CuO–ZnO Micro/Nanoporous Array‐Film‐Based Chemosensors: New Sensing Properties to H2S

CuO–ZnO micro/nanoporous array‐films are synthesized by transferring a solution‐dipped self‐organized colloidal template onto a device substrate and sequent heat treatment. Their morphologies and structures are characterized by X‐ray diffraction, field‐emission scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectrum analysis. Based on the sensing measurement, it is found that the CuO–ZnO films prepared with the composition of [Cu²⁺]/[Zn²⁺]=0.005, 0.01, and 0.05 all show a nice sensitivity to 10 ppm H₂S. Interestingly, three different zones exist in the patterns of gas responses versus H₂S concentrations: a platform zone, a rapidly increasing zone, and a slowly increasing zone. Further experiments show that the hybrid CuO–ZnO porous film sensor exhibits shorter recovery time and better selectivity to H₂S gas against other interfering gases at a concentration of 10 ppm. These new sensing properties may be due to a depletion layer induced by p–n junction between p‐type CuO and n‐type ZnO and high chemical activity of CuO to H₂S. This work will provide a new construction route of ZnO‐based sensing materials, which can be used as H₂S sensors with high performances.     

X-ray absorption near edge structures (xanes) of Cu/ZnO/Al2O3 Co shift catalysts

X-ray absorption near edge structures (XANES) of some Cu/ZnO/Al₂O₃CO shift catalysts have been measured at high resolution using synchrotron radiation, and compared to reference compounds Prior to reduction. CuO and ZnO are present, after reduction ZnO and highly dispersed Cu, no indication was found for Cu₂O or the presence of spinels. The results are qualitatively confirmed by preliminary analysis of EXAFS spectra.     

溶剂极性对微波辐射老化制备前驱体及CuO/ZnO/Al2O3催化剂结构的影响

在制备CuO/ZnO/Al2O3催化剂的老化过程中,采用微波辐射老化技术,着重研究了溶剂极性对前躯体物相组成,烧后CuO/ZnO/Al2O3催化剂结构及其在浆态床合成甲醇工艺中催化性能的影响。通过XRD、DTG、H2-TPR,FTIR、HR-TEM和XPS对前驱体及催化剂表征表明,沉淀母液在微波辐射条件下进行老化,溶剂的极性对前躯体物相组成及催化剂结构影响显著。随着溶剂极性的增大,Zn2+/Cu2+取代Cu2(CO3)(OH)2/Zn5(CO3)2(OH)6中Cu2+/Zn2+的取代反应增强,使得前躯体中(Cu,Zn)5(CO3)2(OH)6和(Cu,Zn)2(CO3)(OH)2物相的含量增多,结晶度提高,导致烧后CuO/ZnO/Al2O3催化剂中CuO-ZnO协同作用增强,且CuO晶粒减小,表面Cu含量增加,催化剂活性和稳定性提高。水溶剂的极性最大,制备的催化剂活性和稳定性最好,甲醇的时空收率(STY)和平均失活率分别为320 mg.g-1.h-1和0.11%.d-1。     

Derivatives (Cu/CuO,Cu/Cu2O,and CuS) of Cu superstructures reduced by biomass reductants

Metallic Cu is considered as the promising functional material owing to its high conductivity and harmlessness. Here, metallic Cu which presents a unique interconnected and continuous structure (Cu superstructure) is prepared using Magnolia grandiflora leaves as the biomass reductant, a green process which avoided the release of harmful gases and massive energy consumption. What's more, Cu/CuO, Cu/Cu₂O, and CuS nanosheets with different sizes were fabricated using Cu superstructure as the substrate via facile methods, and the morphology is regulated by controlling the relevant factors. The electrochemical sensors based on the three derivations were fabricated to study the sensing performance of glucose. The unique structure of nanosheets encapsulating Cu superstructure guarantees the excellent conductivity of Cu/CuO and Cu/Cu₂O composites. Moreover, the electrochemical stability is improved owing to the nanosheet protective layer. Although no metallic Cu was maintained in CuS, the integrated multilayer nanosheets endow CuS with short channels for fast interlayer electronic transmission and with structural stability.     

