CN110412088B - In doping based on Au2O3Xanthate gas sensitive element of nanosphere and preparation method thereof - Google Patents
In doping based on Au2O3Xanthate gas sensitive element of nanosphere and preparation method thereof Download PDFInfo
- Publication number
- CN110412088B CN110412088B CN201910728452.4A CN201910728452A CN110412088B CN 110412088 B CN110412088 B CN 110412088B CN 201910728452 A CN201910728452 A CN 201910728452A CN 110412088 B CN110412088 B CN 110412088B
- Authority
- CN
- China
- Prior art keywords
- doped
- nanospheres
- gas
- gas sensor
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y35/00—Methods or apparatus for measurement or analysis of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
本发明公开了一种基于Au掺杂In2O3纳米球的黄药气体气敏元件及其制备方法,属于金属氧化物半导体材料的气体传感器领域。本发明以硝酸铟为铟源,氯金酸为金源,采用水热法制备具有六方相晶体结构、直径为75~125nm的Au掺杂In2O3纳米球。将制备的Au掺杂In2O3纳米球分散在乙醇溶液中,制备成气敏料浆,然后将其均匀地涂覆在电极元件表面,制备成气敏元件。本发明所述的Au掺杂In2O3纳米球合成方法简单、成本低、无污染、结构稳定。本发明所述的气敏元件灵敏度高、具有良好的响应和恢复特性,并且具有良好的响应可逆性,重复性和稳定性,能够填补目前市场上该类气体定量检测的空白,对于保障选矿厂浮选车间工作人员的生命健康安全具有重要意义。The invention discloses a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres and a preparation method thereof, belonging to the field of gas sensors of metal oxide semiconductor materials. The invention uses indium nitrate as the indium source and chloroauric acid as the gold source, and adopts a hydrothermal method to prepare Au-doped In 2 O 3 nanospheres with a hexagonal crystal structure and a diameter of 75-125 nm. The prepared Au-doped In 2 O 3 nanospheres are dispersed in an ethanol solution to prepare a gas-sensing slurry, which is then uniformly coated on the surface of an electrode element to prepare a gas-sensing element. The Au-doped In 2 O 3 nanospheres of the invention have a simple synthesis method, low cost, no pollution and stable structure. The gas sensing element of the invention has high sensitivity, good response and recovery characteristics, and good response reversibility, repeatability and stability, and can fill the gap in the quantitative detection of this type of gas in the current market. The life, health and safety of the workers in the flotation workshop is of great significance.
Description
技术领域technical field
本发明属于金属氧化物半导体气体传感器领域,具体涉及一种基于 Au掺杂In2O3纳米球的黄药气体气敏元件及其制备方法。The invention belongs to the field of metal oxide semiconductor gas sensors, in particular to a xanthate gas gas sensor element based on Au-doped In 2 O 3 nanospheres and a preparation method thereof.
背景技术Background technique
在矿产资源的综合利用过程中,首先要将矿石中的有用元素进行富集。常见的选别方法有重选、磁选、浮选等。其中,浮选是一种应用十分广泛的矿石选别方法,其基本原理是利用不同矿物表面物理化学性质的差异,使之选择性的附着在矿浆中的空气气泡上,并随气泡上浮到矿浆表面,从而使有用矿物与脉石分离。在浮选作业过程中,为了调控矿石表面的物理化学性质以及矿浆性质,必须向矿浆中加入一定的浮选药剂。黄药一种最为常见的浮选药剂,常用于硫化矿的浮选作业中。但是,黄药溶液易分解挥发,其挥发气体具有很强的刺激性气味,对眼睛、皮肤、呼吸系统、中枢以及外周神经系统有严重的刺激作用,且急性暴露于高浓度(>0.05%) 时可导致麻醉或精神异常。因此,制备高性能气体传感器对浮选车间黄药气体进行定量监测,对保护浮选车间工作人员的生命健康具有重要意义。In the process of comprehensive utilization of mineral resources, the first step is to enrich the useful elements in the ore. Common separation methods include gravity separation, magnetic separation, and flotation. Among them, flotation is a widely used ore sorting method. Its basic principle is to use the difference in physical and chemical properties of the surface of different minerals to selectively attach to the air bubbles in the pulp, and float to the pulp with the bubbles. surface, thereby separating useful minerals from gangue. During the flotation process, in order to control the physical and chemical properties of the ore surface and the properties of the pulp, certain flotation agents must be added to the pulp. Xanthate, one of the most common flotation agents, is often used in the flotation of sulfide ores. However, xanthate solution is easy to decompose and volatilize, and its volatile gas has a strong irritating odor, which has serious irritating effects on eyes, skin, respiratory system, central and peripheral nervous systems, and acute exposure to high concentrations (>0.05%) Can cause anesthesia or psychosis. Therefore, the preparation of high-performance gas sensors to quantitatively monitor the xanthate gas in the flotation workshop is of great significance to protect the life and health of the workers in the flotation workshop.
目前市面上已经有诸如半导体式、催化燃烧式、光化学式、电化学式等多种不同类型的气体传感器,检测气体的种类也已经覆盖了大部分常见的气体。但是目前并没有开发出能够有效检测黄药气体的高性能气体传感器。At present, there are many different types of gas sensors such as semiconductor type, catalytic combustion type, photochemical type, electrochemical type, etc. on the market, and the types of detected gases have covered most of the common gases. However, no high-performance gas sensor has been developed that can effectively detect xanthate gas.
