WO3基气敏传感器*

气敏传感器已在生物、化学、航空、军事等领域获得了广泛的应用。鉴于WO₃基气敏传感器是检测H₂S、NO_x、O₃和NH₃等气体最有前景的新型氧化物气敏传感器之一,本文以不同的敏感气体为分类依据系统阐述了近年来WO₃基气敏传感器的研究进展,详细探讨了制备方法及贵金属掺杂对上述各种气体气敏性能的影响,并指出了目前WO₃基气敏传感器在研究过程中存在的问题。     

二维/一维BiOBr0.5Cl0.5/WO3 S型异质结助力光催化CO2还原

S型异质结不但可以提高载流子的分离效率,还可以维持较强的氧化还原能力。因此,构建S型异质是提高光催化二氧化碳还原反应的有效途径。本研究通过静电自组装法构建了具有近红外光响应(> 780 nm)的二维BiOBr_0.5Cl_0.5纳米片和一维WO₃纳米棒S型异质结光催化剂,并用于高效还原二氧化碳。能带位置和界面电子相互作用的综合分析表明：在光催化二氧化碳还原反应过程中,BiOBr_0.5Cl_0.5/WO₃遵循S型电子转移路径;不仅提高了载流子的高效分离,还维持了两相(BiOBr_0.5Cl_0.5和WO₃)较高的氧化还原能力。此外,二维纳米片/一维纳米棒的结构使得半导体之间具备良好的界面接触,有利于载流子的分离,且暴露更多的活性位点,最终提高催化效率。结果显示,BiOBr_0.5Cl_0.5/WO₃异质结催化剂表现出较高的CO₂还原能力和CO选择性,CO的产率高达16.68 μmol∙g^-1∙h^-1,分别是BiOBr_0.5Cl_0.5的1.7倍和WO₃的9.8倍。本工作为构建S型二维/一维异质结光催化剂高效还原二氧化碳提供了新的思路。     

NiO改性C3N5光催化剂析氢性能研究（英文）

近年来,新型光催化剂氮化碳（C₃N₅）因其优异的光捕获性能和独特的二维结构备受关注。然而,较高的电子-空穴复合率严重影响其光催化性能。本研究采用水热法成功合成了氧化镍（NiO）改性的C₃N₅ p-n异质结纳米光催化剂。结果表明,9-Ni/C₃N₅纳米光催化剂在可见光照射下表现出优异的析氢性能,其析氢速率可高达357μmol/（g·h）,是纯C₃N₅的107倍。这主要归因于9-Ni/C₃N₅纳米光催化剂形成p-n异质结,有效促进了光生电子-空穴对的分离,从而提高了析氢效率。     

集成二维层状CdS/WO3S型异质结及金属化Ti3C2MXene基欧姆结高效光催化产氢

开发低成本的半导体光催化剂以实现可见光下高效、持久的光催化分解水产氢是一个非常具有挑战性的课题.近年来,具有高产氢活性的CdS光催化剂引起了人们的研究兴趣.但是光生电子-空穴对快速复合、反应活性位点不足以及严重的光腐蚀等问题,严重地制约了CdS在光催化领域的实际应用.构建S型异质结和负载助催化剂被认为是促进光生电子空穴分离和加速产氢动力学的有效策略.本文通过在低成本的WO₃和Ti₃C₂MXene(MX)纳米片上生长CdS纳米片,设计并构建了具有二维耦合界面的2D/2D/2D层状异质结光催化剂,以实现高效的可见光光催化分解水产氢.首先通过水热煅烧和刻蚀的方法分别制备了WO₃和MX纳米片,然后以乙酸镉和硫脲为原料在乙二胺溶剂中通过水热法合成了MX-CdS/WO₃层状异质结光催化剂.在可见光下,以乳酸为牺牲剂测试了光催化剂的产氢活性且经过4次连续的循环反应,MX-CdS/WO₃体系展现出良好的活性及稳定性.在可见光的照射下,MX-CdS/WO₃层状异质结光催化剂最高的可见光光催化分解水产氢速率达到了27.5 mmol/g/h,是纯CdS纳米片的11倍.与此同时,在450 nm的光照下,表观量子效率达到了12.0%.为了深入探讨其高效产氢机理,通过X射线衍射、X射线光电子能谱、原子力显微镜、透射电镜、高分辨电子显微镜等对MX-CdS/WO₃体系的组成和结构进行分析.结果表明,实验成功地合成了CdS,WO₃和MX三种纳米片及其复合材料.通过紫外-可见漫反射光谱研究了样品材料的光吸收能力.通过表面光电压、稳态及瞬态荧光光谱等研究了材料的电荷载流子复合和转移行为,发现MX-CdS/WO₃的光生电子空穴对相比与纯CdS或者二元复合材料具有更高的分离效率.UPS和ESR等表征结果说明,材料内部电场的方向和在光照条件下光生载流子的迁移方向,从而证实了S型异质结和欧姆结的成功构建.综上,在MX-CdS/WO₃光催化剂体系中,S型异质结形成较强的界面电场能够有效促进CdS纳米片与WO₃纳米片之间光生电子-空穴对的分离.同时,二维Ti₃C₂MXene纳米片作为辅助催化剂,通过与CdS/WO₃纳米片构建欧姆结,进而提供大量的电子转移途径和更多的析氢反应活性位点,使得CdS光催化剂的光催化活性和稳定性得到了很大的提升.通过构建S型内建电场、欧姆结和2D/2D界面可以协同提高CdS纳米片的光催化性能,从而加速光生电子在异质结中的分离和利用.本文所采用基于S型异质结与欧姆结基助催化剂之间的耦合策略可以作为一种通用策略扩展到其它传统半导体光催化剂的改性中,从而推进高效光催化产氢材料的有效合成.     

