduced.

A route to high-solid coatings: Hydrophobic polyurethane triazoles via bulk polymerization of azide-alkyne cycloaddition

In the present study, we showcase a series bulk polymerized siloxane-decorated polyurethane triazole coatings (Si-PUTs) achieved via azide-alkyne cycloaddition with excellent surface hydrophobicity and anti-corrosion properties. A simple functional modification converts aminopropyl trimethoxy silane to a dialkyne terminated monomer under mild conditions. Concurrently, a series of azide-terminated urethane monomers were synthesized by reacting azidoethanol with three common diisocyanates. Structural elucidation of the monomers was accomplished by FT-IR, 1H and 13C NMR along with ESI-MS. The azide-/alkyne- terminated monomer pairs undergo cycloaddition in absence of solvent and catalyst-free conditions to yield highly crosslinked siloxane-decorated polyurethane (Si-PUT) matrices post curing. FTIR and XPS analysis confirmed the successful formation of these Si-PUTs while the cure kinetics and reaction order was investigated by real-time FTIR. The physico-chemical properties of the polymers achieved were comprehensively assessed prior to evaluating their performance and feasibility as corrosion resistive coatings. The high contact angles in excess of 110°, transparency >85 % in the visible region, low Icorr, high polarization resistance, and corrosion rates in the order of 10−4 mm/year, all underscores the promise of Si-PUTs as excellent corrosion protection coatings. The encouraging results and ease of application demonstrate the potential to formulate environment friendly and multifunctional high-solid protective coatings.

A novel silica-reinforced P(AM/AMPS/SA/TM-SiO2) microspheres for selective adsorption of methylene blue from aqueous solution

The development of adsorption materials with large adsorption capacity, high selectivity and strong regeneration ability is of great significance for the treatment of dye wastewater. With the aim of obtaining a microsphere with stable structure, large adsorption capacity and rich negative charge for selective adsorption of methylene blue (MB) and other cationic dyes from aqueous solution, a novel silica-reinforced P(AM/AMPS/SA/TM-SiO2) microspheres were synthesized from acrylamide (AM), 2-acrylamido-1-methyl-1-propane sulfonic acid (AMPS), sodium alginate (SA) and trimethoxy(vinyl)silane modified silica (TM-SiO2) through microemulsion polymerization method. The structural properties of the microspheres were analyzed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), and dynamic light scattering (DLS). The influences of TM-SiO2 content on particle size distribution, swelling property, and mechanical stability of the microspheres were thoroughly investigated. The results revealed that TM-SiO2 could effectively adjust the particle size distribution range, reduce the swelling degree, and improve the mechanical stability of the microspheres. The effects of temperature, contact time and initial concentration of MB on the adsorption capacity of the microspheres were systematically inquired. The adsorption capacity of P(AM/AMPS/SA/TM-SiO2) microspheres for MB was 362.52 mg/g at 25℃, while that of P(AM/AMPS/SA) microspheres was 307.17 mg/g. Furthermore, P (AM/AMPS/SA/TM-SiO2) nanocomposite microspheres still maintained a complete shape and high adsorption capacity after five adsorption–desorption cycles. The pseudo-second-order kinetic model and Langmuir model were adopted to describe the adsorption process of MB on the microspheres. Moreover, the intermolecular interaction between the microspheres and MB were explored by quantum chemical (QC) calculations. A possible adsorption mechanism was proposed.

Fabrication and Properties of Hydrophobically Modified ZnO–SiO2 Nanocomposite with Polysiloxane

Studies on the wettability properties of solid surfaces are very important in any of the scientific and industrial fields. The most common principle for a superhydrophobic self-cleaning surface is the lotus effect induced by surface roughness. In this study, silicate compounds have been used to produce hydrophobic surfaces. In this way, firstly, SiO2–ZnO nanocomposite was produced, and then vinyl trimethoxy silane was used to increase the water contact angle (WCA). The structure and morphology of nanocomposites were investigated by infrared spectroscopy (FT-IR), X-ray diffraction pattern (XRD), scanning electron microscopy (SEM) and energy-dispersion spectrometer (EDS) analyses. The thermal stability of nanocomposite coatings was examined by thermogravimetric analysis (TGA). In order to investigate the wetting properties, the surface roughness was measured using an atomic force microscope (AFM), where the subsurface roughness average was obtained at 37.79 nm. The WCA of the coated surfaces with ZnO–SiO2 and ZnO–SiO2 @Polysiloxane nanocomposites were measured at 69 and 160°, respectively, indicating the surface superhydrophobic properties of ZnO–SiO2 @Polysiloxane nanocomposites. Finally, superhydrophobic properties of nanocomposites were investigated by the Cassie-Baxter model. The value of the f2 parameter in the model was estimated at 0.9556. This means that air occupies about 95.56% of the contact area between the water droplet and nano-coating, which is responsible for the superhydrophobic property of the surface.

