Synthesis and Characterization of Chromium‐Doped Mesoporous Tungsten Oxide for Gas Sensing Applications

SBA‐15 (2D hexagonal structure) and KIT‐6 (3D cubic structure) silica materials are used as templates for the synthesis of two different crystalline mesoporous WO₃ replicas usable as NO₂ gas sensors. High‐resolution transmission electron microscopy (HRTEM) studies reveal that single‐crystal hexagonal rings set up the atomic morphology of the WO₃ KIT‐6 replica, whereas the SBA‐15 replica is composed of randomly oriented nanoparticles. A model capable of explaining the KIT‐6 replica mesostructure is described. A small amount of chromium is added to the WO₃ matrix in order to enhance sensor response. It is demonstrated that chromium does not form clusters, but well‐distributed centers. Pure WO₃ KIT‐6 replica displays a higher response rate as well as a lower response time to NO₂ gas than the SBA‐15 replica. This behavior is explained by taking into account that the KIT‐6 replica has a higher surface area as demonstrated by Brunauer–Emmett–Teller analyses and its mesostructure is fully maintained after the screen‐printing step involved in sensors preparation. The presence of chromium in the material results in a shorter response time and improved sensor response to the lowest NO₂ concentrations tested. Electrical differences related to mesostructure are reduced as a result of additive introduction.     

Alizarin Complexone on Nanocrystalline TiO2: A Heterogeneous Approach to Anion Sensing

A novel, heterogeneous approach to “naked‐eye” colorimetric and spectrophotometric anion sensing is demonstrated, employing the molecular receptor alizarin complexone adsorbed onto a nanocrystalline, mesoporous TiO₂ film. pH buffer action intrinsic to the TiO₂ film allows dip sensing in aqueous solutions. This heterogeneous sensing system exhibits a high selectivity to F^– and CN^– anions, high sensitivity, a rapid response time, and excellent reusability.     

Nanoscale Membrane Strips for Benign Sensing of HgII Ions: A Route to Commercial Waste Treatments

The integration of actively‐functional receptors into nanoscale networks outperformed competent detection devices and other ion‐sensing designs. Synthesis of azo chromophores with long hydrophobic tails showed an ecofriendly sensing and an extreme selectivity for divalent mercury analytes. In order to tailor the tip to Hg^II ion‐sensing functionality, we manipulated the chromophores into nanoscale membrane discs, which led to small, easy‐to‐use optical sensor strips. The design of these hydrophobic probes into ordered pore‐based membranes transformed the ion‐sensing systems into smart, stable assemblies and portable laboratory assays. The nanosensor membrane strips with chemical and mechanical stability allowed for reversible, stable and reusable detectors without any structural damage, even under rigorous chemical treatment for several numbers of repeated cycles. The optical membrane strips provided Hg^II ion‐sensing recognition for both cost‐ and energy‐saving systems. Indeed, the synthetic strips proved to have an efficient ability for various analytical applications, targeting especially for on‐site and in situ chemical analyses, and for continuous monitoring of toxic Hg^II ions. On the proximity‐sensing front, these miniaturized nanomembrane strips can revolutionize the consumer and industrial market with the introduction of the probe surface‐mount naked‐eye ion‐sensor strips.     

Nanocrystalline Metal Oxides from the Injection of Metal Oxide Sols in Coordinating Solutions: Synthesis,Characterization, Thermal Stabilization,Device Processing,and Gas‐Sensing Properties

Metal oxide (SnO₂, TiO₂, In₂O₃, ZnO) sols are prepared by various sol–gel processes in such a way as to hinder the condensation reactions. The obtained sols are injected at 160 °C into a solution of tetradecene and dodecylamine, and kept under heating for different periods of time. Depending on the starting sol, variously crystallized oxide nanoparticles are obtained, whose phase compositions and chemical structure have been studied by X‐ray diffraction (XRD) and Fourier transform IR spectroscopy. The elimination of the organic residuals has been carried out by thermal treatment, and the thermal evolution of the nanoparticles has been studied by thermal analyses and Raman spectroscopy. High‐resolution transmission electron microscopy studies coupled with XRD measurements show that the thermal treatment does not markedly affect the particle size, which remains in the nanometer‐sized regime (from 3.5 to 8.5 nm, depending on the system), except in the case of ZnO. The thermally purified and stabilized powders, drop‐coated onto alumina substrates with pre‐deposited electrical contacts, have been tested as gas‐sensing devices, displaying outstanding sensing properties even at room temperature.     

