Facile synthesis of mesoporous WO3@graphene aerogel nanocomposites for low-temperature acetone sensing

Ordered mesoporous tungsten oxide@graphene aerogel (mWO3@GA) nanocomposites were synthesized via an interface-induced co-assembly process, which show a high selectivity and great response to acetone at low temperature.     

Protein coverage on polymer nanolayers leading to mesenchymal stem cell patterning

Interactions of gelatin and albumin with a photo-reactive diphenylamino-s-triazine bridged p-phenylene vinylene polymer (DTOPV) were examined by using surface plasmon resonance (SPR) spectroscopy to explore the effect of the polymer structure on protein coverage of DTOPV nanofilms. The SPR data revealed a significant increase of gelatin adsorption on UV-DTOPV nanofilms, while the adsorption of albumin was decreased by UV exposure in the time frame of the experiment. We also found that the selective adsorption of these proteins was highly dependent on the protein concentration; the highest selectivity of protein adsorption was obtained at the lowest concentration (3.5 μg ml(-1)), while no selective adsorption was confirmed at high concentrations (350 and 1000 μg ml(-1)). The selective attachment of mesenchymal stem cells (MSCs) was directly correlated with the selective adsorption of these proteins onto DTOPV nanofilms. The MSCs attachment onto UV-DTOPV films was promoted with only small mass coverage of gelatin, which led to MSC patterning onto the patterned DTOPV nanofilms successfully. The role of cell adhesion proteins that we found in this study will be a clue to elucidate the complex response of biomolecules on functional polymer nanolayers, and contribute to build up biocompatible surfaces on various advanced materials for the sake of cell engineering and medical implants.     

Facile synthesis of mesoporous WO3@graphene aerogel nanocomposites for low-temperature acetone sensing

Nanocomposites constructed by combining mesoporous metal oxides and graphene have received tremendous attention in wide fields of catalysis,energy storage and conversion,gas sensing and so on.Herein,we present a facile interface-induced co-assembly process to synthesize the mesoporous W03@graphene aerogel nanocomposites(denoted as mW03@GA),in which graphene aerogel(GA) was used as a macroporous substrate,mesoporous W03 was uniformly coated on both sides of graphene sheets through a solvent evaporation-induced self-assembly(EISA) strategy using diblock copolymer poly(ethylene oxide)-b-polystyrene(PEO-b-PS) as a template.The resultant mW03@GA nanocomposites possess well-interconnected macroporous graphene networks covered by mesoporous W03 layer with a uniform pore size of 19 nm,high surface area of 167 m~2/g and large pore volume of 0.26 cm~3/g.The gas sensing performance of mW03@GA nanocomposites toward acetone and other gases was studied,showing a high selectivity and great response to acetone at low temperature of 150℃,which could be developed as a promising candidate as novel sensors for VOCs detection.     

Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical properties.However,their synthesis via the flexible and scalable soft-template method remain a great challenge,due to the weak organic-inorganic interaction between the frequently used surfactants(e.g.,Pluronic-type block copolymers) and metal oxide precursors,and the low crystallization temperature of metal oxides.In this study,ordered mesoporous NiO with dual mesopores,high surface area and well-interconnected crystalline porous frameworks have been successfully synthesized via the facile solvent evaporation-induced co-assembly(EICA) method,by using lab-made amphiphilic diblock copolymer polystyrene-b-poly(4-vinylpyridine)(PS-b-P4 VP) as both the structure-directing agent(the soft template) and macromolecular chelating agents for nickel species,THF as the solvent,and nickel acetylacetonate(Ni(acac)2) as inorganic precursor.Similarly,by using Ni(acac)2 and Fe(acac)3 as the binary precursors,ordered mesoporous Fedoped NiO materials can be obtained,which have bimodal mesopores of large mesopores(32.5 nm) and secondary mesopores(4.0-11.5 nm) in the nanocrystal-assembled walls,high specific surface areas(～74.8 m~2/g) and large pore value(～0.167 cm~3/g).The obtained mesoporous Fe-doped NiO based gas sensor showed superior ethanol sensing performances with good sensitivity,high selectivity and fast response-recovery dynamics.     

Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

Ordered mesoporous Fe-doped NiO with dual mesopores, high surface area and well-interconnected crystalline porous frameworks have been synthesized via solvent evaporation-induced co-assembly (EICA) method, by using PS-b-P4VP as structure-directing agent, Ni(acac)₂ and Fe (acac)₃ as binary inorganic precursor, and showed superior ethanol sensing performances with good sensitivity, high selectivity and fast response-recovery dynamics.     

有序介孔材料:历史、现状与发展趋势

有序介孔材料是指孔径在2~50 nm之间的多孔材料, 是一类具有均匀孔径、 高有序度纳米孔道和高比表面积的新材料. 在过去30年里, 有序介孔材料的研究取得了长足的进步, 在可控合成、 结构设计和调控及功能化等方面形成了系统的理论. 同时, 其应用领域也不断被拓展, 包括能源存储与转化、 催化、 生物医药和传感等方面. 本文首先回顾了有序介孔材料的发展历史, 简要介绍发展过程中“里程碑式”的研究工作; 然后根据构效关系总结了其在不同领域应用的最新进展; 最后讨论了有序介孔材料领域进一步发展所面临的挑战与机遇, 并对未来前景进行了展望.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

Synergistic improvement of gas sensing performance by micro-gravimetrically extracted kinetic/thermodynamic parameters

A novel method is explored for comprehensive design/optimization of organophosphorus sensing material, which is loaded on mass-type microcantilever sensor. Conventionally, by directly observing the gas sensing response, it is difficult to build quantitative relationship with the intrinsic structure of the material. To break through this difficulty, resonant cantilever is employed as gravimetric tool to implement molecule adsorption experiment. Based on the sensing data, key kinetic/thermodynamic parameters of the material to the molecule, including adsorption heat −ΔH°, adsorption/desorption rate constants K_a and K_d, active-site number per unit mass N′ and surface coverage θ, can be quantitatively extracted according to physical–chemistry theories. With gaseous DMMP (simulant of organophosphorus agents) as sensing target, the optimization route for three sensing materials is successfully demonstrated. Firstly, a hyper-branched polymer is evaluated. Though suffering low sensitivity due to insufficient N′, the bis(4-hydroxyphenyl)-hexafluoropropane (BHPF) sensing-group exhibits satisfactory reproducibility due to appropriate −ΔH°. To achieve more sensing-sites, KIT-5 mesoporous-silica with higher surface-area is assessed, resulting in good sensitivity but too high −ΔH° that brings poor repeatability. After comprehensive consideration, the confirmed BHPF sensing-group is grafted on the KIT-5 carrier to form an optimized DMMP sensing nanomaterial. Experimental results indicate that, featuring appropriate kinetic/thermodynamic parameters of −ΔH°, K_a, K_d, N′ and θ, the BHPF-functionalized KIT-5 mesoporous silica exhibits synergistic improvement among reproducibility, sensitivity and response/recovery speed. The optimized material shows complete signal recovery, 55% sensitivity improvement than the hyper-branched polymer and 2 ∼ 3 folds faster response/recovery speed than the KIT-5 mesoporous silica.     

Cable-Like Core–Shell Mesoporous SnO2 Nanofibers by Single-Nozzle Electrospinning Phase Separation for Formaldehyde Sensing

In this study, we have developed a simple and efficient single-nozzle electrospinning strategy involving the phase separation of polystyrene and poly(vinylpyrrolidone) to construct cable-like core–shell mesoporous SnO₂ nanofibers. Compared with traditional multi-axial electrospinning approaches to the synthesis of core–shell nanofibers, the single-nozzle electrospinning process requires no complex multi-axial electrospinning setups or post-treatments, just drying and annealing after electrospinning. The obtained SnO₂ nanofibers show promise as a sensing material for formaldehyde at low concentrations, the detection limit being about 1 ppm. Furthermore, the nanofibers exhibited good cycling stability and selectivity, with response and recovery times toward 10 ppm formaldehyde being approximately 18 and 196 s, respectively, at an operating temperature of 195 °C.     

