Preparation of functional ordered mesoporous carbons and their application as the QCM sensor with ultra-low humidity

Ordered mesoporous carbon (OMCs) FDU-15 was synthesized through an EISA (Evaporation-Induced Self-Assembly) method, and the oxidized OMCs (FDU-15-COOH) were obtained by subsequent oxidation treatments in liquid phase to introduce functional groups. The samples were characterized by XRD, TEM, FT-IR and nitrogen adsorption-desorption test. The low humidity sensing performances of FDU-15 and FDU-15-COOH thin films were investigated by using a quartz crystal microbalance (QCM) transducer. The responses of FDU-15-COOH is higher than that of the pristine FDU-15 at very low humidity (< 729 ppm_v) with high long-term stability, implying that FDU-15-COOH is a good candidate for low humidity QCM sensor.     

FDU-15-Pt composites with different Pt loading and their electrocatalytic reduction to ultratrace nitroaromatic compounds

FDU-15 is a hexagonal mesoporous material with nanometer-sized, highly ordered arrays and large special surface area. In this work, FDU-15-Pt with 2.0%, 5.0% and 8.0% Pt loading were synthesised and used for electrochemical detection of trace nitroaromatic compounds (NACs). The FDU-15-Pt samples were characterised by CO Chemisorption, transmission electron microscopy (TEM) and X-ray diffraction (XRD). It has been demonstrated that FDU-15-Pt with 2.0% Pt loading has the smallest Pt particle size of 2.9?nm, highest Pt metal dispersion of 37.7% and largest Pt metal surface area of 21.36?m^2?g^?1. The FDU-15-Pt/PDDA modified electrode were assembled by electrostatic adsorption of Poly (diallyldimethylammonium chloride) (PDDA) and FDU-15-Pt. The 2.0% FDU-15-Pt modified sensor showed higher selectivity for NACs than those of 5.0% and 8.0% FDU-15-Pt, which were verified by electrochemical experiments. A linear response over TNT concentration ranging from 8.8?×?10^?9?M to 1.2?×?10^?5 M was exhibited with a low detection limit of 2.9?×?10^?9?M (S/N?=?3). Moreover, the proposed 2.0% FDU-15-Pt/PDDA modified sensor has been applied to the detection of NACs in spiked environmental water samples and shows promise for fast and accurate determination of trace NACs in real samples.     

Facile Synthesis of Ordered Mesoporous Zirconia for Electrochemical Enrichment and Detection of Organophosphorus Pesticides

Highly crystallized mesoporous ZrO₂ nanomaterials were synthesized by solvent evaporation induced self‐assembly approach. Ordered mesoporous ZrO₂ nanomaterials were characterized by TEM, SEM, BET, XRD and UV‐Vis spectroscopy. The obtained nanomaterials exhibit the close‐packing mesopores with average pore size of 7 nm and a highly crystallized framework with tetragonal phase. A non‐enzyme electrochemical sensor based on ordered mesoporous ZrO₂ is established for selective detection of methyl parathion (MP). The online extraction of MP is firstly achieved by ZrO₂ modified electrode at open‐circuit potential for 5 min., and the sensitive detection of MP is performed by differential pulse voltammetry (DPV) method. By comparison, DPV responses of mesoporous ZrO₂ are 40 times and 25 times larger than that of mesoporous silica and mesoporous carbon with the similar pore structure, implying the specific affinity advantage of zirconia to phosphoric group. The quantitative analysis result shows that the voltammetric currents are linear with concentrations of MP ranging from 1 ng/ml to 2 μg/ml with a detection limit of 0.53 ng/ml. The sensor also exhibits good stability and high selectivity against interfering species. The excellent analytical performances are owed to the accessible and uniform mesoporous structures, highly crystallized frameworks of ZrO₂ and its specific affinity to phosphate groups.     