Solventless Acid‐Free Synthesis of Mesostructured Titania: Nanovessels for Metal Complexes and Metal Nanoclusters

A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The mesostructured titania is obtained by employing self‐assembled structures of non‐ionic alkyl‐poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(IV ) ethoxide and the surfactant (C₁₂EO₁₀) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO‐head groups to form a new titanotropic amphiphile. The new amphiphiles self‐assemble into titanium nanocluster–surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble‐metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X‐ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV‐vis spectroscopy, and micro‐Raman analysis.     

Optical Sensor Based on Nanomaterial for the Selective Detection of Toxic Metal Ions

A heterogeneous “naked‐eye” colorimetric and spectrophotometric cation sensor, SNT‐ 1 , was prepared by immobilization of the azo‐coupled macrocyclic receptor 1 on a silica nanotube (SNT) via sol–gel reaction. The optical sensing ability of SNT‐ 1 was studied by addition of metal ions such as Ag⁺, Co²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Fe³⁺, Cu²⁺, and Hg²⁺ (all as nitrates) in water. Upon the addition of Hg²⁺ in suspension SNT‐ 1 resulted in a color change from yellow to violet. This is novel rare example for chromogenic sensing of a specific metal ion by inorganic nanotubes. On the other hand, no significant changes in color were observed in the parallel experiments with Co²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Fe³⁺, Cu²⁺, and Ag⁺. These findings confirm that SNT‐ 1 can be useful as chemosensors for selective detection of Hg²⁺ over a range of metal ions. More interestingly, after addition of NO₃^– and ClO₄^– SNT‐ 1 was observed to change color from yellow to violet and pink, respectively. However, no color changes were observed upon addition of Cl^–, Br^–, I^–, SCN^–, or SO₄^2–. Furthermore, the extraction ability of SNT‐ 1 was also estimated by measuring the amount of Hg²⁺ adsorbed by ion chromatography, showing that 95 % of the Hg²⁺ ion is extracted by SNT‐ 1 . This suggests that SNT‐ 1 is potentially useful as a stationary phase for the separation of Hg²⁺ in liquid chromatography. In order to extend the above performance to a portable chemosensor kit, SNT‐ 1 was coated as a thin film of 50 μm thickness onto a glass substrate. The supported SNT‐ 1 also changed from yellow to violet when dipped into Hg²⁺ solution. On the other hand, no significant change in color was observed in other metal‐ion solutions. The results imply that the supported SNT‐ 1 is applicable as a portable colorimetric sensor for detection of Hg²⁺ in the field.     

Second Generation Nanostructured Metal Oxide Matrices to Increase the Thermal Stability of CO and NO2 Sensing Layers Based on Iron(II) Phthalocyanine

An iron(II) phthalocyanine (FePc) complex solubilized by decylamine (DA) and benzylamine (BA) is incorporated into a nanoparticulate metal oxide matrix to develop optical sensor films sensitive to NO₂ and CO. Eleven amine solvents have been tested as N‐donor ligands that permit ligand exchange with the gas molecules. We have systematically investigated the suitability of different N‐donor ligands, studied the thermal stability of the NO₂‐ and CO‐sensing films at 4, 25, 60, and 80 °C by photometry, and corroborated our findings by using NMR experiments. A satisfactory thermal stability of the films has not been obtained for chemically unmodified nanoparticulate metal oxide matrices. We have therefore developed a second generation of nanostructured metal oxide supports that show increased thermal stability and adequate sensitivity to NO₂ and CO. These novel nanostructured matrices have been chemically modified using amines, alumina oligomers, and/or anti‐gas‐fading agents. These components have been integrated into the metal oxide matrices to avoid degradation of the optical films and to preserve their sensitivity.     

A Novel Mesoporous CaO‐Loaded In2O3 Material for CO2 Sensing

A mesoporous CaO‐loaded In₂O₃ material (with Ca/In₂O₃ ratios ranging from 2.5 to 8.5 at %) has been synthesized and used as resistive gas sensor for the detection of CO₂. A nanostructured In₂O₃ matrix has been obtained by hard template route from the SBA‐15 silica template. Additive presence does not distort the lattice of In₂O₃, which crystallizes in the Ia3 cubic space group. It has been proved by XRD, HRTEM, Raman and XPS measurements that samples contain not only CaO but also CaCO₃ in calcite phase as a consequence of CaO carbonation. Pure In₂O₃ based sensors are low sensitive to CO₂, whereas those containing the additive show an important response in the 300–5000 ppm range of gas concentrations. As seen by DRIFTS, the electrical response arises from the interaction between CO₃^2– and CO₂, yielding bicarbonates products. The reaction is water‐assisted, so that hydration of the sensing material ensures sensor reliability whilst its dehydration would inhibit sensor response. The use of CaCO₃ instead of CaO does not cause significant differences in electrical and DRIFTS data, which corroborates the important role played by carbonate species in the sensing mechanism.     

