Mesoporous LaVO4/MCM-48 nanocomposite with visible-light-driven photocatalytic degradation of phenol in wastewater.

Dearomatization through photocatalytic oxidation is a swiftly rising phenolic compounds removal technology that works at trifling operations requirements with a special emphasis on the generation of nontoxic products. The study aims to develop a LaVO4/MCM-48 nanocomposite that was prepared via a hydrothermally approach assisting the employment of an MCM-48 matrix, which was then utilized for phenol degradation processes. Various techniques including UV-Vis DRS, FTIR, PL, Raman, TEM, and BET analyses are employed to characterize the developed photocatalyst. The developed photocatalyst presented remarkable characteristics, especially increased light photon utilization, and reduced recombination rate leading to enhanced visible-light-driven photodegradation performance owing to the improved specific surface area, specific porosities, and <2 eV narrow energy bandgap. The LaVO4/MCM-48 nanocomposite was experienced on aqueous phenol solution having 20 mg/L concentration under visible-light exposure, demonstrating exceptional performance in photodegradation up to 99.28%, comparatively higher than pure LaVO4. The conducted kinetic measurements revealed good accordance with pseudo first-order. A possible reaction mechanism for photocatalytic degradation was also predicted. The as-synthesized LaVO4/MCM-48 nanocomposite presented excellent stability and recyclability.

Dendritic mesoporous nanoparticles for the detection, adsorption, and degradation of hazardous substances in the environment: State-of-the-art and future prospects.

Equipped with hierarchical pores and three-dimensional (3D) center-radial channels, dendritic mesoporous nanoparticles (DMNs) make their pore volumes extremely large, specific surface areas super-high, internal spaces especially accessible, and so on. Other entities (like organic moieties or nanoparticles) can be modified onto the interfaces or skeletons of DMNs, accomplishing their functionalization for desirable applications. This comprehensive review emphasizes on the design and construction of DMNs-based systems which serve as sensors, adsorbents and catalysts for the detection, adsorption, and degradation of hazardous substances, mainly including the construction procedures of brand-new DMNs-based materials and the involved hazardous substances (like industrial chemicals, chemical dyes, heavy metal ions, medicines, pesticides, and harmful gases). The sensitive, adsorptive, or catalytic performances of various DMNs have been compared; correspondingly, the reaction mechanisms have been revealed strictly. It is honestly anticipated that the profound discussion could offer scientists certain enlightenment to design novel DMNs-based systems towards the detection, adsorption, and degradation of hazardous substances, respectively or comprehensively.

Synthesis of Hierarchically Porous Bioactive Glass and Its Mineralization Activity.

Mesoporous bioactive glass is a promising biomaterial for bone tissue engineering due to its good biocompatibility and bioactivity. In this work, we synthesized a hierarchically porous bioactive glass (HPBG) using polyelectrolyte-surfactant mesomorphous complex as template. Through the interaction with silicate oligomers, calcium and phosphorus sources were successfully introduced into the synthesis of hierarchically porous silica, and HPBG with ordered mesoporous and nanoporous structures was obtained. The morphology, pore structure and particle size of HPBG can be controlled by adding block copolymer as co-template or adjusting the synthesis parameters. The ability to induce hydroxyapatite deposition in simulated body fluids (SBF) demonstrated the good in vitro bioactivity of HPBG. Overall, this work provides a general method for the synthesis of hierarchically porous bioactive glasses.

Mesoporous silica nanoparticles adsorb aflatoxin B1 and reduce mycotoxin-induced cell damage.