发明内容SUMMARY OF THE INVENTION
针对目前选矿厂浮选车间缺乏有效的黄药气体的检测手段,本发明提供了一种基于Au掺杂In2O3纳米球的黄药气体气敏元件及其制备方法。目的是通过优化制备工艺参数以控制合成分散性好且具有较大比表面积的 Au掺杂In2O3纳米球,并以此为气敏材料制备出能够对黄药气体进行实时检测的气敏元件,从而实现有效预防浮选车间由于黄药气体浓度过高而导致的车间工作人员健康受到危害的事故发生。Aiming at the lack of effective xanthate gas detection methods in the flotation workshop of the current mineral processing plant, the present invention provides a xanthate gas gas sensing element based on Au-doped In 2 O 3 nanospheres and a preparation method thereof. The purpose is to control the synthesis of Au-doped In 2 O 3 nanospheres with good dispersion and large specific surface area by optimizing the preparation process parameters, and use this as a gas-sensing material to prepare a gas sensor capable of real-time detection of xanthate gas. Therefore, the flotation workshop can effectively prevent the occurrence of accidents in which the health of workshop workers is endangered due to the high concentration of xanthate gas in the flotation workshop.
本发明提供了一种基于Au掺杂In2O3纳米球的黄药气体气敏元件,所述气敏元件主要由电极元件和均匀涂覆在电极元件上的Au掺杂In2O3纳米球组成,所述Au掺杂In2O3纳米球为六方相晶体结构,直径为75~125nm,表面粗糙多孔,形貌均一且分散性好。The present invention provides a xanthate gas sensor based on Au - doped In 2 O 3 nanospheres. The Au-doped In 2 O 3 nano-spheres have a hexagonal crystal structure, a diameter of 75-125 nm, a rough and porous surface, a uniform morphology and good dispersibility.
进一步地,上述技术方案中,所述电极元件为陶瓷电极。Further, in the above technical solution, the electrode element is a ceramic electrode.
进一步地,上述技术方案中,所述电极元件的形状为管状电极或平面电极。Further, in the above technical solution, the shape of the electrode element is a tubular electrode or a planar electrode.
进一步地,上述技术方案中,所述Au掺杂In2O3纳米球按照如下方法制备:Further, in the above technical solution, the Au-doped In 2 O 3 nanospheres are prepared according to the following method:
①将硝酸铟、一水合柠檬酸、尿素按照摩尔比为1:2:1.5的比例依次加入到去离子水与乙二醇的混合溶液中,所述去离子水与乙二醇的体积比为 1:1,在室温下搅拌至完全溶解;①Add indium nitrate, citric acid monohydrate, and urea to a mixed solution of deionized water and ethylene glycol in a molar ratio of 1:2:1.5. The volume ratio of deionized water and ethylene glycol is 1:1, stir at room temperature until completely dissolved;
②在搅拌过程中,将一定量的与硝酸铟摩尔比为1:100~5:100的氯金酸溶液缓慢加入到步骤①所得溶液中;② During the stirring process, slowly add a certain amount of chloroauric acid solution with a molar ratio of 1:100 to 5:100 to indium nitrate into the solution obtained in step ①;
③将步骤②得到的溶液转移至水热反应釜,随后将其置于烘箱在120 ~180℃条件下反应6~24h;3. transfer the solution obtained in
④反应结束后,待水热反应釜冷却至室温后,将反应得到的产物洗涤、干燥后,于管式炉中在200~400℃条件下热处理2~5h,即可获得Au掺杂 In2O3纳米球。④ After the reaction is completed, after the hydrothermal reaction kettle is cooled to room temperature, the product obtained by the reaction is washed and dried, and then heat-treated in a tube furnace at 200-400 ° C for 2-5 hours to obtain Au-doped In 2 O 3 nanospheres.
进一步地,上述技术方案中,所述步骤④中的洗涤、干燥过程为分别用去离子水和无水乙醇洗涤沉淀产物至少2次后置于干燥箱中在30~80℃干燥12~48h。Further, in the above technical solution, the washing and drying process in step 4 is to wash the precipitated product with deionized water and absolute ethanol at least twice, respectively, and then place the precipitated product in a drying oven at 30 to 80 ° C for 12 to 48 hours.
本发明还提供了一种基于Au掺杂In2O3纳米球的黄药气体气敏元件的制备方法,包括如下步骤:The present invention also provides a method for preparing a xanthate gas sensor based on Au-doped In 2 O 3 nanospheres, comprising the following steps:
①将硝酸铟、一水合柠檬酸、尿素按照摩尔比为1:2:1.5的比例依次加入到去离子水与乙二醇的混合溶液中,所述去离子水与乙二醇的体积比为 1:1,,在室温下搅拌至完全溶解;在搅拌过程中,将一定量的与硝酸铟摩尔比为1:100~5:100的氯金酸溶液缓慢加入到上述溶液中;将上述得到的溶液转移至水热反应釜,随后将其置于烘箱在120~180℃条件下反应6~24 h;反应结束后,待水热反应釜冷却至室温后,将反应得到的产物洗涤、干燥后,于管式炉中在200~400℃条件下热处理2~5h,即可获得Au掺杂 In2O3纳米球;①Add indium nitrate, citric acid monohydrate, and urea to a mixed solution of deionized water and ethylene glycol in a molar ratio of 1:2:1.5. The volume ratio of deionized water and ethylene glycol is 1:1, and stirred at room temperature until completely dissolved; during the stirring process, a certain amount of chloroauric acid solution with a molar ratio of 1:100 to 5:100 to indium nitrate was slowly added to the above solution; the above obtained The solution was transferred to the hydrothermal reactor, and then placed in an oven to react at 120-180 °C for 6-24 h; after the reaction, after the hydrothermal reactor was cooled to room temperature, the product obtained by the reaction was washed and dried Then, heat treatment in a tube furnace at 200-400° C. for 2-5 hours to obtain Au-doped In 2 O 3 nanospheres;
②将步骤①得到的Au掺杂In2O3纳米球分散到无水乙醇中,经湿法研磨10min后调成糊状料浆,获得气敏料浆;② Disperse the Au-doped In 2 O 3 nanospheres obtained in step 1 into anhydrous ethanol, and after wet grinding for 10 minutes, make a paste-like slurry to obtain a gas-sensing slurry;
③将步骤②得到的气敏料浆均匀地涂覆于电极元件表面;③ Evenly coat the gas-sensing slurry obtained in
④将步骤③中涂覆Au掺杂In2O3纳米球的电极元件连接在六角基座上,然后安装在气敏元件老化台上,于300℃条件下老化12~24h,即得基于 Au掺杂In2O3纳米球的黄药气体气敏元件。④ Connect the electrode element coated with Au-doped In 2 O 3 nanospheres in step ③ on the hexagonal base, then install it on the gas sensor aging table, and age it at 300 ° C for 12 to 24 hours, that is, Au based Xanthate gas sensor doped with In 2 O 3 nanospheres.