Nitrogen-containing mesoporous carbons prepared from melamine formaldehyde resins with CaCl2 as a template

Melamine formaldehyde resins were synthesized with encapsulated CaCl(2) as a template. Carbonization at high temperatures led to the formation of carbon materials containing N atoms. Washing with de-ionized water removed encapsulated CaCl(2), resulting in the formation of mesopores (3-30 nm) with the high surface areas (770-1300 m(2)/g). The template can be recycled and the method is simple and cost effective as compared to the hard template techniques. The mesoporous carbons containing nitrogen (NMC) thus prepared exhibited the amphipathic surfaces (both hydrophilic and lipophilic) and adsorbed great amount of water and benzene. In addition, the incorporated N atoms exhibited quite strong basicity for the adsorption of great amount of SO(2).     

Synthesis and stabilization of Prussian blue nanoparticles and application for sensors

Prussian blue (PB) nanoparticles were synthesized by two methods from FeCl2 and K3Fe(CN)6 and from FeCl3 and K3Fe(CN)6 based on the method published by Fiorito et al., and stabilized by different polymers like polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polyallylamine hydrochloride (PAH), polydiallyl-dimethyldiammonium chloride (PDDA) and polystyrene sulfonate (PSS). The effect of the monomer/Fe3+ ratio was studied regarding the average particle size and zeta-potential. The forming PB structure was checked by X-ray diffraction. The stabilization was successful for every applied polymer, but the average particle size significantly differs. Particle size distributions were determined by Malvern type nanosizer equipment and by transmission electron microscope (TEM) and zeta potential values were determined for the obtained stabile samples. The results revealed that by using FeCl2 and K3Fe(CN)6 for PB preparation particles with narrow size distribution and average diameter of 1.7 nm occurred but stabilization was necessary. By the other method the dispersion was stabile with 182 nm particles but the particle size exponentially decreased to 18 nm with increasing PVP concentration. Ultrathin nanofilms were prepared on glass support by the alternating layer-by-layer (LbL) method from PB particles and PAH. The morphology of the prepared films was investigated also by AFM. The films were immobilized on interdigitated microsensor electrodes (IME) and tested in sensing hydrogen peroxide and different acids like acetic acid, hydrochloric acid vapors.     

Ultrathin hybrid films of clay minerals

Smectites or swelling clay minerals are naturally occurring nanomaterials that can be fully delaminated to elementary clay mineral platelets in dilute aqueous dispersion. This review article gives an overview of the recent progress on how the elementary clay mineral platelets can be reorganized in monolayered or multilayered hybrid nanofilms by layer-by-layer assembly or the Langmuir-Blodgett technique. In the latter case one hybrid layer consists of one layer of elementary clay mineral platelets with a theoretical thickness of 0.96 nm, covered on one side by amphiphilic cations. The organization of the elementary clay mineral platelets and that of the adsorbed amphiphilic cations in the nanofilms has been studied in great detail by ATR-FTIR, UV-Vis and fluorescence spectroscopy, XRD and AFM. The nanofilms carry functional properties, such as chirality, optical nonlinearity and magnetism, which are due to the nature of the amphiphilic cations and to the organization of both the amphiphilic molecules and the elementary clay mineral platelets.     