A Highly Sensitive Hybrid Colorimetric and Fluorometric Molecular Probe for Cyanide Sensing Based on a Subphthalocyanine Dye

A highly sensitive, selective colorimetric and fluorometric molecular probe based on a subphthalocyanine dye has been developed for cyanide‐anion determination in aqueous solution. It has also been shown that a carboxysubphthalocyanine derivative can be covalently anchored to transparent mesoporous nanocrystalline high‐surface‐area metal oxide films to detect low concentrations of cyanide anion in pure water with no interference from other anionic or cationic species.     

One‐Pot Synthesis and Hierarchical Assembly of Hollow Cu2O Microspheres with Nanocrystals‐Composed Porous Multishell and Their Gas‐Sensing Properties

Hierarchical assembly of hollow microstructures is of great scientific and practical value and remains a great challenge. This paper presents a facile and one‐pot synthesis of Cu₂O microspheres with multilayered and porous shells, which were organized by nanocrystals. The time‐dependent experiments revealed a two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ were formed first due to the Ostwald ripening and then reduced by glutamic acid, the resultant Cu₂O nanocrystals were deposited on the hollow intermediate microspheres and organized into finally multishell structures. The special microstructures actually recorded the evolution process of materials morphologies and microstructures in space and time scales, implying an intermediate‐templating route, which is important for understanding and fabricating complex architectures. The Cu₂O microspheres obtained were used to fabricate a gas sensor, which showed much higher sensitivity than solid Cu₂O microspheres.     

Inside Front Cover: One‐Pot Synthesis and Hierarchical Assembly of Hollow Cu2O Microspheres with Nanocrystals‐Composed Porous Multishell and Their Gas‐Sensing Properties (Adv. Funct. Mater. 15/2007)

On p. 2766, Qinshan Zhu and co‐workers report on multishell hollow Cu₂O microspheres that are synthesized by a facile and one‐pot solvothermal route. A two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ are formed first followed by reduction to Cu₂O by glutamic acid, leads to the special multishell and hollow microstructures. Interestingly, a Cu₂O gas sensor fabricated with the multishell microspheres shows a much higher sensitivity to ethanol than solid Cu₂O microspheres. Hierarchical assembly of hollow microstructures is of great scientific and practical value and remains a great challenge. This paper presents a facile and one‐pot synthesis of Cu₂O microspheres with multilayered and porous shells, which were organized by nanocrystals. The time‐dependent experiments revealed a two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ were formed first due to the Ostwald ripening and then reduced by glutamic acid, the resultant Cu₂O nanocrystals were deposited on the hollow intermediate microspheres and organized into finally multishell structures. The special microstructures actually recorded the evolution process of materials morphologies and microstructures in space and time scales, implying an intermediate‐templating route, which is important for understanding and fabricating complex architectures. The Cu₂O microspheres obtained were used to fabricate a gas sensor, which showed much higher sensitivity than solid Cu₂O microspheres.     

Designing the Width and Texture of Vanadium Oxide Macroscopic Fibers: Towards Tuning Mechanical Properties and Alcohol‐Sensing Performance

Macroscopic vanadium oxide fibers have been fabricated by an extrusion process. By varying the shear rate associated with the gel extrusion process we have been able to tune the diameter and transversal geometry of the fibers at macroscopic length scales. At the mesoscopic length scale, small‐angle X‐ray scattering (SAXS) analysis provides evidence for the possibility of fine tuning the degree of alignment of the V₂O₅ ribbons inside the fibers; this alignment is clearly improved upon increasing the shear rate. Nitrogen physisorption measurements (Brunauer–Emmett–Teller (BET)) indicate that the as‐synthesized fibers exhibit poor mesoporosity, largely due to the presence of remaining poly(vinyl alcohol) (PVA) entities. Microscopically, from XRD measurements, the fiber structure appears to be semi‐crystalline. ⁵¹V magic angle spinning NMR (MAS NMR) spectroscopy reveals that the local environment of ⁵¹V is typical of the structure of a V₂O₅·1.8 H₂O xerogel. We demonstrate here that the alignment of the nanoribbon subunits can be tuned via the shear rate applied during the extrusion process, which provides a good handle for tuning the mechanical and sensing properties of the as‐synthesized fibers.     