Clean synthesis of biodiesel over solid acid catalysts of sulfonated mesopolymers

FDU-15-SO₃H, a solid acid material prepared from the sulfonation of FDU-15 mesoporous polymer, has been demonstrated to serve as an efficient catalyst in the esterification of palmitic acid with methanol as well as in the transesterification of fatty acid-edible oil mixture. FDU-15-SO₃H achieved an acid conversion of 99.0% when the esterification was carried out at 343 K with a methanol/palmitic acid molar ratio of 6:1 and 5 wt% catalyst loading. It was capable of giving 99.0% yield of fatty acid methyl esters (FAME) when the transesterification of soybean oil was performed at 413 K and the methanol/oil weight ratio of 1:1. FDU-15-SO₃H was further applied to the transesterification/esterification of the oil mixtures with a varying ratio of soybean oil to palmitic acid, which simulated the feedstock with a high content of free fatty acids. The yield of FAME reached 95% for the oil mixtures containing 30 wt% palmitic acid. This indicated the sulfonated mesopolymer was a potential catalyst for clean synthesis of fuel alternative of biodiesel from the waste oil without further purification.     

Quartz crystal microbalance monitoring of density changes in mesoporous TiO2 phytate films during redox and ion exchange processes

Nanofilm deposits of TiO₂ nanoparticle phytates are formed on gold electrode surfaces by ‘directed assembly’ methods. Alternate exposure of a 3-mercapto-propionic acid modified gold surface to (i) a TiO₂ sol and (ii) an aqueous phytic acid solution (pH 3) results in layer-by-layer formation of a mesoporous film. Ru(NH₃)₆³⁺ is shown to strongly adsorb/accumulate into the mesoporous structure whilst remaining electrochemically active. Scanning the electrode potential into a sufficiently negative potential range allows the Ru(NH₃)₆³⁺ complex to be reduced to Ru(NH₃)₆²⁺ which undergoes immediate desorption. When applied to a gold coated quartz crystal microbalance (QCM) sensor, electrochemically driven adsorption and desorption processes in the mesoporous structure become directly detectable as a frequency response, which corresponds directly to a mass or density change in the membrane. The frequency response (at least for thin films) is proportional to the thickness of the mass-responsive film, which suggests good mechanical coupling between electrode and film. Based on this observation, a method for the amplified QCM detection of small mass/density changes is proposed by conducting measurements in rigid mesoporous structures.     

新型有序介孔磺酸化酚醛树脂FDU-16-SO3H的合成与酸催化性能

通过氯磺酸磺化有序介孔酚醛树脂(FDU-16)制备了新型有序介孔固体酸催化剂FDU-16-SO₃H. X射线衍射(XRD)、氮气吸附以及透射电镜(TEM)等表征结果表明, 经过磺化后的固体酸催化剂依然保持了高度有序性, 大量的磺酸根基团存在于材料的骨架之中. 在酯化反应和酰基化反应中, 这种新型有序介孔固体酸催化剂表现出比工业树脂和磺酸化介孔二氧化硅等材料更高的催化活性, 这主要归因于它具有较大的比表面积、较强的酸性以及骨架的疏水性.     

Factors affecting the endo : exo ratio in diels-alder reactions of cyclopentadiene

The ratio of endo-CHO:exo-CHO in the Diels-Alder addition of a trans-αβ-unsaturated aldehyde to cyclopentadiene can be changed from 1:2 to 8:1, depending on temperature and BF₃-catalysis.     

A vapor selectivity study of microsensor arrays employing various functionalized ligand protected gold nanoclusters