The present study examined the effects of mesoporous silica nanoparticles (MSNs) on its adsorption capacity of aflatoxin B1 (AFB1). Moreover, the study evaluated the toxicity of MSNs with AFB1 using NIH3T3 cells and hemolysis test. The obtained MSNs were spherical, irregular-like in shape, having a mean size of 39.97 ± 7.85 nm and a BET surface area of 1195 m2/g. At 0.1 mg mL-1 concentration of MSN, the AFB1 adsorption capacity was 30%, which reached 70% when the MSN concentration increased to 2.0 mg mL-1. Our findings showed that AFB1 was adsorbed (∼67%) in the first few minutes on being in contact with MSNs, reaching an adsorption capacity of ∼70% after 15 min. Thereafter, the adsorption capacity remained constant in solution, demonstrating that the MSNs adsorbed toxins even beyond overnight. MSN treatment (0.5-2.0 mg mL-1) using NIH3T3 cells did not result in any reduction in cell viability. In addition, MSN treatment completely reversed the cytotoxic effect of AFB1 at all concentrations. Hemolysis test also revealed no hemolysis in MSNs evaluated alone and in those combined with AFB1. To the best of our knowledge, this study is the first to demonstrate that MSN can reduce cell toxicity produced by AFB1 due to its potential to adsorb mycotoxins.

Ultrahigh-Rate Na/Cl2 Batteries Through Improved Electron and Ion Transport by Heteroatom-Doped Bicontinuous-Structured Carbon.

Rechargeable sodium/chlorine (Na/Cl2 ) batteries are emerging candidates for sustainable energy storage owing to their superior energy densities and the high abundance of Na and Cl elements. However, their practical applications have been plagued by the poor rate performance (e.g., a maximum discharge current density of 150 mA g-1 ), as the widely used carbon nanosphere cathodes show both sluggish electron-ion transport and reaction kinetics. Here, by mimicking the sufficient mass and energy transport in a sponge, we report a bicontinuous-structured carbon cubosome with heteroatomic doping, which allows efficient Na+ and electron transport and promotes Cl2 adsorption and conversion, thus unlocking ultrahigh-rate Na/Cl2 batteries, e.g., a maximum discharge current density of 16,000 mA g-1 that is more than two orders of magnitude higher than previous reports. The optimized solid-liquid-gas (carbon-electrolyte-Cl2 ) triple interfaces further contribute to a maximum reversible capacity and cycle life of 2,000 mAh g-1 and 250 cycles, respectively. This study establishes a universal approach for improving the sluggish kinetics of conversion-type battery reactions, and provides a new paradigm to resolve the long-standing dilemma between high energy and power densities in energy storage devices.

Influence of 2D template-assisted (SBA-15) metal oxide Co3O4 for pseudocapacitive and dye degradation application.

Cobalt oxide (Co3O4) is a low-cost material exhibiting excellent physicochemical and photocatalytic properties indicating its potential use for next-generation eco-friendly energy storage and photocatalytic degradation applications. In this study, Co3O4 nanoarcs were synthesized using SBA-15 as a template by microwave-assisted method to form an S15/m-Co3O4 product. Characterization was done by low and wide-angle X-Ray diffraction, and Fourier transformed infra-red spectroscopic studies confirming the presence of S15/m-Co3O4. Scanning Electron Microscope images proved the agglomerated nanotube and nanoarcs like the structure of SBA-15 and S15/m- Co3O4, respectively. Electrochemical studies included cyclic voltammetry, charge/discharge, retention capacity, and electron impedance spectroscopy studies in a 3-electrode system. S15/m-Co3O4 nanoarcs, as the electrode material, was revealed to have a specific capacity of 87.5 C/g in 1 M KOH solution. Upon running 1000 cycles, the material had excellent capacity retention of 87%. The S15/m-Co3O4 product also underwent photocatalytic degradation studies. The Rhodamine R6G dye degradation by S15/m-Co3O4 under UV irradiation exhibited a high degradation percentage of 97.7%, following the first-order kinetics. S15/m-Co3O4 has proven to be biocompatible and can be used to enhance supercapacitors which are an ideal alternative to conventional batteries for energy storage applications. Thus, the data produced proves S15/m-Co3O4 nanoarcs is an excellent electrode material for pseudocapacitive application and a catalyst for photocatalytic degradation of dye molecules.

Dual-Functional Mesoporous Copper(II) Metal-Organic Frameworks for the Remediation of Organic Dyes.