The Synergistic Effect of Prussian‐Blue‐Grafted Carbon Nanotube/Poly(4‐vinylpyridine) Composites for Amperometric Sensing

Because of its high activity and selectivity toward the reduction of hydrogen peroxide and oxygen, Prussian blue (PB) is usually considered as an “artificial enzyme peroxidase” and has been extensively used in the construction of electrochemical biosensors. In this study, we report on the construction of amperometric biosensors via grafting PB nanoparticles on the polymeric matrix of multiwalled carbon nanotubes (MWCNTs) and poly(4‐vinylpyridine) (PVP). The MWCNT/PVP/PB composite films were synthesized by casting films of MWCNTs wrapped with PVP on gold electrodes followed by electrochemical deposition of PB on the MWCNT/PVP matrix. The electrode modified with the MWCNT/PVP/PB composite film shows prominent electrocatalytic activity toward the reduction of hydrogen peroxide, which can be explained by the remarkable synergistic effect of the MWCNTs and PB. Therefore, fast amperometric response of this sensor to hydrogen peroxide was observed with a detection sensitivity of 1.3 μA μM ^–1 of H₂O₂ per square centimeter area and a detection limit of 25 nM . These results are much better than those reported for PB‐based amperometric sensors. In addition, a glucose biosensor fabricated by casting an additional glucose oxidase (GOD) containing Nafion film above the MWCNT/PVP/PB composite film shows promise for the sensitive and fast detection of glucose. The observed high stability, high sensitivity, and high reproducibility of the MWCNT/PVP/PB composite films make them promising for the reliable and durable detection of hydrogen peroxide and glucose.     

In Situ Growth of Mesoporous SnO2 on Multiwalled Carbon Nanotubes: A Novel Composite with Porous‐Tube Structure as Anode for Lithium Batteries

A novel mesoporous‐nanotube hybrid composite, namely mesoporous tin dioxide (SnO₂) overlaying on the surface of multiwalled carbon nanotubes (MWCNTs), was prepared by a simple method that included in situ growth of mesoporous SnO₂ on the surface of MWCNTs through hydrothermal method utilizing Cetyltrimethylammonium bromide (CTAB) as structure‐directing agents. Nitrogen adsorption–desorption, X‐ray diffraction and transmission electron microscopy analysis techniques were used to characterize the samples. It was observed that a thin layer tetragonal SnO₂ with a disordered porous was embedded on the surface of MWCNTs, which resulted in the formation of a novel mesoporous‐nanotube hybrid composite. On the base of TEM analysis of products from controlled experiment, a possible mechanism was proposed to explain the formation of the mesoporous‐nanotube structure. The electrochemical properties of the samples as anode materials for lithium batteries were studied by cyclic voltammograms and Galvanostatic method. Results showed that the mesoporous‐tube hybrid composites displayed higher capacity and better cycle performance in comparison with the mesoporous tin dioxide. It was concluded that such a large improvement of electrochemical performance within the hybrid composites may in general be related to mesoporous‐tube structure that possess properties such as one‐dimensional hollow structure, high‐strength with flexibility, excellent electric conductivity and large surface area.     

面向智能家居的嵌入式传感网网关的研究与设计

为了实现家庭内部网路与Internet以及GSM网的互联,提出了一种嵌入式无线智能家居网关系统的设计方案。该网关系统的硬件平台以ARM920T核处理器S3C2440为主处理器,采用ZigBee协议建家庭内部网络,而且通过以太网模块和GSM模块接入外部网络。软件平台采用Linux操作系统,通过交叉编译设计网关的应用程序。最后,以Qtopia Core为嵌入式GUI,进行家庭网关监测应用软件的功能需求分析,设计图形用户界面,实现家庭内部信息的查询。基于ARM9和Linux的嵌入式网关系统,可扩展性强,数据处理速度快,使用简单,能够对家庭网络内部多项环境信息进行监测。     

A Protein‐Nanocellulose Paper for Sensing Copper Ions at the Nano‐ to Micromolar Level

Tracing heavy metals is a crucial issue in both environmental and medical samples. In this work, a sensing biomolecule, the cyanobacterial C‐phycocyanin (CPC), is integrated into a nanocellulose matrix, and with this, a biosensor for copper ions is developed. The assembly of CPC‐functionalized nanocellulose into a red‐fluorescent, copper‐sensitive hybrid film “CySense”, enhances protein stability and facilitates the reuse and the regeneration of the sensor for several cycles over 7 days. CySense is suitable for the analysis of complex medical samples such as human serum filtrate. The reported biosensor reliably detects copper ion contents with a lower detection limit of 200 × 10^?9m and an IC50 of 4.9 × 10^?6m as changes in fluorescence emission intensity that can be measured with a fluorimeter or a microarray laser scanner.     