We synthesized and tested four different monolayer protected gold nanoclusters (MPCs) as chemically selective interfaces for an organic vapor sensor array. The ligands chosen for capping the nano-Au particles and for selective organic vapor sorption were octanethiol, 2-naphthalenethiol, 2-benzothiazolethiol and 4-methoxythiolphenol. The same set of gold nanoclusters were tested on two different types of sensor platforms, a chemiresistor (CR) and a quartz crystal microbalance (QCM). The sensing properties of both sensor arrays were investigated with 10 organic vapors of various functional groups. Vapor sensing selectivity, dominated by the shell ligand structure of MPC, was demonstrated. The sensitivities of MPC coated CR are better than those of QCM sensors coated with the same material. The average CR/QCM amplification factors are range from 1.9 for 4-methoxythiolphenol MPC to 16.9 for octanethiol MPC. These differences in amplification factors indicate the functional group specific mechanisms for each vapor-MPC pair. The shell penetration mechanism of hydrogen-bonding vapor molecules into the 2-benzothiazolethiol capped MPC reduced the CR/QCM amplification factors. Strong attraction between MPC shell ligands can also reduce the magnitude of resistance changes during vapor sorption.     

Pore structures of ordered large cage-type mesoporous silica FDU-12s

The pore variations of ordered cage-type mesoporous silica FDU-12s have been analyzed in detail by PXRD, SAXS, nitrogen sorption, and electron crystallography. FDU-12s with a cubic symmetry (space group, Fmm) were templated by amphiphilic triblock copolymer F127 with the addition of 1,3,5-trimethylbenzene and KCl under an acidic condition. Three typical samples with different unit cell sizes, pore cage diameters, and entrance sizes were obtained from different synthesis and hydrothermal treatment temperatures, as indicated by the differences in the PXRD and SAXS patterns. The pore structure changes in the three materials were observed by nitrogen adsorption/desorption and 3-D reconstruction of HRTEM images taken from different crystal orientations. The approximate pore structures of FDU-12s can be regarded as a face-centered cubic (fcc) close-packing of spherical cages, each connected to 12 nearest neighboring cages. However, the ideal spherical model is only valid for the FDU-12s prepared at a low temperature (L-FDU-12-100). The cage shape of the FDU-12s synthesized at a high temperature deviates from perfect spheres and is accompanied by an entrance enlargement. The temperature-dependent behavior of the PEO block is discussed with regard to its influence on the micelles and hence the cage configuration. The better understanding of the formation mechanism via the combined characterization techniques and modeling may lead to a more rational approach for tuning the pore cages and entrances of the mesoporous FDU-12 materials.     

Characterization of a reservoir-type capillary optical microsensor for pCO(2) measurements

A reservoir type of capillary microsensor for pCO₂ measurements is presented. The sensor is based on the measurement of the fluorescence intensity of the anionic form of the pH indicator 1-hydroxy-3,6,8-pyrenetrisulfonate in the form of its ion pair with a quaternary ammonium base in an ethyl cellulose matrix. The glass capillary containing the reservoir sensor was prepared by immersing the tip of the optical fiber into the sensing agent very close to the sensor tip thus providing a very small volume for the sensing reaction. The purpose of the sensing approach is to regenerate the dye/buffer system by diffusion, which may be poisoned by interfering acids, or bleach by photolysis. The fresh cocktail from the reservoir takes the place of protonated form of the dye. The internal buffer system also makes the protonation-deprotonation equilibria reversible. The distal tip of the internal buffer containing reservoir is coated with a gas-permeable but ion-impermeable teflon membrane. The dynamic range for the detection of pCO₂ is between 1 and 20 hPa, which corresponds to the range of dissolved CO₂ in water. The response time is 15 s and the detection limit is 1 hPa of pCO_2. The recovery performance of this sensor can be improved by means of mechanical adjustment of the sensor tip in a micrometric scale.     

Highly Ordered Mesoporous Tungsten Oxides with a Large Pore Size and Crystalline Framework for H2S Sensing

An ordered mesoporous WO₃ material with a highly crystalline framework was synthesized by using amphiphilic poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymers as a structure‐directing agent through a solvent‐evaporation‐induced self‐assembly method combined with a simple template‐carbonization strategy. The obtained mesoporous WO₃ materials have a large uniform mesopore size (ca. 10.9 nm) and a high surface area (ca. 121 m² g^?1). The mesoporous WO₃‐based H₂S gas sensor shows an excellent performance for H₂S sensing at low concentration (0.25 ppm) with fast response (2 s) and recovery (38 s). The high mesoporosity and continuous crystalline framework are responsible for the excellent performance in H₂S sensing.     