进一步地,上述技术方案中,所述步骤①中的洗涤、干燥过程为分别用去离子水和无水乙醇洗涤沉淀产物至少2次后置于干燥箱中在30~80℃干燥12~48h。Further, in the above technical solution, the washing and drying process in step ① is to wash the precipitated product with deionized water and absolute ethanol at least twice, respectively, and then place the precipitated product in a drying oven at 30 to 80 ° C for 12 to 48 hours.
进一步地,上述技术方案中,所述步骤②中湿法研磨的具体操作为: 将分散于乙醇中的Au掺杂In2O3纳米球置于玛瑙研钵中,在有乙醇的流体环境下,进行研磨成糊状料浆。Further, in the above-mentioned technical scheme, the concrete operation of wet grinding in the
进一步地,上述技术方案中,所述步骤③中料浆涂覆方法为用勾线笔沾取Au掺杂In2O3纳米球料浆,然后均匀地涂覆在电极元件上,使电极元件表面完全被覆盖且厚度均匀。Further, in the above technical scheme, the slurry coating method in step 3 is to dip the Au-doped In 2 O 3 nano-sphere slurry with a hook pen, and then evenly coat it on the electrode elements, so that the electrode elements The surface is completely covered and uniform in thickness.
与现有技术相比,本发明的特点和有益效果是:Compared with the prior art, the characteristics and beneficial effects of the present invention are:
本发明提供了一种Au掺杂In2O3纳米球的合成方法以及基于此材料的用于检测黄药气体的气敏元件。首先,目前市场上缺乏能够有效对黄药气体进行检测的高性能气敏元件,因此该气敏元件能够填补这个空白。该气敏元件具有较高的灵敏度、良好的稳定性、选择性和可重复性。同时,本发明所述气敏元件使用的气敏材料具有合成方法简单、成本低、结构稳定等特点。The invention provides a synthesis method of Au-doped In 2 O 3 nanospheres and a gas sensing element for detecting xanthate gas based on the material. First of all, there is currently a lack of high-performance gas sensors on the market that can effectively detect xanthate gas, so this gas sensor can fill this gap. The gas sensor has high sensitivity, good stability, selectivity and repeatability. Meanwhile, the gas-sensing material used in the gas-sensing element of the present invention has the characteristics of simple synthesis method, low cost, stable structure and the like.
附图说明Description of drawings
图1为本发明制备的Au掺杂In2O3纳米球的X射线衍射图谱;Fig. 1 is the X-ray diffraction pattern of Au-doped In 2 O 3 nanospheres prepared by the present invention;
图2为本发明制备的Au掺杂In2O3纳米球的(a)低倍率和(b)高倍率扫描电子显微镜照片;Fig. 2 is (a) low magnification and (b) high magnification scanning electron microscope photographs of Au-doped In 2 O 3 nanospheres prepared by the present invention;
图3为实施例1~4中陶瓷电极的结构示意图;其中,1:陶瓷管;2:气敏涂层;3:加热电阻丝;4:金膜;5:铂金引线;6:六角基座;3 is a schematic diagram of the structure of the ceramic electrodes in Examples 1 to 4; wherein, 1: ceramic tube; 2: gas-sensitive coating; 3: heating resistance wire; 4: gold film; 5: platinum lead wire; 6: hexagonal base ;
图4为本发明制备的气体传感器对20ppm黄药气体的灵敏度与工作温度之间的关系图;4 is a graph showing the relationship between the sensitivity of the gas sensor prepared by the present invention to 20ppm xanthate gas and the working temperature;
图5为本发明制备的气敏元件在工作温度300℃时对不同浓度黄药气体的动态响应曲线;Fig. 5 is the dynamic response curve of the gas sensor prepared by the present invention to different concentrations of xanthate gas when the working temperature is 300°C;
图6为本发明制备的气敏元件在工作温度300℃时对不同被检测气体的灵敏度图;FIG. 6 is a graph showing the sensitivity of the gas sensor prepared by the present invention to different detected gases when the working temperature is 300°C;
图7为本发明制备的气敏元件在工作温度300℃时,对50ppm黄药气体6个周期的重复性曲线。Fig. 7 is the repeatability curve of 50ppm xanthate gas for 6 cycles of the gas sensor prepared by the present invention when the working temperature is 300°C.
具体实施方式Detailed ways
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。The following non-limiting examples may enable those of ordinary skill in the art to more fully understand the present invention, but do not limit the present invention in any way.
下述实施例中所述试验方法,如无特殊说明,均为常规方法;所述试剂、材料及设备,如无特殊说明,均可从商业途径获得。The test methods described in the following examples are conventional methods unless otherwise specified; the reagents, materials and equipment can be obtained from commercial sources unless otherwise specified.