A facile construction of heterostructured ZnO/Co_3O_4 mesoporous spheres and superior acetone sensing performance

The rapid development of internet and internet of things brings new opportunities for the expansion of intelligent sensors,and acetone as a major disease detection indicator(i.e.,diabetes) making it become extremely important clinical indicator.Herein,uniform mesoporous ZnO spheres were successfully synthesized via novel formaldehyde-assisted metal-ligand crosslinking strategy.In order to adjust the pore structure of mesoporous ZnO,various mesoporous ZnO spheres were synthesized by changing weight percentage of Zn(NO_3)_2·6 H_2 O to tannic acid(TA).Moreover,highly active heterojunction mesoporous ZnO/Co_3 O_4 has been fabricated based on as-prepared ultra-small Co_3 O_4 nanocrystals(ca.3 nm) and mesoporous ZnO spheres by flexible impregnation technique.Profit from nano-size effect and synergistic effect of p-n heterojunction,mesoporous ZnO/Co_3 O_4 exhibited excellent acetone sensing performance with high selectivity,superior sensitivity and responsiveness.Typically,5 wt% Co_3 O_4 embedded mesoporous ZnO sphere showed prominent acetone response(ca.46 for 50 ppm),which was about 11.5 times higher than that in pure ZnO sensing device,and it was also endowed high cyclic stability.The nanocrystals embedded hybrid material is expected to be used as promising efficient material in the field of catalysis and gas sensing.     

Tuning Fluorescent Response of Nanoscale Film With Polymer Grafting

An effective method for tuning fluorescent response of an ultrathin (5 nm) polymer film, which can be used for generation of sensing arrays, is reported. This method is distinctive in that the modification of the optical response is achieved with polymer grafting of a non‐fluorescent polymer to a fluorescent film. Using this approach, a number of films demonstrating different fluorescent emission when exposed to solvent vapors were synthesized.     

共价嫁接Ru(Ⅱ)配合物杂化材料的制备及氧气传感性能研究

利用十六烷基三甲基溴化铵制备了一种具有MSU型蠕虫状孔道结构, 同时共价嫁接了Ru(Ⅱ)配合物的介孔杂化功能材料, 并研究了其氧气传感性能. 双功能有机改性硅酸酯Bpy-Si不仅是配合物Ru(bpy)2Cl2·2H2O的一个配体, 而且通过与正硅酸乙酯的水解和共聚反应, 把Ru(bpy)2(bpy-Si)Cl2配合物通过Si—C共价键嫁接到二氧化硅的骨架上. 研究结果表明, Ru(Ⅱ)分子在杂化材料中的发光受氧气猝灭明显, 而且具有较快的响应时间, 所得材料具有作为性能优良的氧气传感材料研究的潜质. 由于介孔材料的独特孔道结构有利于氧气在载体中的扩散, 介孔样品表现出比无定形样品更高的灵敏度.     

Solution-phase synthesis of ordered mesoporous carbon as resonant-gravimetric sensing material for room-temperature H_2S detection

H_2S can cause multiple diseases and poses a great threat to human health.However,the precise detection of extremely toxic H_2S at room temperature is still a great challenge.Here,a facile solvent evaporation induced aggregating assembly(EIAA) method has been applied for the production of ordered mesoporous carbon(OMCs) in an acidic THF/H_2 O solution with high-molecular-weight poly(ethylene oxide)-b-polystyrene(PEO-b-PS) copolymers as the structure-directing agent,formaldehyde and resorcinol as carbon precursors.Along with the continuous evaporation of THF from the mixed solution,cylindrical micelles are formed in the solution and further assemble into highly ordered mesostructure.The obtained OMCs possesses a two-dimensional(2 D) hexagonal mesostructure with uniform and large pore diameter(～19.2 nm),high surface area(599 m~2/g),and large pore volume(0.92 cm~3/g).When being used as the resonant cantilever gas sensor for room-temperature H_2S detection,the OMCs has delivered not only a superior gas sensing performance with ultrafast re s ponse(14 s) and recovery(21 s) even at low concentration(2 ppm) but also an excellent selectivity toward H_2S among various common interfering gases.Moreover,the limit of detection is better than 0.2 ppm,indicating its potential application in environmental monitoring and health protection.     