智能材料中特种光纤的研究进展

本文介绍了用于智能材料中几种光纤的结构及使用情况，讨论了今后可能的发展趋势。     

Laser Micro/Nano-Structuring Pushes Forward Smart Sensing: Opportunities and Challenges

Post-pandemic era poses an imperative demand on progressive sensing devices whose performance largely relies on the morphologies and structures of sensing materials. Despite substantial efforts and advances that have been made in sensing materials with different micro/nanoscale dimensionalities, it is still challenging to couple micro/nano platforms with sensing materials together for the precise and scalable production of high-performance sensors toward practical application scenarios. Owing to noncontact, precise, and high-efficiency features, laser micro/nanofabrication offers a promising solution to achieve high-quality micro/nano sensors with novel functionalities in a relatively short time. Herein, this review begins with a glance over the development of micro/nano-structured sensors and briefly discusses the importance of laser micro/nanostructuring technology for micro/nano-engineering of the sensors. Next, representative processing methods are elaborated in detail from a laser-pulse-type point of view, with potential applications toward chemical, physical, and biological targets based on different sensing mechanisms summarized. Finally, the perspectives on the opportunities and challenges of laser micro/nanostructuring strategies and materials for micro/nanosensors are presented.     

Synthesis of New RuO2@SiO2 Composite Nanomaterials and their Application as Catalytic Filters for Selective Gas Detection

RuO₂@SiO₂ nanomaterials are prepared using hybrid mesostructured silica (EtO)₂P(O)(CH₂)₃SiO_1.5/x SiO₂ (x = 9, 16) by anchoring the metal precursor [Ru(COD)(COT)] (COD is 1,3‐cyclooctadiene, COT is 1,3,5‐cyclooctatriene) inside the pores of the organized silica matrix through the phosphonate moieties. Following this task, the nanoparticles are fabricated by i) decomposing the metal precursor with hydrogen at room temperature in tetrahydrofuran to achieve ruthenium nanoparticles and ii) thermally treating the ruthenium particles in silica at 450 °C in air to fabricate RuO₂. The materials containing Ru and RuO₂ nanoparticles are characterized by elemental analysis, transmission electron microscopy (TEM), X‐ray diffraction (XRD), nitrogen sorption measurements, and ³¹P and ¹³C NMR. The obtained RuO₂@SiO₂ nanomaterials are evaluated as catalytic filters when deposited onto gas sensors for the preferential detection of propane in the multicomponent gas mixture propane/carbon monoxide/nitrogen dioxide.     

Learning from Nature: Constructing a Smart Bionic Structure for High-Performance Glucose Sensing in Human Serums

Traditional noble metal-based catalysts for glucose sensing usually suffer from easy deactivation by halides and weak sensing properties. To unravel these limits, herein, a novel nature-inspired design concept (mimicking a “rock–soil–grass” geotexture system) is purposed to build a free-standing hierarchical micro-nano architecture. Thanks to the design (rigid and conductive Ni foam) (“rock”, underlayer, rough and highly disordered graphene nanosheets (GNSs) (“soil”, middle-layer), and strong catalytic activity of multiscale grass-like Co₃O₄ (“grass”, top-layer), the bionic structure achieves ultra-high sensitivity, a low limit of detection (120 × 10^?9 m ), an extremely short response time, broad linear ranges (two stages: 1–10 000 and 10 000–30 040 µm ), good anti-Cl^?-poisoning and anti-interference properties, and long-term stability. Besides the structural design, the “gotong-royong” effects (the strong interface coupling and charge transfer between GNSs and Co₃O₄ and energetically favorable glucose adsorption on Co₃O₄) also contribute to the high sensing properties, as verified by kinetic studies and density functional theory simulation. To determine human blood glucose levels, the self-made glucometer with the self-developed software demonstrates an ultra-high recovery rate (99.0–100.9%), validating the potential for high-performance blood-glucose sensing.