下述实施例中所述气敏测试系统为炜盛科技WS-30A型气敏测试系统;所述老化台为炜盛科技TS-60型老化台。The gas-sensing test system described in the following examples is Weisheng Technology WS-30A gas-sensing test system; the aging table is Weisheng Technology TS-60 aging table.
实施例1Example 1
本实施例所述的基于Au掺杂In2O3纳米球的黄药气体气敏元件,其结构示意图如图3所示,包括陶瓷管1、气敏涂层2、加热电阻丝3、金膜4、铂金引线5和六角基座6,其中金膜4覆盖在陶瓷管1两端,制成陶瓷管电极,气敏涂层2均匀地涂覆在整个陶瓷管1和金膜4表面,加热电阻丝 3横穿在陶瓷管1中,并焊接在六角基座6的加热电极上;铂金引线4一端焊接在金膜4表面,另一端焊接在六角基座6的四个测量电极上制成基于Au掺杂In2O3纳米球的黄药气体气敏元件。所述气敏涂层2的原料为 Au掺杂In2O3纳米球,所述Au掺杂In2O3纳米球形貌均一且具有良好的分散性,直径为75~125nm。所述Au掺杂In2O3纳米球的制备工艺按照以下步骤进行:The xanthate gas sensor based on Au-doped In 2 O 3 nanospheres described in this embodiment has a schematic structural diagram as shown in FIG. 3 , including a ceramic tube 1 , a
①将1mmol硝酸铟、2mmol一水合柠檬酸、1.5mmol尿素依次加入到15ml去离子水与15ml乙二醇的混合溶液中,并在室温下搅拌至完全溶解。①Add 1 mmol of indium nitrate, 2 mmol of citric acid monohydrate, and 1.5 mmol of urea to a mixed solution of 15 ml of deionized water and 15 ml of ethylene glycol in sequence, and stir at room temperature until completely dissolved.
②边搅拌边将3ml氯金酸溶液(4.256g/L)缓慢加入到步骤①所得溶液中。② Slowly add 3 ml of chloroauric acid solution (4.256 g/L) to the solution obtained in step ① while stirring.
③将步骤②得到的溶液转移至聚四氟乙烯水热反应釜,随后将其置于烘箱中在160℃条件下反应12h。③ Transfer the solution obtained in
④反应结束后,待水热反应釜自然冷却至室温后,将反应得到的产物用去离子水和乙醇清至少2次,以去除其中的杂质离子。④ After the reaction is completed, after the hydrothermal reactor is naturally cooled to room temperature, the product obtained by the reaction is washed with deionized water and ethanol at least twice to remove the impurity ions therein.
⑤将清洗后的产物在真空干燥箱中30℃条件下干燥12h,然后于管式炉中在400℃条件下热处理4h,即可获得Au掺杂In2O3纳米球。⑤ The cleaned product was dried in a vacuum drying oven at 30°C for 12 hours, and then heat-treated in a tube furnace at 400°C for 4 hours to obtain Au-doped In 2 O 3 nanospheres.
图1为所制备的Au掺杂In2O3纳米球的XRD图谱。从图中可以看出,所制备Au掺杂In2O3纳米球由立方相的单质Au和六方相In2O3组成且结晶性较好。图2为所制备Au掺杂In2O3纳米球的扫描电子显微镜照片。可以看出,所得产物为球形,直径为75~125nm,表面较为粗糙多孔,由 In2O3纳米颗粒构成,分散性较好。Figure 1 is the XRD pattern of the as-prepared Au-doped In 2 O 3 nanospheres. It can be seen from the figure that the prepared Au-doped In 2 O 3 nanospheres are composed of cubic phase elemental Au and hexagonal phase In 2 O 3 and have good crystallinity. FIG. 2 is a scanning electron microscope photograph of the prepared Au-doped In 2 O 3 nanospheres. It can be seen that the obtained product is spherical with a diameter of 75-125 nm, the surface is relatively rough and porous, and is composed of In 2 O 3 nanoparticles with good dispersibility.
一种基于Au掺杂In2O3纳米球的黄药气体气敏元件的制备方法,按照以下步骤进行:A preparation method of a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres, which is carried out according to the following steps:
①将0.01g上述Au掺杂In2O3纳米球分散到10mL无水乙醇中,于玛瑙研钵中,在有乙醇的流体环境下研磨10min后调成糊状料浆,获得气敏料浆。① Disperse 0.01 g of the above Au-doped In 2 O 3 nanospheres into 10 mL of anhydrous ethanol, grind in an agate mortar for 10 minutes in a fluid environment with ethanol, and then adjust to a paste-like slurry to obtain a gas-sensing slurry .
②将上述气敏料浆均匀地涂覆于陶瓷管电极表面制备成气敏涂层,所述涂覆方法为用勾线笔沾取Au掺杂In2O3纳米球料浆,然后均匀地涂覆在电极元件上,使电极元件表面完全被覆盖且厚度均匀。② The above-mentioned gas - sensing slurry is evenly coated on the surface of the ceramic tube electrode to prepare a gas-sensitive coating. It is coated on the electrode element so that the surface of the electrode element is completely covered and the thickness is uniform.
③将上述制备而成的电极焊接至六角基座上,然后于气敏元件老化台上在300℃条件下老化24h,即得基于Au掺杂In2O3纳米球的黄药气体气敏元件。③ Weld the electrodes prepared above to the hexagonal base, and then age them on the gas sensor aging table at 300°C for 24 hours to obtain a xanthate gas sensor based on Au-doped In 2 O 3 nanospheres .