Different experimental results for the influence of immersion angle on the resonant frequency of a quartz crystal microbalance in a liquid phase: with a comment

This paper presents different experimental results of the influence of an immersion angle (θ, the angle between the surface of a quartz crystal resonator and the horizon) on the resonant frequency of a quartz crystal microbalance (QCM) sensor exposed one side of its sensing surfaces to liquid. The experimental results show that the immersion angle is an added factor that may influence the frequency of the QCM sensor. This type of influence is caused by variation of the reflection conditions of the longitudinal wave between the QCM sensor and the walls of the detection cell. The frequency shifts, measured by varying θ, are related to the QCM sensor used. When a QCM sensor with a weak longitudinal wave is used, its resonant frequency is nearly independent of θ. But, if a QCM sensor with a strong longitudinal wave is employed, the immersion angle is a potential error source for the measurements performed on the QCM sensor. When the reflection conditions of the longitudinal wave are reduced, the influence of θ on the resonant frequency of the QCM sensor is negligible. The slope of the plot of frequency shifts (ΔF) versus (ρη)^1/2, the square root of the product of solution density (ρ) and viscosity (η), may be influenced by θ in a single experiment for the QCM sensor with a strong longitudinal wave in low viscous liquids, which can however, be effectively weakened by using the averaged values of reduplicated experiments. In solutions with a large (ρη)^1/2 region (0-55 wt% sucrose solution as an example, with ρ value from 1.00 to 1.26 g cm⁻³ and η value from 0.01 to 0.22 g cm⁻¹ s⁻¹, respectively), the slope of the plot of ΔF versus (ρη)^1/2 is independent of θ even for the QCM sensor with a strong longitudinal wave in a single experiment. The influence of θ on the resonant frequency of the QCM sensor should be taken into consideration in its applications in liquid phase.     

Materials design and sensing mechanism of novel calix[6]arene composite for sensitively detecting amine drugs

In order to improve the convenience and sensitivity of amphetamines drug testing and reduce the threat of drugs to humans, we have designed a QCM gas sensor to detect amine-containing drugs. The sensing material is designed based on the chemical nature of amine drugs. The sensing mechanism is derived from a reversible Schiff base interaction between the amino group of the drug and the carbonyl group of the novel calix[6]arene derivatives as well as the hydrogen bond interaction between amino group and hydroxyl. The new composite material was well characterized by different analytical techniques including ¹H nuclear magnetic resonance (¹H-NMR), fourier transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), transmission electron microscope (TEM), Raman spectra, powder X-ray diffraction, etc. The sensing experiments were conducted by coating the composite onto quartz crystal microbalance (QCM) transducers. The experimental results indicated that the novel calixarene derivatives and their GO complexes based on the design have excellent selectivity, high sensitivity and repeatability to β-phenylethylamine.     

Towards Vaporized Molecular Discrimination: A Quartz Crystal Microbalance (QCM) Sensor System Using Cobalt‐Containing Mesoporous Graphitic Carbon

A recent study on nanoporous carbon based materials (J. Am. Chem. Soc.­ 2012 , 134, 2864) showed that the presence of abundant graphitized sp² carbon species in the frameworks led to higher affinity for aromatic hydrocarbons than their aliphatic analogues. Herein, improved understanding of the sensitive and selective detection of aromatic substances by using mesoporous carbon (MPC)‐based materials, combined with a quartz crystal microbalance (QCM) sensor system, was obtained. MPCs were synthesized by direct carbonization of mesoporous polymers prepared from resol through a soft templating approach with Pluronic F127. The carbon‐based frameworks can be graphitized through the addition of a cobalt source to the precursor solution, according to the catalytic activity of the cobalt nanoparticles formed during the carbonization process. From the Raman data, the degree of the graphitization was clearly increased by increasing the cobalt content and elevating the carbonization temperature. From a QCM study, it was proved that the highly graphitized MPCs exhibited a higher affinity for aromatic hydrocarbons than their aliphatic analogues. By increasing the degree of graphitization in the carbon‐based pore walls, the MPCs showed both larger adsorption uptake and faster sensor response towards toxic benzene and toluene vapors.     