PdO,Au, CdO修饰SnO2纳米纤维的制备及其气敏特性

采用静电纺丝的方法制备了SnO₂纳米纤维,并分别用PdO、Au、CdO对该纳米纤维材料进行表面修饰.用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(EDX)、X射线光电子能谱(XPS)分析、Brunauer-Emmett-Teller (BET)比表面积测试对材料进行表征.修饰前后, SnO₂纳米纤维都是由约15 nm的纳米颗粒构成的直径约为200 nm的多级结构材料.采用静态测试系统对纯SnO₂及不同物质修饰的SnO₂的气敏特性进行测试,结果表明,未修饰的SnO₂纳米纤维气敏元件对甲醛具有较好的响应.修饰后的SnO₂材料的气敏特性都有明显的改善. CdO修饰的SnO₂气敏元件对甲醛的响应值最高,且响应恢复时间短,选择性好. Au修饰的SnO₂气敏元件对甲醛响应的最佳工作温度从300 ℃降到了200 ℃.经PdO修饰后, SnO₂纳米纤维对甲苯的响应值变得最高.初步分析了经过修饰的SnO₂气敏材料的敏感机理.     

金属氧化物异质结气体传感器气敏增强机理

金属氧化物异质结由于费米能级效应、不同组分之间的协同作用,常被用来提高电阻型金属氧化物半导体气体传感器的气敏特性。本文简述了近年来国内外金属氧化物异质结材料的类别,主要分为混合氧化物结构、层状结构、第二相粒子修饰结构、一维纳米结构和核-壳结构;重点综述了金属氧化物异质结的气敏增强机理,包括异质结效应、协同效应、催化溢流效应、响应反型、载流子分离及微结构调控六大机理;分析了当前异质结气体传感器面临的瓶颈。最后对纳米异质结气体传感器的发展进行了展望,今后金属氧化物异质结气体传感器可以从明确异质结界面机理展开,这将为自下而上地设计出符合实际需要的气体传感器提供一定参考。     

原位生长的α-Fe2O3/ZnO异质纳米棒阵列对乙醇气体的高选择性检测

采用两步溶液法在陶瓷管上原位生长了ZnO纳米棒阵列,然后以ZnO纳米棒为载体,通过水热法在其表面负载α-Fe₂O₃纳米粒子,生成异质α-Fe₂O₃/ZnO复合纳米材料。 α-Fe₂O₃/ZnO纳米棒直径30~80 nm,长1 μm左右,交叉排列形成纳米棒阵列,α-Fe₂O₃纳米粒子粒径约10 nm,均匀分布在ZnO纳米棒表面。 将纯ZnO和α-Fe₂O₃/ZnO纳米棒阵列制成气敏元件,测试并对比了2种气敏元件的气敏性能,揭示其气敏机理。 结果表明:α-Fe₂O₃纳米粒子的复合显著提高了ZnO纳米棒阵列对乙醇气体的灵敏度和选择性,在工作温度370 ℃时,对100 μL/L乙醇气体的响应值为85.4,是同条件下ZnO器件对乙醇响应值(9.4)的9.1倍,响应时间7 s,最低检出限为0.01 μL/L。 相关研究可以应用于痕量乙醇的快速、高灵敏度和高选择性检测。     