含氮中孔碳材料的制备及其双氧水分解活性

以三聚氰胺和甲醛作为碳源和氮源,合成三聚氰胺甲醛树脂前驱体(2);采用模板法,以CaCl_2为模板剂,2经高温碳化处理制备孔结构发达的含氮中孔碳材料(NMC),其结构经N_2吸附/脱附、扫描电镜(SEM),X-射线衍射(XRD)和X-射线光电子能谱(XPS)表征。不同炭化温度(700℃,800℃,900℃)下所合成的NMC表面氮含量为3.85~10.80at%,比表面积为570~870m~2·g~(-1),中孔孔径为4nm和10nm。以H_2O_2分解反应作为探针反应,考察了NMC的催化活性。结果表明:NMC的催化活性随着碳化温度的升高而增大,碳化温度为900℃的NMC分解H_2O_2的升温速率为6.92℃·min~(-1),循环套用5次后,活性基本维持不变。     

Synthesis of mesoporous silica nanobamboo with highly dispersed tungsten carbide nanoparticles

By controlling the interaction between cationic surfactant micelles and ammonium metatungstate during the formation of mesoporous silica structure, highly dispersed tungsten carbide (WC) nanoparticles of 2.0 nm in diameter on mesoporous silica nanospheres were synthesized at lower concentration of ammonium metatungstate. With additional ammonium metatungstate, a novel mesoporous silica nanobamboo structure was formed with bimodal size-distributed WC nanoparticles, in which 2.0 nm WC was homogeneously distributed in nanobamboo's mesoporous silica wall and those with larger diameter (10.0-20.0 nm) were only formed on the nanobamboo's inner surface and at its internodes. The mesoporous silica nanobamboo also had a very high tensile strength due to its bamboo-like structure.     

Responsive Mesoporous Photonic Cellulose Films by Supramolecular Cotemplating

Cellulose‐based materials have been and continue to be exceptionally important for humankind. Considering the bioavailability and societal relevance of cellulose, turning this renewable resource into an active material is a vital step towards sustainability. Herein we report a new form of cellulose‐derived material that combines tunable photonic properties with a unique mesoporous structure resulting from a new supramolecular cotemplating method. A composite of cellulose nanocrystals and a urea–formaldehyde resin organizes into a chiral nematic assembly, which yields a chiral nematic mesoporous continuum of desulfated cellulose nanocrystals after alkaline treatment. The mesoporous photonic cellulose (MPC) films undergo rapid and reversible changes in color upon swelling, and can be used for pressure sensing. These new active mesoporous cellulosic materials have potential applications in biosensing, optics, functional membranes, chiral separation, and tissue engineering.     

Metal-organic frameworks-derived hierarchical ZnO structures as efficient sensing materials for formaldehyde detection

Semiconducting metal oxides have been considered as effective approach for designing high-performance chemical sensing materials. In this paper, a kind of metal-organic frameworks ZIF-8 was used as sacrificed template to prepare porous ZnO hollow nanocubes for the application in gas sensing. It is found that changing calcination temperature and solvent can greatly influence the morphology of the material, which finally affects the gas sensing performance. Acetylene-sensing properties of the sensors were investigated in detail. It can be clearly seen that the material used methanol as reaction solvent with the decomposition at 350 °C for 2 h (ZnO-350-M) showed the optimal formaldehyde-sensing behaviors compared with other materials prepared in this experiment. The dynamic transients of the ZnO-350-M-based sensors demonstrated a high response value (about 10), fast response and recovery rate (4 s and 4 s, respectively) and good selectivity towards 100 ppm (part per million) formaldehyde as well as a low detectable limit (1 ppm). As exemplified for the sensing investigation towards formaldehyde, the porous ZnO hollow nanocubes showed a significantly improved chemical sensitivity due to the highly synergistic effects from the well exposed surfaces, defect states and the robust ZnO.