Studies on QCM-type NO2 Gas Sensor Based on Graphene Composites at Room Temperature

Synthetic graphene composite was modified on a transducer of quartz crystal microbalance(QCM) to fabricate a gas sensor for low concentration nitrogen dioxide(NO₂) detection. The gas sensing properties of the QCM coated with SnO₂-rGO and AgNPs-SnO₂-rGO composites were investigated when exposing QCM to low NO₂ con-centration(2.05-20.5 mg/m³) atmosphere at room temperature. The sensing performances of the QCM with AgNPs-SnO₂-rGO composites were enhanced by the introduction of Ag nanoparticles, and the QCM modified with AgNPs-SnO₂-rGO composites could detect NO₂ at room temperature.     

手性修饰的介孔树脂材料负载铂催化剂上丙酮酸乙酯的不对称氢化反应

采用氯铂酸和二氯四氨合铂为前体通过浸渍法分别制备了介孔树脂材料FDU-14负载的质量分数为5%的铂催化剂Pt/FDU-14, 并利用XRD, TEM, N₂气吸附和CO化学吸附等手段对催化剂进行了表征. 考察了经过手性分子辛可尼定修饰后的Pt/FDU-14催化剂在丙酮酸乙酯不对称氢化反应中的催化性能. 以氯铂酸为前体制备的Pt/FDU-14催化剂因其具有较小的铂粒子和较高的分散度而表现出较高的活性, 乙酸溶剂中的初始活性(TOF)可以达到21902 mol/(mol?h); 而以二氯四氨合铂为前体制备的Pt/FDU-14催化剂则具有较强的手性诱导能力, 乙酸溶剂中(R)-(+)-乳酸乙酯的光学选择性可以达到81.4% e.e.. 更重要的是, 由于FDU-14具有较强的疏水性, Pt/FDU-14催化剂在水溶剂中也表现出较高的催化性能, 并且还可以重复使用10次以上.     

Development of a sensitive detection method of cancer biomarkers in human serum (75%) using a quartz crystal microbalance sensor and nanoparticles amplification system

A simple and sensitive sensor method for cancer biomarkers [prostate specific antigen (PSA) and PSA-alpha 1-antichymotrypsin (ACT) complex] analysis was developed, to be applied directly with human serum (75%) by using antibody modified quartz crystal microbalance sensor and nanoparticles amplification system. A QCM sensor chip consisting of two sensing array enabling the measurement of an active and control binding events simultaneously on the sensor surface was used in this work. The performance of the assay and the sensor was first optimised and characterised in pure buffer conditions before applying to serum samples. Extensive interference to the QCM signal was observed upon the analysis of serum. Different buffer systems were then formulated and tested for the reduction of the non-specific binding of sera proteins on the sensor surface. A PBS buffer containing 200 μg mL⁻¹ BSA, 0.5 M NaCl, 500 μg mL⁻¹ dextran and 0.5% Tween 20, was then selected which eliminated the interfering signal by 98% and enabled the biomarker detection assay to be performed in 75% human serum. By using Au nanoparticles to enhance the QCM sensor signal, a limit of detection of 0.29 ng mL⁻¹ PSA and PSA-ACT complex (in 75% serum) with a linear dynamic detection range up to 150 ng mL⁻¹ was obtained. With the achieved detection limit in serum samples, the developed QCM assay shows a promising technology for cancer biomarker analysis in patient samples.     