Hierarchically porous Fe2O3/CuO composite monoliths: Synthesis and characterization

In this paper, hierarchically porous Fe2O3/CuO composite monoliths were first successfully synthesized by a mild method using silica monoliths as templates. The structure of composite monoliths was characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption-desorption. The results indicated that the molar ratio of Fe to Cu had a great influence on the crystal phase of Fe2O3, pore size and the structure of the macroporous wall. The Fe2O3/CuO composite monoliths consist of hierarchically macroporous and mesoporous structure, while the sample with the Fe/Cu molar ratio of 2 : 1 possesses tighter wall structure than other samples. It is expected that as-prepared Fe2O3/CuO composite monoliths have potential applications in several fields as catalysts, catalyst supports, chemical sensors and high-performance liquid chromatography (HPLC).     

High-Performance Sensor Based on Thin-Film Metallic Glass/Ultra-nanocrystalline Diamond/ZnO Nanorod Heterostructures for Detection of Hydrogen Gas at Room Temperature

This article outlines a novel material to enable the detection of hydrogen gas. The material combines thin-film metallic glass (TFMG), ultra-nanocrystalline diamond (UNCD), and ZnO nanorods (ZNRs) and can be used as a device for effective hydrogen gas sensing. Three sensors were fabricated by using combinations of pure ZNRs (Z), UNCD/ZNRs (DZ), and TFMG/UNCD/ZNRs (MDZ). The MDZ device exhibited a performance superior to the other configurations, with a sensing response of 34 % under very low hydrogen gas concentrations (10 ppm) at room temperature. Remarkably, the MDZ-based sensor exhibits an ultra-high sensitivity of 60.5 % under 500 ppm H₂. The MDZ sensor proved very fast in terms of response time (20 s) and recovery time (35 s). In terms of selectivity, the sensors were particularly suited to hydrogen gas. The sensor achieved the same response performance even after two months, thereby demonstrating the superior stability. It is postulated that the superior performance of MDZ can be attributed to defect-related adsorption as well as charge carrier density. This paper also discusses the respective energy band models of these heterostructures and also the interface effect on the gas sensing enhancements. The results indicate that the proposed hybrid TFMG/UNCD/ZNRs nanostructures could be utilized as high-performance hydrogen gas sensors.     

CuO/ZnO/Y2O3/γ-Al2O3双功能催化剂上二甲醚水蒸气重整制氢

将沉积-沉淀法制备的CuO/ZnO/Y2O3催化剂同γ-Al2O3进行机械混合, 制备了CuO/ZnO/Y2O3/γ-Al2O3双功能催化剂, 用于二甲醚水蒸气重整制氢反应, 实验结果表明其活性、稳定性等均优于常用的CuO/ZnO/Al2O3/γ-Al2O3催化剂. 结合N2吸附-脱附(BET)、N2O化学吸附(N2O chemisorption)、NH3程序升温脱附(NH3-TPD)、X射线衍射(XRD)、H2程序升温还原(H2-TPR)等表征手段研究了两种催化剂在表面酸性及微观结构上的差异, 发现CuO/ZnO/Y2O3催化剂具有相对较高的铜分散度, 铜晶粒更加细小化, 并且具有高温稳定性的Y2O3可能起到隔离铜的作用, 在一定程度上防止了铜晶粒的团聚, 从而改善了重整组分的性能, 提高了双功能催化剂的重整制氢活性及稳定性.     

Simple self-assembly of 3D laminated CuO/SnO2 hybrid for the detection of triethylamine

Tin dioxide is important gas sensor material and has wide applications in the detection of toxic gases and volatile organic compounds. Here, we synthesized a 3D laminated structural CuO/SnO₂ material possessing p-n heterostructures. The morphology and structure were characterized by XRD, SEM, TEM and XPS techniques and the sensing properties were investigated for the detection of triethylamine (TEA). The results indicate that 3D laminated CuO/SnO₂ material, assembled by lamellae consisting of ordered nanoparticles, exhibit an enhanced sensing performance compared with SnO₂, and notably, CuO/SnO₂ with size less than 1 μm has obvious high selectivity in the detection of 100 ppm TEA. Particularly, it has a high response and stability to 1 and 5 ppm TEA (S is 8 and 33), and that is higher than SnO₂ material, suggesting 3D laminated CuO/SnO₂ is an effective candidate material served as sensor platform to detect low-concentration amines.     