Z-机制g-C3N4/Bi/BiOBr异质结光催化剂制备及其可见光降解甲醛气体研究

通过将BiOBr纳米片与g-C₃N₄复合,然后原位还原,合成了具有纳米花状结构的三元异质结光催化剂g-C₃N₄/Bi/BiOBr.对g-C₃N₄/Bi/BiOBr的结构、形貌、元素价态和光学性能等进行了表征和研究.评估了g-C₃N₄/Bi/BiOBr对气体甲醛的光催化降解活性. g-C₃N₄/Bi/BiOBr在可见光照射下降解甲醛的活性与g-C₃N₄、 BiOBr单体和g-C₃N₄/BiOBr二元复合物相比显著提高. 20%-g-C₃N₄/Bi/BiOBr复合物可以在60 min内(λ> 400 nm)降解80%的气态甲醛(初始浓度0.16 mg·L^-1).     

瓶状InN-In2O3纳米复合材料的制备及增强的甲醛气敏性能

采用溶胶-凝胶法制备了In₂O₃纳米粉体, 通入NH₃进行反应得到了中间产物InN基底材料, 再通过原位氧化过程最终获得了InN-In₂O₃纳米复合材料, 并利用X射线衍射仪(XRD)、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线光电子能谱仪(XPS)等对所制备材料的组成、 形貌及结构等进行了表征测试. 结果表明, 该纳米复合材料呈瓶状结构. 气敏性能测试结果表明, 其在较低工作温度(75 ℃)下对甲醛气体的检出限可低至ppb级(1 ppb=1.3 μg/m³), 具有灵敏度较高(对0.13 mg/m³即100 ppb甲醛的灵敏度为12)、 响应时间较短(2 s)以及选择性和稳定性较强的优良性能. 在湿度对传感器灵敏度的影响测试中, 由于甲醛的水溶特性, 随着湿度的变化, 传感器的灵敏度发生变化. 在低甲醛浓度时湿度的变化对灵敏度的影响较大, 高浓度时影响反而较小.     

平面型乙醇快速响应气敏传感器的制备

采用水热法合成了纳米In₂O₃颗粒,将其旋涂于陶瓷基片上经氮化处理获得InN基片,再对InN基片进行氧化,合成出气敏材料并在一种微型平面电极片上制备了传感器件.采用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）仪、X射线光电子能谱（XPS）等手段对材料的形貌、组成进行了表征与分析,结果表明,最终获得了松枝状结构的InN-In₂O₃纳米复合材料.对器件的气敏性能进行了测试,发现基于此材料制备的平面型气敏传感器对乙醇气体具有良好的气敏性能：检测浓度为1.025 mg/m³（500 ppb）的乙醇蒸汽的灵敏度可达18;检测2.05 mg/m³（1 ppm）的乙醇的响应-恢复时间最快仅为1 s;最佳工作温度低,仅为50℃.     

NiO@ZnO heterostructured nanotubes: coelectrospinning fabrication, characterization, and highly enhanced gas sensing properties

Novel NiO@ZnO heterostructured nanotubes (NTs) were fabricated by the coelectrospinning method, consisting of external hexagonal ZnO shell and internal cubic NiO NTs. They are carefully investigated by scanning electron microscopy, transmission electron microscopy, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy mapping, X-ray diffraction, and X-ray photoelectron spectroscopy techniques. A reasonable formation mechanism of the hierarchical NiO@ZnO NTs is proposed, which is discussed from the view of degradation temperature of different polymers and the amount of inorganic salts. They were then explored for fabrication of H(2)S gas sensors. The gas sensing test reveals that compared with the pure ZnO, NiO, and the ZnO-NiO mixed gas sensors, hierarchical gas sensor exhibits highly improved sensing performances to dilute hydrogen sulfide (H(2)S) gas. The response of the optimum NiO@ZnO NTs sensor to 50 ppm H(2)S increases as high as 2.7-23.7 times compared to the other sensors, whereas the response and recovery times also become shorter considerably. These enhanced gas sensing properties are closely related to the change of nanostructure and activity of ZnO and NiO nanocrystals as well as combination of homo- and heterointerfaces in the optimum gas sensor, which are confirmed by a series of well-designed experiments.     