Architecture of a functionalized SBA-15 (SBA-Pr-N-BFE) chemosensor for the detection of Fe3+ ions in aqueous media

SBA-Pr-N-BFE was designed as a chemosensor starting from mesoporous silica SBA-15, (3-aminopropyl)trimethoxy silane, and 1,2-bis(2-formylphenoxy)ethane (BFE), characterized by various techniques and applied as a selective fluorescent chemosensor. Photoluminescence (PL) spectroscopy has been employed to examine the sensing prowess of the functionalized SBA-Pr-N-BFE, which could selectively detect the Fe3+ ions in H2O over various metal ions; notable quenching in the fluorescence intensity was discerned after adding Fe3+ ions in H2O. Furthermore, the fluorescence studies established the linear correlation of fluorescence intensity of SBA-Pr-N-BFE and the concentration of Fe3+ ions with a detection limit of 1.209 × 10-6 M.

Impact of porosity and surface functionalization of hard templates on the preparation of mesoporous silica microspheres

Mesoporous silica microspheres (MPSMs) find broad application as separation materials in high liquid chromatography (HPLC). A promising preparation strategy uses p(GMA-co-EDMA) as hard templates to control the pore properties and a narrow size distribution of the MPMs. Here six hard templates were prepared which differ in their porosity and surface functionalization. This was achieved by altering the ratio of GMA to EDMA and by adjusting the proportion of monomer and porogen in the polymerization process. The various amounts of GMA incorporated into the polymer network of P1-6 lead to different numbers of tetraethylene pentamine in the p(GMA-co-EDMA) template. This was established by a partial least squares regression (PLS-R) model, based on FTIR spectra of the templates. Deposition of silica nanoparticles (SNP) into the template under Stoeber conditions and subsequent removal of the polymer by calcination result in MPSM1-6. The size of the SNPs and their incorporation depends on the pore parameters of the template and degree of TEPA functionalization. Moreover, the incorporated SNPs construct the silica network and control the pore parameters of the MPSMs. Functionalization of the MPSMs with trimethoxy (octadecyl) silane allows their use as a stationary phase for the separation of biomolecules. The pore characteristics and the functionalization of the template determine the pore structure of the silica particles and, consequently, their separation properties.

A negative-response strain sensor towards wearable microclimate changes for body area sensing networks

Wearable and stretchable strain sensors have attracted much attention for their unique applications in monitoring human motion and health. However, state-of-the-art sensors lack sensing reliability on temperature and humidity changes at the wearable microinterface, leading to suboptimal sensing accuracy in body area sensing networks. For that, we design and fabricate a strain sensor using silk/polyurethane composite yarns with a core-sheath structure. The silk is modified using graphene with the assistance of 3-glycidyloxypropyl trimethoxy silane as coupling agent. The sensor exhibits fast response speed (i.e., 80 ms), high durability (>1500 cycles), remarkable linear sensing feature (R2 = 99.8 %) throughout the whole working range, and negative resistance response towards strain deformation. More importantly, the sensor performance will not be affected by temperature and humidity changes in typical use conditions. Testing is conducted and sensor responses in various body motions are also reported. In addition, a demonstration for the real-time body area sensing network using the fabricated sensor is provided. Experimental results from this study show that the fabricated strain sensor will have huge potentials for future personalized healthcare and public health management.

Palladium-catalyzed synthesis of 2,3-disubstituted indoles via arylation of ortho-alkynylanilines with arylsiloxanes.

In this study, we report the electrophilic cyclization of N,N-dimethyl-o-alkynylanilines with arylsiloxanes in the presence of [Pd(OAc)2] and Ag2O catalytic system, which leads to the efficient synthesis of indoles, similar to the one that is obtained through Larock indole synthesis. A range of aryl(trimethoxy)silanes with EDGs and EWGs were successfully utilized for the synthesis of a diverse variety of substituted indoles via the cleavage of the C-Si bond. This protocol exhibits good functional group tolerance and wide substrate scope to provide 2,3-diaryl-N-methylindoles in 26-88% yields.