微波辐射对浆态床合成甲醇CuO/ZnO/Al2O3催化剂前驱体晶相转变的影响

在微波辐射条件下,对CuO/ZnO/Al2O3催化剂的沉淀母液进行老化,通过XRD、TG、H2-TPR,FTIR、HR-TEM和XPS对前驱体及催化剂微观结构的进行表征,探讨了CuO/ZnO/Al2O3催化剂前驱体晶相转变过程中微波辐射的作用。结果表明,微波辐射有利于Cu2+取代Zn5(CO3)2(OH)6中Zn2+的同晶取代反应。微波辐射的老化过程中,首先发生Cu2+取代Zn5(CO3)2(OH)6中Zn2+生成(Cu,Zn)5(CO3)2(OH)6的同晶取代反应,并于1.0 h内基本完成;随着老化时间继续延长,主要进行Zn2+取代Cu2(CO3)(OH)2中Cu2+生成(Cu,Zn)2(CO3)(OH)2的同晶取代反应,同时(Cu,Zn)5(CO3)2(OH)6进一步结晶。与常规老化1 h制备的前驱体相比,微波辐射老化1.0 h制备的前驱体含有较多的(Cu,Zn)5(CO3)2(OH)6物相,有助于增强焙烧后CuO/ZnO/Al2O3催化剂中CuO-ZnO协同作用,提高表面铜含量,进而提高CuO/ZnO/Al2O3催化剂在浆态床合成甲醇的催化活性和稳定性,在400 h浆态床合成甲醇评价期间,甲醇时空收率最大达318.9 g.kg-1.h-1,失活率仅为0.11%.d-1。     

Humidity sensors using in situ synthesized sodium polystyrenesulfonate/ZnO nanocomposites

Thin film humidity sensors have been prepared using in situ synthesized inorganic/organic nanocomposites of sodium polystyrenesulfonate (NaPSS) and ZnO. Its humidity sensing characteristics and the sensing mechanism have been investigated by measuring the complex impedance spectra of the sensor at different humidities. The logarithm of the impedance of sensor based on composite film changes linearly by four-orders of magnitude over almost whole humidity range (11-97% RH). Furthermore, the sensor exhibits a quick response (absorption: 2 s, desorption: 2 s) and small hysteresis (less than 2% RH). The composite film shows better sensing properties than NaPSS film, such as better linearity, quicker response. Explanation to the improvement is attempted by taking into account of the composition and structure of the nanocomposites.     

Cr2O3-modified ZnO thick film resistors as LPG sensors

Thick films of pure ZnO were obtained by screen-printing technique. Surface functionalized ZnO thick films by Cr₂O₃ were obtained by dipping pure ZnO thick films into 0.01 M aqueous solution of chromium trioxide (CrO₃). The dipped films were fired at 500 °C for 30 min. Upon firing, the CrO₃ would reduce to Cr₂O₃. Cr₂O₃-activated (0.47 mass%) ZnO thick films resulted in LPG sensor. Upon exposure to 100 ppm LPG, the barrier height between Cr₂O₃ and ZnO grains decreases markedly, leading to a drastic decrease in resistance. The sensor was found to sense LPG at 350 °C and no cross sensitivity was observed to other hazardous, polluting and inflammable gases. The quick response (∼18 s) and fast recovery (∼42 s) are the main features of this sensor. The effects of microstructures and dopant concentrations on the gas sensing performance of the sensor were studied and discussed.     

Hierarchically Structure SnO2/ZnO Nanocomposites: Preparation,Growth Mechanism and Gas Sensing Property

SnO₂/ZnO nanocomposite was synthesized from mixed ethanol and water systems and the ethanol-sensing properties of sensors based on SnO₂/ZnO were investigated. The structure and morphology of the products was characterized by x-ray diffraction (XRD) and a field emission scanning electron microscope (FE-SEM). The results showed that the diameter of the liked pine needle SnO₂ was about 40 nm with a length about 300 nm, which are uniformly dispersed on the surface of the ZnO nanosheets. The growth process of the SnO₂/ZnO nanocomposite was discussed. The results of gas sensing properties of SnO₂/ZnO nanocomposite sensor showed high and quick response to ethanol vapor at 5.0 v. This sensor showed the advantages of high selectivity, strong stability, and prompt response/recovery characteristics in detecting ethanol vapor at 5.0 v.     

