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.     

Synthesis,Characterization, and Application of Mesoporous Silica Functionalized with Alkyl‐Hydroperoxides

A variety of alkyl hydroperoxides such as tert‐butyl‐, tert‐octyl‐, 1‐cyclopentyl‐, 1‐cyclohexyl‐, 3,4‐disubstituted‐1‐cyclohexyl‐, n‐propyl, and n‐undecyl‐hydroperoxides have been functionalized onto ordered mesoporous silica, SBA‐15, from the corresponding covalently anchored synthons. All the tert‐hydroperoxides are prepared by autoxidation using molecular O₂ and an initiator, whereas other hydroperoxides are obtained by reaction with H₂O₂. For autoxidation, the use of a combination of an azoinitiator (AIBN) and N‐hydroxyphthalimide increased the hydroperoxide yield compared with using the azoinitiator alone. Synthons containing two or more tert‐ and sec‐hydrogens lead to higher peroxide yield compared to synthons with a single reactive site. Oxidation of Si–OH (silanol groups) with acidic H₂O₂ at low temperature produces Si–OOH. Reusability of these alkyl hydroperoxides is carried out by oxidation of alcohols obtained from the corresponding alkyl hydroperoxides using H₂O₂. Both the covalently anchored synthons and the resulting hydroperoxides are thoroughly characterized by powder X‐ray diffraction, ¹³C cross‐polarized magic angle spinning NMR, TG/DTA, Fourier transform IR spectroscopy, sorption, and surface area measurements. The quantification of the amount of alkyl hydroperoxide was carried out by iodometric titration using a thio solution. The hydroperoxides exhibit high activity for the epoxidation of styrene to styrene oxide and exhibit reasonably high efficiency for oxygen transfer.     

Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.     

Surfactant‐Assisted Synthesis of Alumina with Hierarchical Nanopores

Using surfactant‐assisted synthesis, aluminas with hierarchical nanopores are produced. The hierarchical structures are composed of mesopores of 4 nm diameter, and macropores with diameters of about 300 nm. The structures were found to be stable to the thermal removal of the surfactant. Synthesis factors affecting the appearance of the hierarchically structured alumina material are presented. A potential mechanism for the formation of the uniquely structured aluminas is proposed.     

Synthesis and Characterization of Bifunctionalized Ordered Mesoporous Materials

Direct synthesis (co‐condensation reaction) and post‐synthesis reaction (grafting) are combined for the first time to efficiently fabricate bifunctionalized ordered mesoporous materials (OMMs). Ethylenediamine‐containing OMMs (ED‐MCM‐41) were first synthesized via direct synthesis and then further modified by the phenyl (PH) group in a supercritical fluid (SCF) medium via grafting reaction, resulting in OMMs with ED and PH groups (PH‐ED‐MCM‐41). X‐ray diffraction (XRD) patterns, N₂ sorption properties, transmission electron microscopy (TEM), ²⁹Si and ¹³C magic angle spinning (MAS) NMR, chemical analysis, and hydrothermal treatment were used to characterize the bifunctionalized materials. Experiments show that bifunctionalized OMMs can be efficiently prepared by modifying the directly synthesized monofunctionalized OMMs via grafting reaction in a supercritical fluid medium. Both functional groups are distributed uniformly at the surfaces. The advantage of bifunctionalized OMMs over monofunctionalized OMMs was illustrated by introducing thiol groups into ED‐MCM‐41 materials and the subsequent formation of CdS nanocrystals inside thiol‐ and ED‐functionalized MCM‐41 (HS‐ED‐MC‐41). Because of the variety of the functional groups that can be introduced into OMMs by direct synthesis or post‐synthesis reaction, it is expected that the present strategy could provide a generally applicable approach to the design of OMMs with two functional groups.     

Single‐Source Precursors For Synthesizing Bifunctional Periodic Mesoporous Organosilicas

A new class of bifunctional periodic mesoporous organosilicas (PMOs) composed of organosilicate building blocks with two different silicon sites have been synthesized from the single‐source bifunctional organosilica precursors tris(triethoxysilylethyl)ethoxysilane and bis(triethoxysilylethyl)diethoxysilane, respectively denoted MT³‐PMO and DT²‐PMO. The synthesis of these PMOs is achieved by the co‐assembly of a triblock‐copolymer Pluronic P123 template with the bifunctional organosilica precursor under acid‐catalyzed and inorganic‐salt‐assisted conditions. After template removal through solvent extraction, the MT³‐PMO and DT²‐PMO so obtained show well‐ordered mesopores and display large pore diameters (6–7 nm) and pore volumes (0.6–0.8 cm³ g^–1) with a narrow pore‐size distribution and high surface areas (700–800 m³ g^–1).     