图4为本发明制备的气体传感器对20ppm黄药气体的灵敏度与工作温度之间的关系图,可以看出,该气体传感器对相同浓度黄药气体的灵敏度随着工作温度的升高,呈现先升高后下降的趋势,并且在工作温度300℃时获得对黄药气体的最大灵敏度。图5为气敏元件在工作温度300℃时对不同浓度黄药气体的灵敏度,可以看出,该气敏元件的灵敏度随着黄药气体浓度的升高而增大。同时,气敏元件还表现出优异的可逆性、可重复性和稳定性。图6为气敏元件在工作温度300℃时对不同气体的灵敏度。可以看出,该气敏元件对黄药气体的灵敏度远高于对其它常见的干扰性气体的灵敏度,表明该气敏元件对黄药气体具有良好的选择性,能够用于对黄药气体的特异性识别。图7为气敏元件在工作温度300℃时对50ppm黄药气体6个周期的重复性曲线。可以看出,该气敏元件在连续6个测试周期中,其响应和恢复特性几乎相同,波动性较小。同时,在进行连续6次测试后,其电阻仍然可以很快地恢复到初始值,表明其具有优异的稳定性。4 is a graph showing the relationship between the sensitivity of the gas sensor prepared by the present invention to 20 ppm xanthate gas and the working temperature. It can be seen that the sensitivity of the gas sensor to xanthate gas of the same concentration increases with the increase of the working temperature. The trend of decreasing after increasing, and the maximum sensitivity to xanthate gas was obtained at the working temperature of 300 °C. Figure 5 shows the sensitivity of the gas sensor to different concentrations of xanthate gas when the working temperature is 300°C. It can be seen that the sensitivity of the gas sensor increases with the increase of the concentration of xanthate gas. At the same time, the gas sensor also exhibits excellent reversibility, repeatability and stability. Figure 6 shows the sensitivity of the gas sensor to different gases at an operating temperature of 300°C. It can be seen that the sensitivity of the gas sensor to xanthate gas is much higher than the sensitivity to other common interfering gases, indicating that the gas sensor has good selectivity for xanthate gas and can be used for xanthate gas detection. specific identification. Figure 7 is the repeatability curve of the gas sensor for 6 cycles of 50ppm xanthate gas when the working temperature is 300°C. It can be seen that the gas sensor has almost the same response and recovery characteristics in 6 consecutive test cycles, and the fluctuation is small. At the same time, after 6 consecutive tests, its resistance can still quickly recover to the initial value, indicating its excellent stability.
实施例2Example 2
本实施例所述的基于Au掺杂In2O3纳米球的黄药气体气敏元件,其结构示意图如图3所示,包括陶瓷管1、气敏涂层2、加热电阻丝3、金膜4、铂金引线5和六角基座6,其中金膜4覆盖在陶瓷管1两端,形成陶瓷管电极,气敏涂层2均匀地涂覆在整个陶瓷管1和金膜4表面,加热电阻丝 3横穿在陶瓷管1中,并焊接在六角基座6的加热电极上;铂金引线4一端焊接在金膜4表面,另一端焊接在六角基座6的四个测量电极上制成基于Au掺杂In2O3纳米球的黄药气体气敏元件。所述气敏涂层2的原料为 Au掺杂In2O3纳米球,所述Au掺杂In2O3纳米球形貌均一且具有良好的分散性,直径为75~125nm。所述Au掺杂In2O3纳米球的制备工艺按照以下步骤进行:The xanthate gas sensor based on Au-doped In 2 O 3 nanospheres described in this embodiment has a schematic structural diagram as shown in FIG. 3 , including a ceramic tube 1 , a
①将1mmol硝酸铟、2mmol一水合柠檬酸、1.5mmol尿素依次加入到15ml去离子水与15ml乙二醇的混合溶液中,并在室温下搅拌至完全溶解。①Add 1 mmol of indium nitrate, 2 mmol of citric acid monohydrate, and 1.5 mmol of urea to a mixed solution of 15 ml of deionized water and 15 ml of ethylene glycol in sequence, and stir at room temperature until completely dissolved.
②边搅拌边将3ml氯金酸溶液(4.256g/L)缓慢加入到步骤①所得溶液中。② Slowly add 3 ml of chloroauric acid solution (4.256 g/L) to the solution obtained in step ① while stirring.
③将步骤②得到的溶液转移至聚四氟乙烯水热反应釜,随后将其置于烘箱中在160℃条件下反应8h。③ Transfer the solution obtained in
④反应结束后,待水热反应釜自然冷却至室温后,将反应得到的产物用去离子水和乙醇清洗至少2次,以去除其中的杂质离子。④ After the reaction, after the hydrothermal reactor is naturally cooled to room temperature, the product obtained by the reaction is washed at least twice with deionized water and ethanol to remove the impurity ions therein.
⑤将清洗后的产物在真空干燥箱中40℃条件下干燥15h,然后于管式炉中在400℃条件下热处理4h,即可获得Au掺杂In2O3纳米球。⑤ The cleaned product was dried in a vacuum drying oven at 40°C for 15h, and then heat-treated in a tube furnace at 400°C for 4h to obtain Au-doped In 2 O 3 nanospheres.
所得Au掺杂In2O3纳米球为六方相晶体结构且结晶性较好。纳米球直径为75~125nm,表面较为粗糙多孔,由In2O3纳米颗粒构成,分散性较好。The obtained Au-doped In 2 O 3 nanospheres have a hexagonal crystal structure and good crystallinity. The diameter of the nanosphere is 75-125nm, the surface is relatively rough and porous, it is composed of In 2 O 3 nanoparticles, and the dispersibility is good.