UV-Enhanced Room Temperature Ozone Sensor Based on Hierarchical SnO2-In2O3

SnO₂-In₂O₃ hierarchical microspheres were prepared by the hydrothermal and solvothermal method. The morphology, phase crystallinity of the obtained SnO₂-In₂O₃ were measured by X-ray diffraction(XRD), scan electron microscopy(SEM), respectively. A room temperature ozone sensor based on SnO₂-In₂O₃ hierarchical microspheres was fabricated and investigated. The gas sensing properties of the sensor using SnO₂-In₂O₃ strongly depended on the proportion of SnO₂ and In₂O₃. The sensitivity and response/recovery speed were greatly enhanced by UV illumination. A gas sensing mechanism related to oxygen defect was suggested.     

气敏半导体材料Cd2Sb2O6.8的制备及其性能研究

采用化学共沉淀法,在较低温度(750℃)下制备了具有缺陷烧绿石结构的复合氧化物Cd₂Sb₂O_6.8的纯相超微粉;研究了制备条件对物相、结构和气敏性能的影响,并对其反应过程机理进行了探讨,气敏性能测试结果表明,纯相Cd₂Sb₂O_6.8气敏元件对乙炔气体有较高的灵敏度和较好的选择性.     

Defect and transport properties of the NdCoO3 catalyst and sensor material

The NdCoO₃ perovskite has been investigated using a combination of atomistic simulation and experimental techniques to examine its possible use as an oxidation catalyst and/or sensor material. The sensing properties of NdCoO₃ and Nd_0.8Sr_0.2CoO₃ towards CO have been investigated by employing thin films deposited by means of radio-frequency (RF) magnetron sputtering onto polycrystalline Al₂O₃. The response of the films was monitored by performing four-probe DC-conductivity measurements. The conductivity variation induced by switching between a CO-free atmosphere (air) and a CO-rich one with the same composition of residual gas was recorded and analysed as a function of temperature; results are compared for the two samples. Simulation studies focussed on the dopant, transport and redox properties of the pure material; the results indicate that Sr and Ca on the Nd site are the most soluble dopants and that when divalent dopants are incorporated in the structure, charge compensation occurs via oxygen ion vacancies. The low activation energy for oxygen vacancy migration suggests high oxide-ion mobility through the lattice. Particular attention is paid to the electronic processes because of their importance with respect to practical applications of the material.     

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

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

毫秒激光烧蚀镍靶高效率制备NiO纳米立方体

利用长脉宽毫秒激光烧蚀浸没在循环水中的金属镍靶制备了大量的氧化镍(NiO)纳米立方体, 通过透射电子显微镜(TEM)、 选区电子衍射(SAED)、 X射线衍射(XRD)和能量色散谱(EDS)等手段表征了产物的形貌和结构. 结果表明, 高功率密度激光产生的高温高压条件是形成NiO纳米立方体的最重要因素. 激光功率密度高于10⁴ W/cm²时可以生成NiO纳米立方体, 当功率高于该阈值时激光首先将镍靶烧蚀为金属液滴, 高温的金属液体加热周围液体, 并由于液体的限制效应使得压力进一步升高, 最后金属液滴与液体发生表面反应生成NiO纳米立方体.     

The gas sensing properties of TiO_2 nanotubes synthesized by hydrothermal method

In this paper,the TiO₂ nanotubes were synthesized by hydrothermal method using a 10 mol/L NaOH aqueous solution at 150℃. The structure of prepared materials was characterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）. scanning electron microscope（SEM） and Brunauer-Emmett-Teller（BET）.The prepared TiO₂ nanotubes were used to prepare thick film gas sensors and the gas sensing properties to various gases were tested.Results show the prepared TiO₂ nanotube gas sensors responses to ethanol under dry condition at 450℃.This could be attributed to the fact that it had high porous morphology and a higher pore volume,which can promote the diffusion of ethanol deep inside the films and improve the sensor response. Moreover,the gas sensor made with nanotubes exhibit high selective response towards ethanol gas compared with H₂,CO,acetone.     

NASICON-based H2 Sensor Using CoCrMnO4 Insensitive Reference Electrode and Buried Au Sensing Electrode

This work focuses on the H2 sensing performance of the sensor with buried Au sensing electrode and spi- nel-type oxide CoCrMnO4 insensitive reference electrode within sodium super ionic conductor（NASICON） film. The sensor showed the highest response to H2 gas on the insensitive material sintering at 800 ~C. Compared with those of the traditional structure device, the sensitivity and selectivity of the sensor using buried sensing electrode were greatly improved, giving a response of-177 mV in 9x10 5 g/L H2, which was about 3.5 times higher than that of sensors with traditional structure. Moreover, the AV value of the sensing device exhibited linear relationship to the logarithm of H2 concentration and the sensitivity（slope） was -135 mV/decade. A sensing mechanism related to the mixed potential was proposed for the present sensor.