Nanosensor Design Packages: A Smart and Compact Development for Metal Ions Sensing Responses

With recent advances in mesostructured materials and nanotechnologies, new methods are emerging to design optical sensors and biosensors, and to develop highly sensitive solid sensors. Here, highly sensitive, low cost, simple nanosensor designs for naked‐eye detection of toxic metal ions are successfully developed by the immobilization of commercially available α,β,γ,δ‐tetrakis(1‐methylpyridinium‐4‐yl)porphine p‐toluenesulfonate (TMPyP) and diphenylcarbazide (DPC), and chemically synthesized 4‐n‐dodecyl‐6‐(2‐thiazolylazo) resorcinol (DTAR) and 4‐n‐dodecyl‐6‐(2‐pyridylazo) phenol (DPAP) chromophore molecules into spherical nanosized cavities and surfaces. A rational strategy was crucial to develop optical nanosensors that can be used to control accurate recognition and signaling abilities of analyte species for ion‐sensing purposes. This is the first reported evidence of the significant key factors of the development of receptors as ‘indicator dyes' and surface‐confinement materials as ‘carriers' to broadening the applicability of optical chemical sensors for selective discrimination of trace levels of toxic analytes. In all the nanosensor design techniques presented here, a dense pattern of immobilized hydrophobic ‘neutral' and hydrophilic ‘charged' chromophores with intrinsic mobility, as a result of extremely robust constructed sequences on nanoscale structures, is a key to enhancing the sensing functionality of optical nanosensors. These nanosensor designs can be used as cage probe sinks with reliable control, for the first time, over the colorimetric recognition of cadmium ions to low levels of concentration in the range of 10^–9 to 10^–10 M . Optimization of control sensing conditions is established to achieve enhanced signal response and color intensities. These chemical nanosensors are reversible and have the potential to serve effectively in on‐site field analysis of environmental samples, which eliminates the necessity for instrument‐dependent analysis. Moreover, these new classes of optical cage sensors exhibit long‐term stability of signaling and recognition functionalities that in general provide extraordinary sensitivity, selectivity, reusability, and fast kinetic detection and quantification of various deleterious metal ions in our environment.     

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.     

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.     

Transparent Mesoporous Nanocomposite Films for Self‐Cleaning Applications

A versatile approach is studied for the elaboration of TiO₂ based photocatalytic coatings for self‐cleaning applications on transparent substrates. The basic principle of the synthesis relies on the use of preformed TiO₂ colloidal particles that are further dispersed within a transparent silica binder with a mesoporous structure. Film porosity in the nanometer range is controlled by achieving the sol–gel silica condensation around self‐organized micellar assemblies of a templating copolymer surfactant. The latter also acts as a stabilizer for the TiO₂ particles, thus preserving their high dispersion within the film so that excellent optical properties are maintained even for high TiO₂ loading (up to 50 %). Studies of photodegradation kinetics show that such mesoporous films are at least 15 times more active than films synthesized with a usual microporous silica binder. Moreover, the measured quantum‐yield efficiency (1.1 %) is found to be among the highest reported up to now. Improved photoactivity of the films is discussed as resulting from the closer proximity between the organic molecules and the surface of the TiO₂ crystallites as well as the improved diffusion rate of water and oxygen through the interconnected pore network.     

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.     

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.     

Synthesis and Characterization of a Composite Zeolite–Metglas Carbon Dioxide Sensor

The synthesis of a faujasite–Metglas composite material that can be used in gas‐sensing applications is presented. A continuous faujasite film was synthesized on a Metglas magnetoelastic strip using the secondary growth method. The ability of the new composite to remotely sense carbon dioxide in a nitrogen atmosphere at room temperature over a wide range of concentrations is demonstrated by monitoring the changes in the resonance frequency of the strip. The novel sensor combines the electromagnetic properties of the magnetoelastic material with the adsorption properties of the faujasite crystals. Experiments performed over a period of a few months showed that the composite sensor remained fully operational, thus indicating its long‐term stability. Furthermore, the present work demonstrates that a zeolite–Metglas composite can be used as a sensor of an analyte in a mixture as long as it adsorbs selectively larger amounts of the particular analyte than other compounds present in the mixture.     

Two‐Dimensional Nanostructured Materials for Gas Sensing

Two‐dimensional (2D) nanostructures are highly attractive for fabricating nanodevices due to their high surface‐to‐volume ratio and good compatibility with device design. In recent years 2D nanostructures of various materials including metal oxides, graphene, metal dichalcogenides, phosphorene, BN and MXenes, have demonstrated significant potential for gas sensors. This review aims to provide the most recent advancements in utilization of various 2D nanomaterials for gas sensing. The common methods for the preparation of 2D nanostructures are briefly summarized first. The focus is then placed on the sensing performances provided by devices integrating 2D nanostructures. Strategies for optimizing the sensing features are also discussed. By combining both the experimental results and the theoretical studies available, structure‐properties correlations are discussed. The conclusion gives some perspectives on the open challenges and future prospects for engineering advanced 2D nanostructures for high‐performance gas sensors devices.     

