技术领域Technical Field
本发明属于半导体气体敏感材料领域，尤其涉及一种用于室温氢气气体检测的超灵敏金属氧化物Pd/CeO2立方体纳米复合材料。The invention belongs to the field of semiconductor gas sensitive materials, and in particular relates to an ultra-sensitive metal oxide Pd/CeO2 cubic nanocomposite material for room temperature hydrogen gas detection.
背景技术Background technique
金属氧化物是一种常用的半导体气敏材料，因其稳定性高、灵敏度好而备受青睐。通过制备高性能的金属氧化物气敏材料，并设计小型、廉价且响应速度快的气体传感器，可以实现对氢气等小分子气体的低温、实时检测，这对于诸如安全监测、环境保护等领域具有重要的意义。氢敏材料的形貌可以影响其表面积、表面能和孔隙结构等一系列性质，从而影响其气敏性能。因此，在设计和优化气敏材料时，通过合适的方法进行形貌控制以实现所需的气敏性能。纯CeO2气体传感器由于高带隙能、低本征载流子浓度和高载流子复合率，使其工作温度高（200~400℃）、室温下响应速率慢和多组分气氛中选择性差等缺点限制了其实用性。Metal oxide is a commonly used semiconductor gas-sensitive material, which is favored for its high stability and good sensitivity. By preparing high-performance metal oxide gas-sensitive materials and designing small, cheap and fast-responding gas sensors, low-temperature and real-time detection of small molecular gases such as hydrogen can be achieved, which is of great significance in fields such as safety monitoring and environmental protection. The morphology of hydrogen-sensitive materials can affect a series of properties such as surface area, surface energy and pore structure, thereby affecting their gas-sensitive performance. Therefore, when designing and optimizing gas-sensitive materials, morphology control is carried out by appropriate methods to achieve the desired gas-sensitive performance. Pure CeO2 gas sensors have high operating temperatures (200~400℃), slow response rates at room temperature and poor selectivity in multi-component atmospheres due to their high band gap energy, low intrinsic carrier concentration and high carrier recombination rate, which limit their practicality.
发明内容Summary of the invention
本发明针对现有技术的不足，解决氢气传感器工作温度高、响应速率慢和选择性差的问题。制备一种Pd/CeO2金属氧化物纳米复合材料，该材料为立方体结构，并在室温下实现了对氢气气体的快速响应和良好的选择性探测。The present invention aims at the deficiencies of the prior art and solves the problems of high operating temperature, slow response rate and poor selectivity of hydrogen sensors. A Pd/CeO2 metal oxide nanocomposite material is prepared, which has a cubic structure and achieves rapid response and good selective detection of hydrogen gas at room temperature.
本发明采用的技术方案为：一种室温氢气敏感材料的制备方法，包括以下步骤：The technical solution adopted by the present invention is: a method for preparing a room temperature hydrogen sensitive material, comprising the following steps:
1)将NaOH溶液加入到Ce(NO3)3•6H2O的水溶液中，对所得溶液进行水热反应，反应结束后将产物分离、洗涤；所述Ce(NO3)3•6H2O与NaOH的质量比为1:9.6-2:1；所述水热反应的温度为100-190℃，反应时间为12-24h；1) Adding NaOH solution to Ce(NO3 )3 •6H2 O aqueous solution, subjecting the obtained solution to hydrothermal reaction, separating and washing the product after the reaction is completed; the mass ratio of Ce(NO3 )3 •6H2 O to NaOH is 1:9.6-2:1; the temperature of the hydrothermal reaction is 100-190° C., and the reaction time is 12-24 hours;
2)将步骤1)的水热产物洗涤烘干后置于马弗炉煅烧，获得立方体的CeO2纳米颗粒；2) washing and drying the hydrothermal product of step 1) and calcining it in a muffle furnace to obtain cubicCeO2 nanoparticles;
3)将上述CeO2纳米颗粒超声分散于去离子水中，混合均匀后加入PdCl2溶液，PdCl2与CeO2质量比为1:100-10:100；再加入抗坏血酸陈化后将产物分离、洗涤、烘干，最终获得金属氧化物室温氢气敏感材料。3) Ultrasonic dispersion of theCeO2 nanoparticles in deionized water, uniformly mixed, and then addingPdCl2 solution, wherein the mass ratio ofPdCl2 toCeO2 is 1:100-10:100; ascorbic acid is then added, and the product is separated, washed, and dried after aging, to finally obtain a metal oxide room temperature hydrogen sensitive material.