一种基于Au掺杂In2O3纳米球的黄药气体气敏元件的制备方法,按照以下步骤进行:A preparation method of a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres, which is carried out according to the following steps:
①将0.01g上述Au掺杂In2O3纳米球分散10mL到无水乙醇中,于玛瑙研钵中,在有乙醇的流体环境下研磨10min后调成糊状料浆,获得气敏料浆。① Disperse 0.01 g of the above Au-doped In 2 O 3 nanospheres in 10 mL of anhydrous ethanol, grind in an agate mortar for 10 minutes in a fluid environment with ethanol, and then adjust to a paste-like slurry to obtain a gas-sensing slurry .
②将上述气敏料浆均匀地涂覆于电极元件表面制备成气敏涂层,所述涂覆方法为用勾线笔沾取Au掺杂In2O3纳米球料浆,然后均匀地涂覆在电极元件上,使电极元件表面完全被覆盖且厚度均匀。② The above-mentioned gas-sensitive slurry is uniformly coated on the surface of the electrode element to prepare a gas-sensitive coating. The coating method is to dip the Au-doped In 2 O 3 nano-sphere slurry with a hook pen, and then evenly apply Cover the electrode element so that the surface of the electrode element is completely covered and the thickness is uniform.
③将上述制备而成的电极焊接至六角基座上,于气敏元件老化台上在 300℃条件下老化24h,即得基于Au掺杂In2O3纳米球的黄药气体气敏元件。③ Weld the electrodes prepared above to the hexagonal base, and age them on the gas sensor aging table at 300° C. for 24 hours to obtain a xanthate gas sensor based on Au-doped In 2 O 3 nanospheres.
经检测,本实施例制备的气敏元件在工作温度200~325℃条件下对黄药气体具有良好的气敏特性。After testing, the gas-sensing element prepared in this example has good gas-sensing properties for xanthate gas under the condition of working temperature of 200-325°C.
实施例3Example 3
本实施例所述的基于Au掺杂In2O3纳米球的黄药气体气敏元件,其结构示意图如图3所示,包括陶瓷管1、气敏涂层2、加热电阻丝3、金膜4、铂金引线5和六角基座6,其中金膜4覆盖在陶瓷管1两端,形成陶瓷管电极,气敏涂层2均匀地涂覆在整个陶瓷管1和金膜4表面,加热电阻丝 3横穿在陶瓷管1中,并焊接在六角基座6的加热电极上;铂金引线4一端焊接在金膜4表面,另一端焊接在六角基座6的四个测量电极上制成基于Au掺杂In2O3纳米球的黄药气体气敏元件。所述气敏涂层2的原料为 Au掺杂In2O3纳米球,所述Au掺杂In2O3纳米球形貌均一且具有良好的分散性,直径为75~125nm。所述Au掺杂In2O3纳米球的制备工艺按照以下步骤进行:The xanthate gas sensor based on Au-doped In 2 O 3 nanospheres described in this embodiment has a schematic structural diagram as shown in FIG. 3 , including a ceramic tube 1 , a
①将1mmol硝酸铟、2mmol一水合柠檬酸、1.5mmol尿素依次加入到15ml去离子水与15ml乙二醇的混合溶液中,并在室温下搅拌至完全溶解。①Add 1 mmol of indium nitrate, 2 mmol of citric acid monohydrate, and 1.5 mmol of urea to a mixed solution of 15 ml of deionized water and 15 ml of ethylene glycol in sequence, and stir at room temperature until completely dissolved.
②边搅拌边将3ml氯金酸溶液(4.256g/L)缓慢加入到步骤①所得溶液中。② Slowly add 3 ml of chloroauric acid solution (4.256 g/L) to the solution obtained in step ① while stirring.
③将步骤②得到的溶液转移至聚四氟乙烯水热反应釜,随后将其置于烘箱中在180℃条件下反应8h。③ Transfer the solution obtained in
④反应结束后,待水热反应釜自然冷却至室温后,将反应得到的产物用去离子水和乙醇清洗至少2次,以去除其中的杂质离子。④ After the reaction, after the hydrothermal reactor is naturally cooled to room temperature, the product obtained by the reaction is washed at least twice with deionized water and ethanol to remove the impurity ions therein.
⑤将清洗后的产物在真空干燥箱中30℃条件下干燥12h,然后于管式炉中在400℃条件下热处理4h,即可获得Au掺杂In2O3纳米球。⑤ The cleaned product was dried in a vacuum drying oven at 30°C for 12 hours, and then heat-treated in a tube furnace at 400°C for 4 hours to obtain Au-doped In 2 O 3 nanospheres.
所得Au掺杂In2O3纳米球为六方相晶体结构且结晶性较好。纳米球直径为75~125nm,表面较为粗糙多孔,由In2O3纳米颗粒构成,分散性较好。The obtained Au-doped In 2 O 3 nanospheres have a hexagonal crystal structure and good crystallinity. The diameter of the nanosphere is 75-125nm, the surface is relatively rough and porous, and it is composed of In 2 O 3 nanoparticles with good dispersibility.
一种基于Au掺杂In2O3纳米球的黄药气体气敏元件的制备方法,按照以下步骤进行:A preparation method of a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres, which is carried out according to the following steps:
①将0.01g上述Au掺杂In2O3纳米球分散10mL到无水乙醇中,于玛瑙研钵中,在有乙醇的流体环境下研磨10min后调成糊状料浆,获得气敏料浆。① Disperse 0.01 g of the above Au-doped In 2 O 3 nanospheres in 10 mL of anhydrous ethanol, grind in an agate mortar for 10 minutes in a fluid environment with ethanol, and then adjust to a paste-like slurry to obtain a gas-sensing slurry .