The impact of surface Cu2+ of ZnO/(Cu1−xZnx)O heterostructured nanowires on the adsorption and chemical transformation of carbonyl compounds

The surface cation composition of nanoscale metal oxides critically determines the properties of various functional chemical processes including inhomogeneous catalysts and molecular sensors. Here we employ a gradual modulation of cation composition on a ZnO/(Cu_1−xZn_x)O heterostructured nanowire surface to study the effect of surface cation composition (Cu/Zn) on the adsorption and chemical transformation behaviors of volatile carbonyl compounds (nonanal: biomarker). Controlling cation diffusion at the ZnO(core)/CuO(shell) nanowire interface allows us to continuously manipulate the surface Cu/Zn ratio of ZnO/(Cu_1−xZn_x)O heterostructured nanowires, while keeping the nanowire morphology. We found that surface exposed copper significantly suppresses the adsorption of nonanal, which is not consistent with our initial expectation since the Lewis acidity of Cu²⁺ is strong enough and comparable to that of Zn²⁺. In addition, an increase of the Cu/Zn ratio on the nanowire surface suppresses the aldol condensation reaction of nonanal. Surface spectroscopic analysis and theoretical simulations reveal that the nonanal molecules adsorbed at surface Cu²⁺ sites are not activated, and a coordination-saturated in-plane square geometry of surface Cu²⁺ is responsible for the observed weak molecular adsorption behaviors. This inactive surface Cu²⁺ well explains the mechanism of suppressed surface aldol condensation reactions by preventing the neighboring of activated nonanal molecules. We apply this tailored cation composition surface for electrical molecular sensing of nonanal and successfully demonstrate the improvements of durability and recovery time as a consequence of controlled surface molecular behaviors.

Unexpected features of surface Cu²⁺ on ZnO/(Cu1−xZnx)O nanowires for molecular transformation and electrical sensing of carbonyl compounds were found.     

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.     

Humidity sensing characteristics of Sn doped Zinc oxide based quartz crystal microbalance sensors

The electrical, optical and humidity sensor properties of nanostructured ZnO samples were investigated. The structural properties of Sn doped ZnO samples were characterized by X-ray diffraction and atomic force microscopy. It was found that the all samples have a hexagonal crystal structure. The electrical conductivity of the samples indicates that undoped and Sn doped ZnO samples exhibit the semiconducting behavior. The optical absorption method was used to determine the optical band gaps of the samples. The optical band gap and activation energy values of the ZnO samples were changed with Sn doping. The ZnO based on quartz crystal microbalance humidity sensors were prepared and sensing properties of the sensors were changed with Sn doping. The response time required to reach 70 % is about 13–16 s, while the recovery time from 70 to 30 % RH is about 13–15 s. The fast response of the sensors is due to easy diffusion of water molecules between ZnO nanopowders. The prepared sensors have a high reproducibility and sensitivity for humidity sensing applications.     

H2S Dosimetry by CuO: Towards Stable Sensors by Unravelling the Underlying Solid-State Chemistry

The precise detection of the toxic gas H₂S requires reliable sensitivity and specificity of sensors even at minute concentrations of as low as 10 ppm, the value corresponding to typical exposure limits. CuO can be used for H₂S dosimetry, based on the formation of conductive CuS and the concomitant significant increase in conductance. In theory, at elevated temperature the reaction is reversed and CuO is formed, ideally enabling repeated and long-term use of one sensor. Yet, the performance of CuO tends to drop upon cycling. Utilizing defined CuO nanorods we thoroughly elucidated the associated detrimental chemical changes directly on the sensors, by Raman and electron microscopy analysis of each step during sensing (CuO→CuS) and regeneration (CuS→CuO) cycles. We find the decrease in the sensing performance is mainly caused by the irreversible formation of CuSO₄ during regeneration. The findings allowed us to develop strategies to reduce CuSO₄ formation and thus to substantially maintain the sensing stability even for repeated cycles. We achieved CuO-based dosimeters possessing a response time of a few minutes only, even for 10 ppm H₂S, and prolonged life-time.     