By using tritopic and ditopic organic linkers derived from the same 2,4,6-triphenylpyridine core, copper(II) metal-organic frameworks with different three-dimensional structures have been successfully synthesized under ambient conditions. The crystalline framework, PTB MOF ([Cu3 (PTB)2 (H2 O)3 ]n , where H3 PTB=4,4',4''-(pyridine-2,4,6-triyl)tribenzoic acid, was observed to be mesoporous in nature and exhibited dual functionality in the removal of organic dyes. While cationic dyes such as methylene blue and malachite green, which are of different sizes, were adsorbed by PTB MOF; anionic dyes such as tartrazine could be effectively degraded in a photo-Fenton-like reaction catalyzed by the MOFs under irradiation with visible light.

Universality of mesoporous coal gasification slag for reinforcement and deodorization in four common polymers.

Mesoporous adsorbents and polymer deodorants are difficult to implement on a large scale because of their complicated preparation methods. Herein, a mesoporous adsorbent (CGSA) with a specific surface area of 564 m2g-1and a pore volume of 0.807 cm3g-1was prepared from solid waste coal gasification slag using a simple acid leaching process. The adsorption thermodynamics and adsorption kinetics results verified that the adsorption mechanism of propane on CGSA was mainly physisorption. Then the universality of CGSA in different polymers was investigated by introducing CGSA and its commercialized counterparts (CaCO3, and zeolite) into four common polymers. When the filler content was 30 wt%, the average reinforcement effect of CGSA on the tensile, flexural, and impact strengths of the four polymers was 46.68%, 83.62%, and 211.90% higher than that of CaCO3, respectively. Gas chromatography results also showed that CGSA significantly decreased total volatile organic compound emissions from the composites, and its optimal deodorization performance reached 69.58%, 81.33%, and 91.09% for different polymers, respectively, far exceeding that of zeolite. Therefore, this study showed that low-cost, high-performance, and multifunctional mesoporous polymer fillers with excellent universality can be manufactured from solid contaminants.

Complex Pore Structure of Mesoporous Zeolites: Unambiguous TEM Imaging Using Platinum Tracking.

The article proposes a new way for visualization of mesopores and quantitative evaluation of the pore structure in zeolite crystals. The approach is based on platinum tracking inside the zeolite material after its incorporation from a gaseous precursor using an electron beam prior to preparing a TEM specimen by the focused ion beam technique. The pores in mesoporous silica and purely microporous zeolite Y were visualized in TEM images in a demonstration of the capabilities of the approach. Finally, platinum tracking was used for studying the pore structure of zeolite Y (CBV 720) containing mesopores both inside the crystal and those emerging at its surface, which were unambiguously distinguished from each other. The obtained sizes of the mesopores and the calculated material porosity are in good agreement with the results obtained by the low-temperature argon sorption isotherms method.

One-pot synthesis of SiO2@SiO2 core-shell microspheres with controllable mesopore size as a new stationary phase for fast HPLC separation of alkyl benzenes and ß-agonists.

Monodisperse SiO2@SiO2 core-shell silica microspheres (CSSM) with enlarged mesopores perpendicular to the particles surface were prepared using a dual-templating approach. With cetyltrimethyl ammonium bromide as the template and octyltrimethyl ammonium bromide as an auxiliary chemical, the pore size can be enlarged from 2.6 to 10.6 nm. The average shell thickness can be increased from 31 nm to 97 nm by adjusting the concentrations of the surfactants under continuous addition of tetraethyl orthosilicate. After coating twice, the resulting CSSM has a uniform mesoporous shell of about 198 nm thickness and a narrow pore size distribution. The CSSM were then modified with octadecyltrichlorosilane to give a material referred to as CS-C18. It was evaluated by separating the mixture of methylbenzene (toluene), ethylbenzene, n-propylbenzene, n-butylbenzene, n-amylbenzene and hexylbenzene. The baseline separation of the six alkyl benzenes is achieved within 2 min. Compared to a commercial column of type BEH-C18, CS-C18 shows a faster and better separation even at lower back pressure. It was also applied to the fast separation of benzo[a]pyrene, salbutamol, ractopamine and clenbuterolin residues in pork samples. The high column efficiency and better reproducibility suggest that the CSSM can be used as a matrix for fast separation and analysis of several kinds of small analytes. Graphical abstract A dual-templating approach was utilized to produce the core shell microsphere with controllable mesopore channels by using hexadecyltrimethylammonium bromide (CTAB) as the template and trioctylmethylammonium bromide (TOMAB) as an auxiliary chemical to enlarge the size of CTAB micelles.