Amino-functionalized mesoporous silica modified glassy carbon electrode for ultra-trace copper(II) determination

This paper described a facile and direct electrochemical method for the determination of ultra-trace Cu²⁺ by employing amino-functionalized mesoporous silica (NH₂-MCM-41) as enhanced sensing platform. NH₂-MCM-41 was prepared by using a post-grafting process and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and fourier transform infrared (FTIR) spectroscopy. NH₂-MCM-41 modified glassy carbon (GC) electrode showed higher sensitivity for anodic stripping voltammetric (ASV) detection of Cu²⁺ than that of MCM-41 modified one. The high sensitivity was attributed to synergistic effect between MCM-41 and amino-group, in which the high surface area and special mesoporous morphology of MCM-41 can cause strong physical absorption, and amino-groups are able to chelate copper ions. Some important parameters influencing the sensor response were optimized. Under optimum experimental conditions the sensor linearly responded to Cu²⁺ concentration in the range from 5 to 1000 ng L⁻¹ with a detection limit of 0.9 ng L⁻¹ (S/N = 3). Moreover, the sensor possessed good stability and electrode renewability. In the end, the proposed sensor was applied for determining Cu²⁺ in real samples and the accuracy of the results were comparable to those obtained by inductively coupled plasma optical emission spectrometry (ICP-OES) method.     

Quartz Crystal Microbalance for Selenite Sensing Based on Growth of Cadmium Selenite Crystals Immobilized on a Monolayer of Phosphorylated 11-Mercapto-1-Undecanol

 A quartz crystal microbalance (QCM) sensor for selenite ions in aqueous solution was constructed based on crystal formation of cadmium selenite, immobilized with a self-assembly monolayer (SAM) of phosphorylated 11-mercapto-1-undecanol (MUD) on a QCM gold electrode surface. The mass change caused by the selective adsorption of selenite ions on the cadmium selenite crystals at the solid/solution interface was detected by the QCM. The response (−ΔF) of the modified QCM oscillator increased with increasing selenite ion concentrations in sample solutions, ranging from 9.7×10⁻⁵ to 9.0×10⁻⁴ M at pH 7.4. The synthetic process of anchoring cadmium selenite crystals on the phosphorylated MUD organic film was also followed by using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The atomic concentrations measured by XPS confirmed the crystal growth of cadmium selenite on the phosphorylated MUD SAM at the QCM gold electrode surface. From the AFM images, changes in surface topographic features were followed: the MUD SAM and phosphorylated MUD on the QCM gold electrode had similar surface roughness; however the difference for the cadmium selenite film on the phosphorylated MUD SAM was clearly seen. The observed QCM frequency change of the modified QCM oscillator per unit time was found to be proportional to the square of the supersaturation of cadmium selenite, indicating the crystal growth of cadmium selenite at the solid/solution interface. The modified QCM oscillator exhibited selectively strong QCM response to SeO₃ ²⁻ ion. In contrast, the responses to tested interfering anions were almost negligible. The order of anion selectivities of the present modified QCM sensor was SeO₃ ²⁻≫CO₃ ²⁻>SeO²⁻ ₄, SO₄ ²⁻, Br⁻, I⁻, NO₃ ⁻. These selectivities were basically attributable to the differences in solubility products and solubilities for the salts of each anion with cadmium (II) ion. Received May 12, 1998. Revision December 29, 1998.     

Acoustic Wave Mass Sensors

The application of acoustic wave microsensors for mass sensing will be reviewed with focus on the quartz crystal microbalance (QCM) and surface acoustic wave (SAW) devices. The use of QCM and SAW devices in chemical sensing as well as in the determination of solid and liquid properties will be described. In chemical sensing, it is unlikely that a single sensor with a single coating will display a selective and reversible response to a given analyte in a mixture. Alternative strategies such as the use of sensor arrays and the use of sampling devices can be used to improve performance. QCM sensors (QCMs) will oscillate under liquids; their use in under-liquid sensing will be discussed. This revised version was published online in July 2006 with corrections to the Cover Date.