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.     

Generation of Self‐Assembled 3D Mesostructured SnO2 Thin Films with Highly Crystalline Frameworks

Crack‐free, mesoporous SnO₂ films with highly crystalline pore walls are obtained by evaporation‐induced self‐assembly using a novel amphiphilic block‐copolymer template (“KLE” type, poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide)), which leads to well‐defined arrays of contracted spherical mesopores by suitable heat‐treatment procedures. Because of the improved templating properties of these polymers, a facile heat‐treatment procedure can be applied whilst keeping the mesoscopic order intact up to 600–650 °C. The formation mechanism and the mesostructural evolution are investigated by various state‐of‐the‐art techniques, particularly by a specially constructed 2D small‐angle X‐ray scattering setup. It is found that the main benefit from the polymers is the formation of an ordered mesostructure under the drastic conditions of using molecular Sn precursors (SnCl₄), taking advantage of the large segregation strength of these amphiphiles. Furthermore, it is found that the crystallization mechanism is different from other mesostructured metal oxides such as TiO₂. In the case of SnO₂, a significant degree of crystallization (induced by heat treatment) already starts at quite low temperatures, 250–300 °C. Therefore, this study provides a better understanding of the general parameters governing the preparation of mesoporous metal oxides films with crystalline pore walls.     

Extremely High Silver Ionic Conductivity in Composites of Silver Halide (AgBr,AgI) and Mesoporous Alumina

The silver ionic conductivity in heterogeneous systems of AgBr:Al₂O₃ and AgI:Al₂O₃ is highly enhanced by utilizing mesoporous Al₂O₃ as the insulating phase. The highest Ag⁺ conductivity of 3.1 × 10^–3 Ω^–1 cm^–1 (at 25 °C) has been obtained for the AgI:Al₂O₃ composite with an Al₂O₃ volume fraction of 0.3. For AgBr:Al₂O₃, the enhancement of the conductivity is satisfactorily explained in the framework of the ideal space‐charge model, while in the case of AgI:Al₂O₃ stacking disorder is also considered to contribute to the ionic conductivity.     

Synthesis,Mechanism, and Gas‐Sensing Application of Surfactant Tailored Tungsten Oxide Nanostructures

Widely applicable nonaqueous solution routes have been employed for the syntheses of crystalline nanostructured tungsten oxide particles from a tungsten hexachloride precursor. Here, a systematic study on the crystallization and assembly behavior of tungsten oxide products made by using the bioligand deferoxamine mesylate (DFOM) (product I ), the two chelating ligands hexadecyltrimethylammoniumbromide (CTAB) ( II ) and poly(alkylene oxide) block copolymer (Pluronic P123) ( III ) is presented. The mechanistic pathways for the material synthesis are also discussed in detail. The tungsten oxide nanomaterials and reaction solutions are characterized by Fourier transform IR, ¹H, and ¹³C NMR spectroscopies, powder X‐ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), high‐resolution TEM, and selected‐area electron diffraction. The indexing of the line pattern suggests WO₃ is in its monoclinic structure with a = 0.7297 nm, b = 0.7539 nm, c = 0.7688 nm, and β‐i; = 90.91 °. The nanoparticles formed have various architectures, such as chromosomal shapes (product I ) and slates ( II ), which are quite different from the mesoporous one ( III ) that has internal pores or mesopores ranging from 5 to 15 nm. The nanoparticles obtained from all the synthetic procedures are in the range of 40–60 nm. The investigation of the gas‐sensing properties of these materials indicate that all the sensors have good baseline stability and the sensors fabricated from material III present very different response kinetics and different CO detection properties. The possibility of adjusting the morphology and by that tuning the gas‐sensing properties makes the preparation strategies used interesting candidates for fabricating gas‐sensing materials.     

A New Mesoporous Hybrid Material: Porphyrin‐Doped Aerogel as a Catalyst for the Epoxidation of Olefins

A new hybrid organic–inorganic material has been obtained by the incorporation of a manganese(III ) porphyrin into a mesoporous aerogel matrix. The new heterogeneous catalyst was active in the epoxidation of a variety of olefins and polycyclic aromatic hydrocarbons, using iodosylbenzene as oxidizing agent. The catalyst was stable, readily recovered, and re‐used without loss of activity. The hybrid aerogel catalyst was more active than the corresponding metalloporphyrin in homogeneous solution.