Mesoporous graphitic carbon nitride as an efficient sorbent for extraction of sulfonamides prior to HPLC analysis.

Mesoporous graphitic carbon nitride (MCN) is shown to be a viable sorbent for the enrichment of sulfonamides (SAs). To overcome the difficulty of separating the sorbent from the matrix, a novel type kind of column-assisted dispersive solid-phase extraction (CA-dSPE) method was designed. The MCN was characterized by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, fourier transform infrared spectroscopy and nitrogen adsorption-desorption measurements. The amount of sorbent, the pH value of the sample, the adsorption time, type and volume of the eluent and desorption time were optimized. The SAs were eluted from the sorbent with elution solvent of methanol containing 10% (v/v) ammonia and then submitted to HPLC analysis. Under the optimized conditions, the limits of detection for the SAs investigated (sulfadiazine, sulfameter, sulfachloropyridazine, sulfabenzamide and sulfadimethoxine) range from 20 to 5 pg·mL-1. Satisfactory recoveries were obtained for spiked environmental water (90.1-110.5%) and milk samples (82.3-102.7%), with relative standard deviations of 0.5-3.8% and 1.1-4.4%, respectively. The method is simple, time saving and sensitive. Graphical abstract Schematic presentation of a column assisted dispersive solid-phase extraction by using mesoporous graphitic carbon nitride as sorbent combined with high performance liquid chromatography for sensitive analysis of sulfonamides in environmental water and milk samples.

A hollow CuOx/NiOy nanocomposite for amperometric and non-enzymatic sensing of glucose and hydrogen peroxide.

The authors report that CuOx/NiOy hollow nanocomposites are an effective bifunctional catalyst capable of oxidizing glucose and reducing hydrogen peroxide. Synthesis is based on a solvothermal process and subsequent thermal treatment. The structure can be controlled by adjusting the amounts of added NiCl2 during the solvothermal etching process, and core-shell, yolk-shell or hollow structures can be obtained. The porous hollow structure composite of type CuO30/NiO90 was used to modify a glassy carbon electrode. It exhibits excellent electrocatalytic activity towards glucose oxidation in solution of pH 13, typically at a working potential of +0.60 V (vs. Ag/AgCl). This enables voltammetric sensing of glucose with (a) a low limit of detection (0.08 µM, at S/N = 3), (b) over a wide linear range (0.20 µM - 2.5 mM), and (c) high sensitivity (2043 µA·mM-1·cm-2). The sensor is reproducible, selective and stable. It can be used to detect glucose in spiked human serum. The CuO30/NiO90 composite also displays good electrocatalytic activity towards reduction of H2O2 in neutral aqueous medium, typically at an applied potential of -0.35 V. It has a detection limit of 90 nM, a sensitivity of 271.1 µA·mM-1·cm-2, and a linear detection range that extends from 0.30 µM to 9.0 mM. Graphical abstract CuOx/NiOy nanocomposites with three different structures were synthesized by coordinated etching precipitation method. The hollow structure CuO30/NiO90 was coated on the surface of glassy carbon electrode for the amperometric determination of glucose and hydrogen peroxide.

Molecular Simulation of Naphthalene, Phenanthrene, and Pyrene Adsorption on MCM-41.