Controlled Silanization of Transparent Conductive Oxides as a Precursor of Molecular Recognition Systems

The search for new molecular recognition systems has become the goal of modern electrochemistry. Creating a matrix in which properties can be controlled to obtain a desired analytical signal is an essential part of creating such tools. The aim of this work was to modify the surface of electrodes based on transparent conductive oxides with the use of selected alkoxysilanes (3-aminopropyltrimethoxysilane, trimethoxy(propyl)silane, and trimethoxy(octyl)silane). Electrochemical impedance spectroscopy and cyclic voltammetry techniques, as well as contact angle measurements, were used to determine the properties of the obtained layers. Here, we prove that not only was the structure of alkoxysilanes taken into account but also the conditions of the modification process-reaction conditions (time and temperature), double alkoxysilane modification, and mono- and binary component modification. Our results enabled the identification of the parameters that are important to ensure the effectiveness of the modification process. Moreover, we confirmed that the selection of the correct alkoxysilane allows the surface properties of the electrode material to be controlled and, consequently, the charge transfer process at the electrode/solution interface, hence enabling the creation of selective molecular recognition systems.

Control strategies for atmospheric pressure plasma polymerization of fluorinated silane thin films with antiadhesive properties

AbstractFinding proper strategies to control plasma polymerization processes is a crucial aspect to produce thin films with tailored characteristics. In this work, the validity of the Yasuda parameter W/FM (W: discharge power and FM: precursor feed rate) as a controlling parameter for a polymerization process assisted by an atmospheric pressure single electrode plasma jet and the aerosolized fluorinated silane precursor trimethoxy(3,3,3‐trifluoropropyl)silane is demonstrated. The properties of thin films deposited under different W/FM values are discussed using attenuated total reflectance—Fourier transform infrared (ATR‐FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS), water contact angle (WCA) measurements, and scanning electron microscopy (SEM). Results suggest the presence of two deposition domains as a function of W/FM (an energy‐deficient domain and a monomer‐deficient domain), each inducing coatings with different chemical and physical properties. Furthermore, coatings deposited under the same W/FM values exhibit similar characteristics regardless of the power and feed rate values adopted. Considering the potential use of the deposited coatings to increase the antiadhesive properties of implantable medical devices, preliminary results on coatings' antiadhesive activity against Pseudomonas aeruginosa and Staphylococcus aureus are presented.

Silane treated starch dispersed PBAT/PHBV-based composites: Improved barrier performance for single-use plastic alternatives

The objective of this study is to include 5 wt% silane-treated starch (S-t-Starch) into biodegradable flexible poly(butylene adipate-co-terephthalate) (PBAT)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) blend matrix, which can facilitate superior barrier and balanced mechanical properties. With the intension of improving compatibilization between matrix and filler, starch (biological macromolecule) was efficiently treated with 15 wt% of 3-glycidoxypropyl trimethoxy silane (GPTMS), a coupling agent. Various analyses such as barrier, mechanical, thermal, surface morphology and rheological were performed using cast extruded PBAT/PHBV-based composite films. Comprehensive characterizations suggested that cast extruded PBAT/PHBV with 5 wt% S-t-Starch composites exhibited 91 and 82 % improvement in oxygen and water vapor barrier, respectively, compared to PBAT film. The increment in % crystallinity (as supported by DSC analysis) of PBAT/PHBV/5%S-t-Starch composite due to the silane component was one of the reasons for barrier improvement. The other reason was the improved interfacial adhesion between matrix and S-t-Starch particles (as supported by SEM analysis), which restricted the mobility of the polymer chains. The elongation at break (%EB) of the cast extruded PBAT/PHBV/5%Starch film was slightly improved from 536 to 542 % after silane treatment. Hence, the developed polymer composite in this research work can contribute to flexible packaging applications that require improved barrier properties.