Enhanced ethanol sensing properties of WO3 modified TiO2 nanorods

Pristine and WO₃ decorated TiO₂ nanorods (NRs) were synthesised to investigate n-n-type heterojunction gas sensing properties. TiO₂ NRs were fabricated via hydrothermal method on fluorine-doped tin oxide coated glass (FTO) substrates. Then, tungsten was sputtered on the TiO₂ NRs and thermally oxidised to obtain WO₃ nanoparticles. The heterostructure was characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy. Fabricated sensor devices were exposed to VOCs such as toluene, xylene, acetone and ethanol, and humidity at different operation temperatures. Experimental results demonstrated that the heterostructure has better sensor response toward ethanol at 200 °C. Enhanced sensing properties are attributed to the heterojunction formation by decorating TiO₂ NRs with WO₃.     

Determination of minor components in mixtures using EXAFS

An EXAFS spectrum, obtained by taking the difference between a weighted absorptivity spectrum of a known compound and that of a mixture containing this compound, contained information mainly on the remaining phase(s) in the mixture. The optimum weighting factor was that which gave the minimum value of the definite integral of the radial distribution function (RDF). The efficacy of this technique was demonstrated by the easy identification of Cu₂O, after removal of the CuO contribution, from the spectrum of a mixture of 5% Cu₂O in a ca. 1 + 1 mixture of CuO and ZnO. The method was also used to probe the minor component(s) of a CuO and ZnO calcined catalyst precursor; these showed features consistent with copper dissolved in the ZnO lattice.     

HFIP-Functionalized Co3O4 Micro-Nano-Octahedra/rGO as a Double-Layer Sensing Material for Chemical Warfare Agents

Semiconductor metal oxides (SMO)-based gas-sensing materials suffer from insufficient detection of a specific target gas. Reliable selectivity, high sensitivity, and rapid response–recovery times under various working conditions are the main requirements for optimal gas sensors. Chemical warfare agents (CWA) such as sarin are fatal inhibitors of acetylcholinesterase in the nerve system. So, sensing materials with high sensitivity and selectivity toward CWA are urgently needed. Herein, micro-nano octahedral Co₃O₄ functionalized with hexafluoroisopropanol (HFIP) were deposited on a layer of reduced graphene oxide (rGO) as a double-layer sensing materials. The Co₃O₄ micro-nano octahedra were synthesized by direct growth from electrospun fiber templates calcined in ambient air. The double-layer rGO/Co₃O₄-HFIP sensing materials presented high selectivity toward DMMP (sarin agent simulant, dimethyl methyl phosphonate) versus rGO/Co₃O₄ and Co₃O₄ sensors after the exposure to various gases owing to hydrogen bonding between the DMMP molecules and Co₃O₄-HFIP. The rGO/Co₃O₄-HFIP sensors showed high stability with a response signal around 11.8 toward 0.5 ppm DMMP at 125 °C, and more than 75 % of the initial response was maintained under a saturated humid environment (85 % relative humidity). These results prove that these double-layer inorganic–organic composite sensing materials are excellent candidates to serve as optimal gas-sensing materials.     

Hierarchically porous Fe_2O_3 /CuO composite monoliths:Synthesis and characterization

In this paper,hierarchically porous Fe2O3 /CuO composite monoliths were first successfully synthesized by a mild method using silica monoliths as templates.The structure of composite monoliths was characterized by X-ray diffraction,scanning electron microscopy,nitrogen adsorption-desorption.The results indicated that the molar ratio of Fe to Cu had a great influence on the crystal phase of Fe2O3,pore size and the structure of the macroporous wall.The Fe2O3 /CuO composite monoliths consist of hierarchically macroporous and mesoporous structure,while the sample with the Fe/Cu molar ratio of 2:1 possesses tighter wall structure than other samples.It is expected that asprepared Fe2O3/CuO composite monoliths have potential applications in several fields as catalysts,catalyst supports,chemical sensors and high-performance liquid chromatography (HPLC).