The adsorption of three typical polycyclic aromatic hydrocarbons (PAHs), naphthalene, phenanthrene, and pyrene with different ring numbers, on a common mesoporous material (MCM-41) was simulated based on a well-validated model. The adsorption equilibriums (isotherms), states (angle distributions and density profiles), and interactions (radial distribution functions) of three PAHs within the mesopores were studied in detail. The results show that the simulated isotherms agreed with previous experimental results. Each of the PAHs with flat molecules showed an adsorption configuration that was parallel to the surface of the pore, in the following order according to the degree of arrangement: pyrene (Pyr) > phenanthrene (Phe) > naphthalene (Nap). In terms of the interaction forces, there were no hydrogen bonds or other strong polar forces between the PAHs and MCM-41, and the O⁻H bond on the adsorbent surface had a unique angle in relation to the PAH molecular plane. The polarities of different H atoms on the PAHs were roughly the same, while those of the C atoms on the PAHs decreased from the molecular centers to the edges. The increasing area of the π-electron plane on the PAHs with the increasing ring number could lead to stronger adsorption interactions, and thus a shorter distance between the adsorbate and the adsorbent.

Stabilization of Formate Dehydrogenase in a Metal-Organic Framework for Bioelectrocatalytic Reduction of CO2.

The efficient fixation of excess CO2 from the atmosphere to yield value-added chemicals remains crucial in response to the increasing levels of carbon emission. Coupling enzymatic reactions with electrochemical regeneration of cofactors is a promising technique for fixing CO2 , while producing biomass which can be further transformed into biofuels. Herein, a bioelectrocatalytic system was established by depositing crystallites of a mesoporous metal-organic framework (MOF), termed NU-1006, containing formate dehydrogenase, on a fluorine-doped tin oxide glass electrode modified with Cp*Rh(2,2'-bipyridyl-5,5'-dicarboxylic acid)Cl2 complex. This system converts CO2 into formic acid at a rate of 79±3.4 mm h-1 with electrochemical regeneration of the nicotinamide adenine dinucleotide cofactor. The MOF-enzyme composite exhibited significantly higher catalyst stability when subjected to non-native conditions compared to the free enzyme, doubling the formic acid yield.

Visual detection of melamine by using a ratiometric fluorescent probe consisting of a red emitting CdTe core and a green emitting CdTe shell coated with a molecularly imprinted polymer.

A composite ratiometric fluorescent probe is described for visual detection of melamine (MEL) in milk samples. It is based on the use of red emitting and green emitting CdTe quantum dots, and a mesoporous molecularly imprinted polymer. The red emitting QDs are embedded in the silica microsphere to serve as a core, and the green emitting QDs are coated on the surface of the silica microsphere as a shell. A molecularly imprinted polymer (MIP) with specific recognition sites for MEL was placed on the shell. If MEL is bound by the MIP, the green fluorescence is quenched due to hydrogen bond interaction. The red emission, in contrast, remains unchanged. Quenching leads to a change in the color of fluorescence from red-green to purely red. This effect allows for visual and instrumental detection of MEL. The mesoporous structure of the MIP reduces the mass transfer resistance and enhances the accessibility of sites for MEL. Response is linear in the 50-1000 ng mL-1 MEL concentration range, and the limit of detection is 13 ng mL-1. The fluorescent probe was successfully applied to the analysis of MEL-spiked milk samples and gave recoveries between 94.1 and 98.7%, with 3.6-5.1% relative standard deviations. Graphical abstract Schematic of the preparation and detection of the composite probe. The probe was applied for the selective recognition and visual detection of melamine (MEL).

Preparation of a Mesoporous Structure of SnO2 for Increasing the Oral Bioavailability and Dissolution Rate of Nitrendipine.

In this study, mesoporous SnO2 (MSn) with a three-dimensional mesoporous structure was prepared using MCM-48 as the template in order to increase the oral bioavailability and dissolution rate of insoluble drugs. The model drug, nitrendipine (NDP), was loaded into the MSn by the adsorption method. The structural features of MSn were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and N2 adsorption (desorption) analysis. NDP was existed in the pore channels of MSn in an amorphous state, which was characterized by powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). MSn showed a good biocompatibility in the cell toxicity assay for Caco-2 cells. In vitro dissolution results suggested that MSn could significantly enhance the dissolution rate of NDP compared with commercial NDP tablets. Pharmacokinetic studies indicated that NDP-MSn tablets effectively enhanced the oral bioavailability of NDP. In conclusion, MSn was found to be a potential carrier for improving the solubility of insoluble drugs.