②将上述气敏料浆均匀地涂覆于电极元件表面制备成气敏涂层,所述涂覆方法为用勾线笔沾取Au掺杂In2O3纳米球料浆,然后均匀地涂覆在电极元件上,使电极元件表面完全被覆盖且厚度均匀。② The above-mentioned gas-sensitive slurry is uniformly coated on the surface of the electrode element to prepare a gas-sensitive coating. The coating method is to dip the Au-doped In 2 O 3 nano-sphere slurry with a hook pen, and then evenly apply Cover the electrode element so that the surface of the electrode element is completely covered and the thickness is uniform.
③将上述制备而成的电极焊接至六角基座上,于气敏元件老化台上在 300℃条件下老化12~24h,即得基于Au掺杂In2O3纳米球的黄药气体气敏元件。③ Weld the electrode prepared above to the hexagonal base, and age it on the gas sensor aging table at 300°C for 12-24 hours, to obtain a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres element.
经检测,本实施例制备的气敏元件在工作温度200~325℃条件下对黄药气体具有良好的气敏特性。After testing, the gas-sensing element prepared in this example has good gas-sensing properties for xanthate gas under the condition of working temperature of 200-325°C.
实施例4Example 4
本实施例所述的基于Au掺杂In2O3纳米球的黄药气体气敏元件,其结构示意图如图3所示,包括陶瓷管1、气敏涂层2、加热电阻丝3、金膜4、铂金引线5和六角基座6,其中金膜4覆盖在陶瓷管1两端,形成陶瓷管电极,气敏涂层2均匀地涂覆在整个陶瓷管1和金膜4表面,加热电阻丝 3横穿在陶瓷管1中,并焊接在六角基座6的加热电极上;铂金引线4一端焊接在金膜4表面,另一端焊接在六角基座6的四个测量电极上制成基于Au掺杂In2O3纳米球的黄药气体气敏元件。所述气敏涂层2的原料为 Au掺杂In2O3纳米球,所述Au掺杂In2O3纳米球形貌均一且具有良好的分散性,直径为75~125nm。所述Au掺杂In2O3纳米球的制备工艺按照以下步骤进行:The xanthate gas sensor based on Au-doped In 2 O 3 nanospheres described in this embodiment has a schematic structural diagram as shown in FIG. 3 , including a ceramic tube 1 , a
①将1mmol硝酸铟、2mmol一水合柠檬酸、1.5mmol尿素依次加入到15ml去离子水与15ml乙二醇的混合溶液中,并在室温下搅拌至完全溶解。①Add 1 mmol of indium nitrate, 2 mmol of citric acid monohydrate, and 1.5 mmol of urea to a mixed solution of 15 ml of deionized water and 15 ml of ethylene glycol in sequence, and stir at room temperature until completely dissolved.
②边搅拌边将3ml氯金酸溶液(4.256g/L)缓慢加入到步骤①所得溶液中。② Slowly add 3 ml of chloroauric acid solution (4.256 g/L) to the solution obtained in step ① while stirring.
③将步骤②得到的溶液转移至聚四氟乙烯水热反应釜,随后将其置于烘箱中在160℃条件下12h。③ Transfer the solution obtained in
④反应结束后,待水热反应釜自然冷却至室温后,将反应得到的产物用去离子水和乙醇清洗至少2次,以去除其中的杂质离子。④ After the reaction, after the hydrothermal reactor is naturally cooled to room temperature, the product obtained by the reaction is washed at least twice with deionized water and ethanol to remove the impurity ions therein.
⑤将清洗后的产物在真空干燥箱中30℃条件下干燥12h,然后于管式炉中在300℃条件下热处理4h,即可获得Au掺杂In2O3纳米球。⑤ The cleaned product was dried in a vacuum drying oven at 30°C for 12 hours, and then heat-treated in a tube furnace at 300°C for 4 hours to obtain Au-doped In 2 O 3 nanospheres.
所得Au掺杂In2O3纳米球为六方相晶体结构且结晶性较好。纳米球直径为75~125nm,表面较为粗糙多孔,由In2O3纳米颗粒构成,分散性较好。The obtained Au-doped In 2 O 3 nanospheres have a hexagonal crystal structure and good crystallinity. The diameter of the nanosphere is 75-125nm, the surface is relatively rough and porous, and it is composed of In 2 O 3 nanoparticles with good dispersibility.
一种基于Au掺杂In2O3纳米球的黄药气体气敏元件的制备方法,按照以下步骤进行:A preparation method of a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres, which is carried out according to the following steps:
①将0.01g上述Au掺杂In2O3纳米球分散到10mL无水乙醇中,于玛瑙研钵中,在有乙醇的流体环境下研磨10min后调成糊状料浆,获得气敏料浆。① Disperse 0.01 g of the above Au-doped In 2 O 3 nanospheres into 10 mL of anhydrous ethanol, grind in an agate mortar for 10 minutes in a fluid environment with ethanol, and then adjust to a paste-like slurry to obtain a gas-sensing slurry .
②将上述气敏料浆均匀地涂覆于电极元件表面制备成气敏涂层,所述涂覆方法为用勾线笔沾取Au掺杂In2O3纳米球料浆,然后均匀地涂覆在电极元件上,使电极元件表面完全被覆盖且厚度均匀。② The above-mentioned gas-sensitive slurry is uniformly coated on the surface of the electrode element to prepare a gas-sensitive coating. The coating method is to dip the Au-doped In 2 O 3 nano-sphere slurry with a hook pen, and then evenly apply Cover the electrode element so that the surface of the electrode element is completely covered and the thickness is uniform.