Synthesis of Transparent ZnO–TiO2 and Its Nanocomposites for Ultraviolet Protection of a Polyethylene Terephthalate (PET) Film

The goal of this research was to investigate the effects of ZnO–TiO2 and its nanocomposites, on the physical, mechanical, and ultraviolet protection of polyethylene terephthalate (PET). Exposure to ultraviolet (UV) rays is a major cause of the degradation of the quality and optical properties of materials in addition to skin cancer; therefore, research on UV-blocking materials that are safe and have fewer side effects than currently available products is being actively conducted. In this study, a material with UV-blocking capability was synthesized while ensuring the transparency of ZnO and TiO2. ZnO–TiO2 and its various composites were successfully synthesized via a hydrothermal method followed by ball milling and their properties were systematically analyzed by using scanning electron microscopy, X-ray diffractometry, Fourier-transform infrared spectroscopy, and water contact angle measurements. Furthermore, a simple dip-coating method was employed to prepare transparent polyethylene terephthalate (PET) films coated with the composites, which were subsequently investigated for UV-blocking properties by exposing them to UV irradiation. The hydroxyl groups of ZnO and TiO2, as representative inorganic sunblock components, were removed by using 3-chloropropyl trimethoxy silane as a coupling agent to improve their wettability in an organic solvent as well as their dispersibility and stability. The addition of a small amount of Tinuvin® allowed the hybrid organic and inorganic components to exhibit transparent UV-blocking characteristics, with a UV transmittance of ≤20% and 90% visible transmittance. These results, thus, serve as a basis for contributing to applications in the field of packaging, health, and hygiene industries.

In-Capillary Photodeposition of Glyphosate-Containing Polyacrylamide Nanometer-Thick Films.

The present research reports on in-water, site-specific photodeposition of glyphosate (GLP)-containing polyacrylamide (PAA-GLP) nanometer-thick films (nanofilms) on an inner surface of fused silica (fused quartz) microcapillaries presilanized with trimethoxy(octen-7-yl)silane (TMOS). TMOS was chosen because of the vinyl group presence in its structure, enabling its participation in the (UV light)-activated free-radical polymerization (UV-FRP) after its immobilization on a fused silica surface. The photodeposition was conducted in an aqueous (H2O/ACN; 3:1, v/v) solution, using UV-FRP (λ = 365 nm) of the acrylamide (AA) functional monomer, the N,N'-methylenebis(acrylamide) (BAA) cross-linking monomer, GLP, and the azobisisobutyronitrile (AIBN) UV-FRP initiator. Acetonitrile (ACN) was used as the porogen and the solvent to dissolve monomers and GLP. Because of the micrometric diameters of microcapillaries, the silanization and photodeposition procedures were first optimized on fused silica slides. The introduction of TMOS, as well as the formation of PAA and PAA-GLP nanofilms, was determined using atomic force microscopy (AFM), scanning electron microscopy with energy-dispersive X-ray (SEM-EDX) spectroscopy, and confocal micro-Raman spectroscopy. Particularly, AFM and SEM-EDX measurements determined nanofilms' thickness and GLP content, respectively, whereas in-depth confocal (micro-Raman spectroscopy)-assisted imaging of PAA- and PAA-GLP-coated microcapillary inner surfaces confirmed the successful photodeposition. Moreover, we examined the GLP impact on polymer gelation by monitoring hydration in a hydrogel and a dried powder PAA-GLP. Our study demonstrated the usefulness of the in-capillary micro-Raman spectroscopy imaging and in-depth profiling of GLP-encapsulated PAA nanofilms. In the future, our simple and inexpensive procedure will enable the fabrication of polymer-based microfluidic chemosensors or adsorptive-separating devices for GLP detection, determination, and degradation.

Highly Oxidation‐Resistant Electrolyte for 4.7 V Sodium Metal Batteries Enabled by Anion/Cation Solvation Engineering

AbstractSodium metal batteries (SMBs) are considered as promising battery system due to abundant Na sources. However, poor compatibility between electrolyte and cathode severely impedes its development. Herein, we proposed an anion/cation solvation strategy for realizing 4.7 V resistant SMBs electrolyte with NaClO4 and trimethoxy(pentafluorophenyl)silane (TPFS) as dual additives (DA). The ClO4− can rapidly transfer to the cathode surface and strongly coordinate with Na+ to form stable polymer‐like chains with solvents. Meanwhile, TPFS can preferentially enter into the PF6− anion solvation sheath for reducing PF6‐solvent interaction and effectively scavenge adverse electrolyte species for protecting electrode electrolyte interphases. Thus, such electrolyte elevates the oxidative stability of carbonate electrolytes from 3.77 to 4.75 V, and enables Na||Na3V2(PO4)2O2F (NVPF) battery with a capacity retention of 93 % and an average Coulombic efficiency (CE) of 99.6 % after 500 cycles at 4.7 V.