Development of a Textile Nanocomposite as Naked Eye Indicator of the Exposition to Strong Acids.

Chemical burns, mainly produced by acids, are a topic of concern. A new sensing material for the detection of strong acids able to be incorporated into textiles has been developed. The material is prepared by the covalent attachment of 2,2',4,4',4″-pentamethoxy triphenyl methanol to a mesoporous material which further is included in a nitro resin to obtain a colourless composite. The response of this composite to diverse acid solutions was tested showing the appearance of an intense purple colour (with a colour difference higher than 160) that can be monitored by the naked eye or could be easily digitised to feed an instrumental sensor. Reversibility and resistance to washing cycles were studied with positive results. Finally, the response of the sensing composite to acid vapours was assayed, observing a colour change similar to that found in solution.

Adsorptive removal of phosphate from water using mesoporous materials: A review.

Mesoporous materials have significant potential for use as adsorbents for removal of phosphate from water. The chemical and structural properties of materials greatly affect their capacity and rate in the phosphate adsorption process. This paper reviews recent activities in the development of mesoporous materials as phosphate adsorbents. In particular, it mainly focuses on the synthesis, properties and phosphate removal efficiency of various materials with mesoporosity, including metal-coordinated amino-functionalized silicas, ammonium-functionalized silicas, metal-doped mesoporous silicas, metal oxides, metal sulfate and carbon.

Mesoporous silica chip: enabled peptide profiling as an effective platform for controlling bio-sample quality and optimizing handling procedure.

BACKGROUND: High quality clinical samples are critical for meaningful interpretation of data obtained in both basic and translational medicine. More specifically, optimized pre-analysis handling to bio-sample is crucial for avoiding biased analysis in a clinical setting. A universally applicable method for the evaluation of sample quality and pre-analysis handling is therefore in great demand. METHODS: The fingerprint pattern of low molecular weight (LMW) peptides in sera is directly associated with sample quality and handling process. Previous studies for enrichment/isolation of LMW peptides have shown that LMW peptides can be enriched by silica meso-porous material in a sensitive and high-throughput manner. Here, a peptide profile approach utilizing mesoporous silica chip-based sample preparation combined with MALDI MS analysis was used as a new platform for evaluation of bio-sample quality. Rat sera were selected as model sample and analyzed according to their LMW peptide fingerprint spectra. RESULTS: This novel method can complete the entire sample preparation procedure in a short period of time (<40 min), requires minimum amounts of sample (<10 µL), is of high sensitivity (LOD 10 ng/mL) as well as high reproducibility (CV% < 15%). According to the acquired LMW peptide spectra, we were able to distinguish the serum samples processed under different conditions (including different storage temperature, time, and freezing/thaw cycles) with the help of bioinformatics tools (principle composition analysis and significant difference analysis), and identify the samples that had significantly changed due to the inappropriate processing. Based on the percentage of significantly changed peaks in LMW peptide mass spectrum after handling, a judgment standard was established that can be used to evaluate the status of preservation of a biological sample. In addition, our principle study established recommendations for storage time, storage temperature and freeze/thaw conditions. CONCLUSION: Our novel method for analysis of bio-samples allows for effective identification of variations in composition within samples, and provides a cost-effective tool for simple sample manipulation in a clinical setting.

Asymmetric block copolymers for supramolecular templating of inorganic nanospace materials.

This review focuses on polymeric micelles consisting of asymmetric block copolymers as designed templates for several inorganic nanospace materials with a wide variety of compositions. The presence of chemically distinct domains of asymmetric triblock and diblock copolymers provide self-assemblies with more diverse morphological and functional features than those constructed by EOn POm EOn type symmetric triblock copolymers, thereby affording well-designed nanospace materials. This strategy can produce unprecedented nanospace materials, which are very difficult to prepare through other conventional organic templating approaches. Here, the recent development on the synthesis of inorganic nanospace materials are mainly focused on, such as hollow spheres, tubes, and porous oxides, using asymmetric triblock copolymers.