③将上述制备而成的电极焊接至六角基座上,于气敏元件老化台上在300℃条件下老化12~24h,即得基于Au掺杂In2O3纳米球的黄药气体气敏元件。③ Weld the electrode prepared above to the hexagonal base, and age it on the gas sensor aging table at 300°C for 12-24 hours, to obtain a xanthate gas gas sensor based on Au-doped In 2 O 3 nanospheres element.
经检测,本实施例制备的气敏元件在工作温度200~325℃条件下对黄药气体具有良好的气敏特性。After testing, the gas-sensing element prepared in this example has good gas-sensing properties for xanthate gas under the condition of working temperature of 200-325°C.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910728452.4A CN110412088B (en) | 2019-08-08 | 2019-08-08 | In doping based on Au2O3Xanthate gas sensitive element of nanosphere and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910728452.4A CN110412088B (en) | 2019-08-08 | 2019-08-08 | In doping based on Au2O3Xanthate gas sensitive element of nanosphere and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110412088A CN110412088A (en) | 2019-11-05 |
CN110412088B true CN110412088B (en) | 2020-12-25 |
Family
ID=68366387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910728452.4A Active CN110412088B (en) | 2019-08-08 | 2019-08-08 | In doping based on Au2O3Xanthate gas sensitive element of nanosphere and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110412088B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111735857A (en) * | 2020-07-07 | 2020-10-02 | 华准科技(绍兴)有限公司 | In supporting Ru2O3Nano material and preparation method and application thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103183374B (en) * | 2013-03-13 | 2014-10-01 | 济南大学 | A kind of preparation method of monodisperse indium oxide nanoporous microsphere |
CN104229871A (en) * | 2014-06-24 | 2014-12-24 | 济南大学 | Preparation method of flower type indium oxide gas-sensitive material with hierarchical structure |
CN105084308B (en) * | 2015-07-17 | 2016-11-30 | 济南大学 | A kind of preparation method of the hollow hierarchy Indium sesquioxide. gas sensitive of load gold nano grain |
CN105301062B (en) * | 2015-10-29 | 2017-12-01 | 东北大学 | One kind is based on classifying porous WO3Gas sensor of micron ball and preparation method thereof |
CN107140682B (en) * | 2017-06-12 | 2019-03-01 | 吉林大学 | A kind of the indium oxide powder and its low-temperature hydro-thermal synthesis of morphology controllable |
CN108254416A (en) * | 2018-01-02 | 2018-07-06 | 吉林大学 | Meso-hole structure In is supported based on Au2O3The NO of nano sensitive material2Sensor, preparation method and applications |
CN108426924B (en) * | 2018-05-03 | 2020-05-01 | 吉林大学 | Ammonia gas sensor, preparation method and application thereof |
-
2019
- 2019-08-08 CN CN201910728452.4A patent/CN110412088B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN110412088A (en) | 2019-11-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105301062B (en) | One kind is based on classifying porous WO3Gas sensor of micron ball and preparation method thereof | |
CN106093140B (en) | Composite structure doped gas-sensing material for NO2 gas, gas-sensing element and its manufacturing method and application | |
CN108732207A (en) | A kind of sensitive material used in formaldehyde examination and preparation method and application | |
CN107561133A (en) | A kind of preparation method and application of precious metal doping WO3 base formaldehyde gas sensitive materials | |
CN110606504B (en) | Hierarchical nuclear shell SnO2Microsphere and preparation method and application thereof | |
CN106865628A (en) | One kind is used for room temperature H2S gas sensing materials nickel oxide and preparation method thereof | |
CN103713016B (en) | Palladium doping stannic oxide enveloped carbon nanometer tube and its preparation method and application | |
CN108946815B (en) | WO (WO)3Nanoparticles, method for the production thereof and use thereof in sensors | |
CN108398408A (en) | A kind of composite air-sensitive material and preparation method thereof for formaldehyde gas detection | |
CN109781796B (en) | NO for preparing ZnS-ZnO heterojunction nano-particles based on sphalerite2Gas sensor | |
CN108715457A (en) | Based on MOF template controlledly synthesis nano structure of zinc oxide gas sensors | |
CN107572601A (en) | A kind of synthetic method of CoO appearance of nano material regulation and control | |
Zhai et al. | High sensitivity and fast response sensor for formaldehyde based on In2O3/Sn2O3 heterojunction | |
CN108195908A (en) | A kind of palladium-class graphite phase carbon nitride-carbon nano-tube combination electrode and its preparation method and application | |
CN110412088B (en) | In doping based on Au2O3Xanthate gas sensitive element of nanosphere and preparation method thereof | |
CN110108760B (en) | A kind of H2S gas sensor and preparation method thereof | |
CN110887890A (en) | Method for electrochemically detecting heavy metal ions by doping modified reinforced nano material | |
CN111217387A (en) | Three-dimensional flower-like hydroxyl zinc fluoride material, preparation method thereof and application thereof in gas-sensitive detection | |
CN110412086A (en) | A kind of isopropanol gas sensor based on perovskite structure ZnSnO3 nanosphere and its preparation method | |
CN109115843A (en) | A kind of Cu doping ZnFe2O4Nano particle and its preparation method and application | |
CN113104886A (en) | Co-doped echinoid SnO2Preparation method and application of-ZnO heterostructure gas-sensitive material | |
CN113219009A (en) | Sulfur dioxide gas-sensitive material, preparation method thereof, sulfur dioxide gas-sensitive element and preparation method thereof | |
CN112362712A (en) | Electrochemical sensor electrode capable of simultaneously detecting heavy metal lead and cadmium ions in grains | |
CN112067666A (en) | Preparation method of tin dioxide gas sensor gas sensor material doped with silver phosphate | |
CN100432012C (en) | Nanometer gas-sensing material of ternary composite metal oxide and production thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |