Sorption of malachite green on vinyl-modified mesoporous poly(acrylic acid)/SiO2 composite nanofiber membranes

Vinyl-modified mesoporous poly(acrylic acid)/SiO₂ (PAA/SiO₂) composite nanofiber membranes were prepared through a sol-gel electrospinning process. The sorption behavior of malachite green on the membranes was studied. Fourier transform infrared (FTIR) results demonstrated that vinyl groups were grafted onto the silica skeleton. Transmission electron microscopy (TEM) images confirmed the formation of mesopores on the electrospun nanofibers and the pore size was 3.8 nm based on the Barrett-Joyner-Halenda (BJH) model. According to Brunauer-Emmett-Teller (BET) method, the specific surface area of the membranes was 523.84 m²/g. Three widely used isotherms, the Freundlich, Langmuir, and Redlich-Peterson isotherms, were used to model the experimental data of malachite green adsorption on PAA/SiO₂ nanofiber membranes. The best fit was found to be Redlich-Peterson isotherm and the equilibrium adsorption capacity was 220.49 mg/g. The adsorption kinetics followed a pseudo-second-order model. The removal of malachite green from the aqueous phase reached 98.8% in 240 min. The membranes can be regenerated by treated with alcohol solution and reused for multiple cycles, which is beneficial for practical application.     

The optical properties of PVA/TiO2 composite nanofibers

The electrospun nanofibers emerge several advantages because of extremely high specific surface area and small pore size. This work studies the effect of PVA nanofibers diameter and nano‐sized TiO₂ on optical properties as reflectivity of light and color of a nanostructure assembly consisting polyvinyl alcohol and titanium dioxide (PVA/TiO₂) composite nanofibers prepared by electrospinning technique. The PVA/TiO₂ composite spinning solution was prepared through incorporation of TiO₂ nanoparticles as inorganic optical filler in polyvinyl alcohol (PVA) solution as an organic substrate using the ultrasonication method. The morphological and optical properties of collected composites nanofibers were highlighted using scanning electron microscopy (SEM) and reflective spectrophotometer (RS). The reflectance spectra indicated the less reflectance and lightness of composite with higher nanofiber diameter. Also, the reflectance and lightness of nanofibers decreased with increasing nano‐TiO₂ concentration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of graphene oxide/carboxymethyl chitosan/polyvinyl alcohol composite nanofiber membranes by electrospinning for heavy metal adsorption

In this paper, a graphene-oxide/carboxymethyl-chitosan/polyvinyl-alcohol (GO/CMC/PVA) composite nanofiber membrane was prepared by electrospinning and cross-linking with glutaraldehyde (GA) to improve the water resistance. The composite nanofiber membrane can be used in the field of heavy metal adsorption. The membrane was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The effects of GO concentration, adsorption time, and initial concentration of heavy-metal ion (Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺) solution on the adsorption performance of the fiber membranes were investigated. The results showed that the addition of GO can reduce the diameter of nanofibers. GO, CMC, and PVA exhibited good compatibility, and the intermolecular hydrogen bonding improved. The addition of GO also improved the crystalline properties of the composite fiber membrane. In the optimal cross-linking condition, GA was saturated by steam cross-linking for 6 h. The introduction of GO improved the adsorption capacity of the membrane for heavy metals in water. The utmost adsorption capacities for Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺ were 262.1, 237.9, 319.3, and 413.6 mg/g when using the cross-linked composite fiber membranes, respectively. The results of adsorption kinetics and thermodynamics showed that the adsorption process accorded with the pseudo-second-order kinetic model and Langmuir–Freundlich isotherm model.     

Preparation of a PVA/HAP composite polymer membrane for a direct ethanol fuel cell (DEFC)

A novel PVA/Hydroxyapatite (HAP) composite polymer membrane was prepared by the direct blend process and solution casting method. The characteristic properties of the PVA/HAP composite polymer membranes were investigated using thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and the AC impedance method. An alkaline direct ethanol fuel cell, consisting of an air cathode with MnO₂ carbon inks based on Ni-foam, an anode with PtRu black on Ni-foam, and the PVA/HAP composite polymer membrane, was assembled and investigated. It was found that the alkaline direct ethanol fuel cell comprising of a novel cheap PVA/HAP composite polymer membrane showed an improved electrochemical performance in ambient temperature and air. As a result, the maximum power density of the alkaline DEFC, using a PtRu anode based on Ni-foam (10.74 mW cm⁻²), is higher than that of DEFC using an E-TEK PtRu anode based on carbon (7.56 mW cm⁻²) in an 8M KOH + 2M C₂H₅OH solution at ambient temperature and air. These PVA/HAP composite polymer membranes are a potential candidate for alkaline DEFC applications.     

Study of pervaporation for dehydration of caprolactam through PVA/nano silica composite membranes

We investigated nano silica/PVA composite membranes to propose an improved caprolactam pervaporation (PV) dehydration process. The membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and contact angle measurement. Compared with the pure PVA membranes, the nano silica/PVA composite membranes showed different surface morphologies with enhanced hydrophilicity because of their unique formation. To evaluate PV performance and mechanism, we assessed the permeation flux, separation factor, diffusivity/sorptivity selectivity, and activation energy of the composite membranes. The evaluated results indicate that the nano silica/PVA composite membranes induced a breakthrough in the dehydration of a caprolactam-water mixture with a maximum flux of 3.8 kg m^? 2 h^? 1 and an acceptable separation factor of 150.     

Solution-blow spun PLA/SiO2 nanofiber membranes toward high efficiency oil/water separation

With the ever frequent of industrial organic solvent emissions and oil spillages, the development of high efficiency oil/water separation materials has attracted extensive attention. Here, PLA-based nanofiber membranes modified with metal oxides (SiO₂, TiO₂, Al₂O₃, and CeO₂) are fabricated through blow spinning the mixed solution of polylactic acid (PLA) and metal oxide nanoparticles (NPs). Results shows that the addition of SiO₂ NPs significantly increases the hydrophobicity of the membranes, while maintaining the excellent superoleophilicity. The PLA/SiO₂ nanofiber membranes demonstrate a higher separation performance than pure PLA, PLA/TiO₂, PLA/Al₂O₃, and PLA/CeO₂ nanofiber membranes with high separation efficiency (~100%) and permeation flux (17,800 L m⁻² h⁻¹ for n-heptane), as well as prominent oil adsorption capacity (19.9 g/g for n-hexane). The successful fabrication of metal oxides modified PLA nanofiber membranes with high separation and adsorption ability, and excellent durability hold great application potential in the field of oily wastewater treatment.     

Preparation of a Cu(II)-PVA/PA6 Composite Nanofibrous Membrane for Enzyme Immobilization

PVA/PA6 composite nanofibers were formed by electrospinning. Cu(II)-PVA/PA6 metal chelated nanofibers, prepared by the reaction between PVA/PA6 composite nanofibers and Cu²⁺ solution, were used as the support for catalase immobilization. The result of the experiments showed that PVA/PA6 composite nanofibers had an excellent chelation capacity for Cu²⁺ ions, and the structures of nanofibers were stable during the reaction with Cu²⁺ solution. The adsorption of Cu(II) onto PVA/PA6 composite nanofibers was studied by the Langmuir isothermal adsorption model. The maximum amount of coordinated Cu(II) (q_m) was 3.731 mmol/g (dry fiber), and the binding constant (K_l) was 0.0593 L/mmol. Kinetic parameters were analyzed for both immobilized and free catalases. The value of V_max (3774 μmol/mg·min) for the immobilized catalases was smaller than that of the free catalases (4878 μmol/mg·min), while the K_m for the immobilized catalases was larger. The immobilized catalases showed better resistance to pH and temperature than that of free form, and the storage stabilities, reusability of immobilized catalases were significantly improved. The half-lives of free and immobilized catalases were 8 days and 24 days, respectively.     

Preparation and characterization of graphene oxide/poly(vinyl alcohol) composite nanofibers via electrospinning

Graphene oxide (GO) was well dispersed in poly(vinyl alcohol) (PVA) diluted aqueous solution, and then the mixture was electrospun into GO/PVA composite nanofibers. Electron microscopy and Raman spectroscopy on the as‐prepared and calcined samples confirm the uniform distribution of GO sheets in the nanofibers. The thermal and mechanical properties of the nanofibers vary considerably with different GO filler contents. The decomposition temperatures of the GO/PVA composite nanofiber dropped by 38–50°C compared with pure PVA. A very small loading of 0.02 wt % GO increases the tensile strength of the nanofibers by 42 times. A porous 3D structure was realized by postcalcining nanofibers in H₂. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flexible Electrospun strawberry-like structure SiO2 aerogel nanofibers for thermal insulation

Herein, a novel flexible SiO₂ aerogel composite nanofiber membrane with strawberry-like structure and excellent thermal insulation properties, in which SiO₂ aerogel particles act as thermal insulation filler, was prepared by electrospinning technology. With the addition of nano-pore structure SiO₂ aerogel particles, the heat transfer path of the fibers inside the membrane became discontinuous, endowing the as-prepared membrane an ultra-low thermal conductivity of 30.3 mW/(m?K) and large surface area of 240 m²/g. Moreover, the nanofibers membrane also possesses the combined merits of excellent fire resistance, high-temperature stability, and temperature-invariant flexibility, rendering it a promising in the application of insulation and gas adsorption. The successful preparation of this flexible nanofiber membrane paves a new way to design materials with excellent thermal insulation and adsorption properties.     

Electrospun hydrophilic fumed silica/polyacrylonitrile nanofiber-based composite electrolyte membranes

Hydrophilic fumed silica (SiO₂)/polyacrylonitrile (PAN) composite electrolyte membranes were prepared by electrospinning composite solutions of SiO₂ and PAN in N,N-dimethylformamide (DMF). Among electrospinning solutions with various SiO₂ contents, the 12 wt% SiO₂ in PAN solution has highest zeta potential (−40.82 mV), and exhibits the best dispersibility of SiO₂ particles. The resultant 12 wt% SiO₂/PAN nanofiber membrane has the smallest average fiber diameter, highest porosity, and largest specific surface area. In addition, this membrane has a three-dimensional network structure, which is fully interconnected with combined mesopores and macropores because of a good SiO₂ dispersion. Composite electrolyte membranes were prepared by soaking these porous nanofiber membranes in 1 M lithium hexafluorophosphate (LiPF₆) in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 vol%). It is found that 12 wt% SiO₂/PAN electrolyte membrane has the highest conductivity (1.1 × 10⁻² S cm⁻¹) due to the large liquid electrolyte uptake (about 490%). In addition, the electrochemical performance of composite electrolyte membranes is also improved after the introduction of SiO₂. For initial cycle, 12 wt% SiO₂/PAN composite electrolyte membrane delivers the discharge capacity of 139 mAh g⁻¹ as 98% of theoretical value, and still retains a high value of 127 mAh g⁻¹ as 89% at 150th cycle, which is significantly higher that of pure PAN nanofiber-based electrolyte membranes.     

Palladium nanoparticles embedded chitosan/poly(vinyl alcohol) composite nanofibers as an efficient and stable heterogeneous catalyst for Heck reaction

In this study, palladium nanoparticles were successfully embedded into modified chitosan/poly(vinyl alcohol) composite nanofibers (Pd-CS/PVA nanofibers) by electrospinning. Then, the Pd-CS/PVA nanofibers were treated at evaluated temperature to improve its solvent resistance and in situ reduce Pd²⁺ cations into Pd⁰ active species. The incorporated palladium nanoparticles with ultra small mean diameter of 3.73 ± 1.04 nm are evenly distributed inside the Pd-CS/PVA nanofiber. The resulting Pd-CS/PVA nanofiber mat exhibits high catalytic activity for Heck reaction of aromatic iodides with alkenes and can be recycled for 18 times without loss of initial activity. The high catalytic activity and stability of Pd-CS/PVA nanofiber mat can be attributed to the ultra small diameter nanofibers, strong chelating ability of chitosan, and fine embedment of palladium species inside the nanofiber. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48026.     

Electrospun mesoporous carbon nanofibers produced from phenolic resin and their use in the adsorption of large dye molecules

Mesoporous carbon nanofibers (CNFs) were prepared by a sol–gel/electrospinning process using phenolic resin precursor as carbon source and triblock copolymer Pluronic F127 as template. The final CNFs were obtained after carbonization of as-spun nanofibers and removal of SiO₂. Three samples (C-1, C-2, and C-3) with different pore textures were synthesized. The CNF structures were characterized by scanning and transmission electron microscopy, and N₂ adsorption–desorption measurements, demonstrating that the samples consisted of nanofibers with mesopores and the mesopore volumes depended on the amount of tetraethyl orthosilicate in the spinnable sols. According to thermogravimetric analysis, the CNF yields of 2.57%, 2.78%, and 2.13% from the spinnable sols for sample C-1, C-2, and C-3 were obtained, respectively. The mesoporous CNFs were used as highly efficient adsorbents for large dye molecules. The relationship between the pore textures and adsorption properties was studied. It is suggested that the adsorption of different dyes depend on an appropriate pore size distribution in addition to surface area. However, the adsorption capacity of the regenerated adsorbents gradually decreased with the number of regeneration cycles. The adsorption of acid red 1 could reach 186 mg g^?1 for C-3 after seven regeneration cycles. Furthermore, the mechanical strength of CNFs needs improvement.     

Organic/inorganic composite membranes based on polybenzimidazole and nano-SiO2

Organic/inorganic composite membranes based on polybenzimidazole (PBI) and nano-SiO₂ were prepared in this work. However, the preparation of PBI/SiO₂ composite membrane is not easy since PBI is insoluble in water, while nano-SiO₂ is hydrophilic due to the hydrophilicity of nano-SiO₂ and water-insolubility of PBI. Thus, a solvent-exchange method was employed to prepare the composite membrane. The morphology of the composite membranes was studied by scanning electron microscopy (SEM). It was revealed that inorganic particles were dispersed homogenously in the PBI matrix. The thermal stability of the composite membrane is higher than that of pure PBI, both for doped and undoped membranes. PBI/SiO₂ composite membranes with up to 15 wt% SiO₂ exhibited improved mechanical properties compared with PBI membranes. The proton conductivity of the composite membranes containing phosphoric acid was studied. The nano-SiO₂ in the composite membranes enhanced the ability to trap phosphoric acid, which improved the proton conductivity of the composite membranes. The membrane with 15 wt% of inorganic material is oxidatively stable and has a proton conductivity of 3.9 × 10⁻³ S/cm at 180 °C.     

Preparation and performance of the novel PVDF ultrafiltration membranes blending with PVA modified SiO2 hydrophilic nanoparticles

In this study, PVA‐SiO₂ was synthesized by modifying silica (SiO₂) with polyvinyl alcohol (PVA), then a novel polyvinylidene fluoride (PVDF) ultrafiltration (UF) membrane was prepared by incorporating the prepared PVA‐SiO₂ into membrane matrix using the non‐solvent induced phase separation (NIPS) method. The effects of PVA‐SiO₂ particle on the properties of the PVDF membrane were systematically studied by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT‐IR), surface pore size, porosity, and water contact angle. The results indicated that with the addition of PVA‐SiO₂ particles in the PVDF UF membranes, membrane mean pore size increased from 80.06 to 126.00 nm, porosity improved from 77.4% to 89.1%, and water contact angle decreased from 75.61° to 63.10°. Furthermore, ultrafiltration experiments were conducted in terms of pure water flux, bovine serum albumin (BSA) rejection, and anti‐fouling performance. It indicated that with the addition of PVA‐SiO₂ particles, pure water flux increased from 70 to 126 L/m² h, BSA rejection increased from 67% to 86%, flux recovery ratio increased from 60% to 96%, total fouling ratio decreased from 50% to 18.7%, and irreversible fouling ratio decreased from 40% to 4%. Membrane anti‐fouling property was improved, and it can be expected that this work may provide some references to the improvement of the anti‐fouling performance of the PVDF ultrafiltration membrane. POLYM. ENG. SCI., 59:E412–E421, 2019. © 2018 Society of Plastics Engineers     

Solid acidities of SiO2–TiO2/montmorillonite composites synthesized under different pH conditions

SiO₂–TiO₂/montmorillonite composites were prepared under acidic, neutral and basic conditions and the solid acidity of the resulting composites were determined. All the SiO₂/TiO₂ ratio of the colloidal particles was set at 10 but the resulting SiO₂/TiO₂ ratios were significantly richer in TiO₂. The XRD patterns of the acidic composite showed expanding and broadening of the (001) reflection by intercalation of colloidal SiO₂–TiO₂ particles, but the neutral and basic composites showed only broadening of the reflections and no intercalation. The specific surface areas of the acidic, neutral and basic composites (375, 237 and 247 m²/g, respectively) were much larger than of montmorillonite (6 m²/g). The average pore sizes were about 4, 15 and 50 nm, and the amounts of solid acidic sites measured by the NH₃-TPD were 178, 95 and 86 µmol/g for the acidic, neutral and basic composites, respectively. The solid acid amount of the acidic composite was twice that of a commercial catalyst, K-10, (85 µmol/g) and much higher than the guest phase SiO₂–TiO₂ gel (16 µmol/g) or the host phase montmorillonite (6 µmol/g). The TPD peak temperatures reflect the acid strength, and were similar in all the samples, ranging from 175° to 200 °C.     

ITO electrode modified by self-assembling multilayer film of polyoxometallate on poly(vinyl alcohol) nanofibers and its electrocatalytic behavior

Poly(vinyl alcohol) (PVA) nanofiber mats were collected on indium tin oxide (ITO) substrate by electrospinning method. A multilayer film composed of α-[P₂W₁₈O₆₂]⁶⁻ (abbr. P₂W₁₈), a polyoxometallate (POM) anion, and poly(diallymethylammonium chloride) (abbr. PDDA) was fabricated by layer-by-layer (LBL) self-assembly technique on the PVA/ITO electrode. The PDDA/P₂W₁₈ multilayer film could be unselectively or selectively deposited on the PVA/ITO electrode via changing the amount of PVA nanofibers on the ITO substrate. The scanning electron microscope (SEM) images showed that when the electrospun time was short the PDDA/P₂W₁₈ multilayer film was unselectively deposited on PVA nanofiber mats because the amount of PVA nanofibers was too little to cover most of the ITO substrate. However, when the electrospun time was long enough, the PDDA/P₂W₁₈ multilayer film was selectively deposited on PVA nanofiber mats because of the larger surface area and higher surface energy of PVA nanofibers in comparison with the flat ITO substrate. Growth process of the multilayer film was determined by cyclic voltammetry (CV). Electrocatalytic effects of the PDDA/P₂W₁₈ multilayer film unselectively and selectively deposited on the PVA/ITO electrode on NO₂⁻ were observed.     

Freestanding hematite nanofiber membrane for visible-light-responsive photocatalyst

Freestanding mesoporous hematite (α-Fe₂O₃) nanofiber membranes were successfully fabricated by sol–gel electrospinning process using ferratrane precursor for use as a high-performance material for visible-light-responsive photocatalyst. Non-porous nanofiber membranes spun on the heated collector at 300 °C were crystalline α-Fe₂O₃ phase. Upon calcination, pure mesoporous nanofiber membranes were obtained even at a low temperature of 400 °C. The photocatalytic membrane calcined at 400 °C showed the highest efficiency for methylene blue (MB) degradation under visible-light irradiation. The synergetic effects of higher surface area, pore volume and pore diameter promoted the photocatalytic efficiency for MB degradation under visible light. The utilization of photocatalyst in the form of membrane could not only solve the problems of catalyst separation and recovery, but also produce high photodegradation efficiency for both systems without and with hydrogen peroxide even at a catalyst loading as low as 0.04 g/L. No appreciable loss in photocatalytic activity was observed and structural integrity was retained, even after five cycles of photodegradation, which predicted the stability and reusability of these nanofiber membranes for practical use in environmental applications.     

Preparation of TiO<Subscript>2</Subscript> incorporated polyacrylonitrile electrospun nanofibers for adsorption of heavy metal ions

This paper describes the adsorption of lead and cadmium ions from an aqueous solution using a composite of titanium dioxide (TiO₂)-incorporated polyacrylonitrile (PAN) electrospun nanofibers. Adsorption capacities and the mechanical response of the PAN/TiO₂ composite electrospun nanofibers are investigated at different weight percentages of TiO₂ (0.5, 1.0, 2.0, and 5.0 wt.%). The adsorption capacities of the composite PAN/TiO₂ (2.0 and 5.0 wt.%) for Pb(II) and Cd(II) are remarkably increased by approximately 114 and 47%, respectively, compared to those of pure PAN electrospun nanofibers. Moreover, the adsorption of Pb(II) and Cd(II) by PAN/TiO₂ nanofibers reaches an equilibrium within 60 min, and the process can be described using the nonlinear pseudo-second-order kinetic model. The adsorption isotherm study can be represented by the Langmuir model, which suggests the homogeneous distribution of monolayer adsorptive sites on the composite nanofiber surface. Furthermore, the ultimate tensile strength and ductility of all nanofiber membranes are measured through a uniaxial tension test. Mechanical tests reveal a reduction in the tensile strength of the PAN/TiO₂ composite nanofibers with increase in TiO₂ amount due to the possible formation of agglomerates and voids in the nanofiber structure.     

Solvent-free infiltration method for mesoporous SnO2 using mesoporous silica templates

Mesoporous tin oxide (SnO₂) materials, exhibiting high surface areas, crystalline frameworks and various mesostructures, were successfully obtained by a facile solvent-free infiltration method from mesoporous silica templates. Various kinds of mesoporous silica materials, such as KIT-6 (bicontinuous 3-D cubic, Ia3d), SBA-15 (2-D hexagonal, p6mm), SBA-16 (3-D cubic with cage-like pores, Im3m) and spherical mesoporous silica (disordered), were utilized as the hard templates. Tin precursor (SnCl₂ · 2H₂O, m.p. 310–311 K) was infiltrated spontaneously within the mesopores of silica templates by melting the precursor at 353 K without using any solvent. The heat-treatment of SnCl₂-infiltrated composite materials at 973 K under static air conditions and subsequent removal of silica templates by using HF result in the successful preparation of mesoporous SnO₂ materials. The mesostructures as well as the morphologies of mesoporous SnO₂ materials thus obtained were very similar with those of the mesoporous silica templates. The mesoporous SnO₂ materials exhibit high surface areas of 84–121 m²/g as well as high pore volumes in the range of 0.22–0.35 cm³/g. The present solvent-free infiltration method is believed to be a simple and facile way for the preparation of mesoporous materials via nano-replication from mesoporous silica templates.     

Adsorption and photocatalytic properties of TiO<Subscript>2</Subscript>/mesoporous silica composites from two silica sources (acid-leached kaolinite and Si-alkoxide)

Two different mesoporous silicas (MPS) were synthesized by hydrothermal treatment in NaOH solution of two SiO₂ sources. These were microporous silica (MicroPS) derived from selectively acid leached metakaolinite and tetraethylorthosilicate (TEOS). The hydrothermal syntheses of the MPSs were performed at a ratio of SiO₂/cetyltrimethyl- ammonium bromide (CTABr)/NaOH/H₂O = 1/0.1/0.3/150. The specific surface areas (S _BET) of the MPSs from MicroPS (MPS(M)) and TEOS (MPS(T)) were 1070 and 1020 m²/g, respectively. Composites of MPS (75 mass%) with TiO₂ (25 mass%) were prepared using both SiO₂ and two commercial TiO₂ powders, P25 and ST-01. The adsorption–desorption behavior of methylene blue (MB) by the four resulting composites and the two MPSs alone was unique in showing partially reversible behavior. The maximum MB adsorption, observed in the composite of ST-01 with MPS(M), designated (S/M), was 0.034 mmol/g. The rates of MB adsorption in the dark and photodecomposition under UV illumination were considerably different for the four composites and two TiO₂ powers, and followed the order ST-01 < S/T < P25 < P/T ≈ P/M ≪ S/M. The removal rate of MB by the composite S/M by adsorption and photodecomposition was further enhanced by heating at 700 °C. Direct photodecomposition of MB without adsorption in the dark was greatly enhanced in the composites, especially in that composed of MPS(M) and ST-01.