所述马弗炉升温速率为5-10℃/min。The heating rate of the muffle furnace is 5-10°C/min.
所述马弗炉煅烧温度为400-550℃。The muffle furnace calcination temperature is 400-550°C.
所述马弗炉煅烧时间为3-5h。The muffle furnace calcination time is 3-5h.
所述抗坏血酸与CeO2质量比为1:100-5:100。The mass ratio of ascorbic acid toCeO2 is 1:100-5:100.
所述陈化的时间为12-24h。The aging time is 12-24h.
本发明的另一目的是，采用上述制备方法制得室温氢气敏感立方体材料。Another object of the present invention is to prepare room temperature hydrogen sensitive cubic material by using the above preparation method.
所述室温氢气敏感立方体材料具有立方体状结构。The room temperature hydrogen sensitive cubic material has a cubic structure.
一种室温氢气传感器，该传感器中包含上述室温氢气敏感立方体材料。A room temperature hydrogen sensor comprises the room temperature hydrogen sensitive cubic material.
本发明相对现有技术的有益效果：本发明制得的Pd/CeO2纳米颗粒为立方体，其具有高比表面积，有利于表面气体吸附和脱附，获得良好的气体敏感特性。本发明中制备的Pd/CeO2纳米复合材料在室温下实现对氢气的检测。本发明中制备的Pd/CeO2纳米复合材料对氢气具有良好的选择性。本发明中制备的Pd/CeO2纳米复合材料在室温下对3%氢气的响应时间为2s。复合材料中具有氧化还原能力的Ce(IV)↔Ce(III)被富含羟基的抗坏血酸还原后，构建了"羟基-氧空位模型"。该模型不仅促进了氧空位（簇）在氧化铈晶格中的形成，而且表面Ce(III)的相对含量和氧空位（OVs）的大小与高活性氧呈线性相关，更有利于分子氧的捕获和活化，这些优势极大地促进了H2的响应和恢复时间。另一方面，CeO2纳米立方体增加了活性表面积，为贵金属Pd NPs提供了更多的负载位点，从而参与了吸附、解吸和扩散过程，实现了室温下氢气的快速检测。The beneficial effects of the present invention relative to the prior art are as follows: the Pd/CeO2 nanoparticles prepared by the present invention are cubic, have a high specific surface area, are conducive to surface gas adsorption and desorption, and obtain good gas sensitive properties. The Pd/CeO2 nanocomposite prepared in the present invention can detect hydrogen at room temperature. The Pd/CeO2 nanocomposite prepared in the present invention has good selectivity for hydrogen. The response time of the Pd/CeO2 nanocomposite prepared in the present invention to 3% hydrogen at room temperature is 2s. After the redox-capable Ce(IV)↔Ce(III) in the composite material is reduced by hydroxyl-rich ascorbic acid, a "hydroxyl-oxygen vacancy model" is constructed. This model not only promotes the formation of oxygen vacancies (clusters) in the cerium oxide lattice, but also the relative content of surface Ce(III) and the size of oxygen vacancies (OVs) are linearly correlated with highly active oxygen, which is more conducive to the capture and activation of molecular oxygen. These advantages greatly promote the response and recovery time ofH2 . On the other hand,CeO2 nanocubes increase the active surface area and provide more loading sites for the noble metal Pd NPs, thereby participating in the adsorption, desorption, and diffusion processes, achieving rapid detection of hydrogen at room temperature.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1实施例1-3制备的立方体、球形和棒状气敏复合材料的X射线衍射（XRD）谱图。FIG1 X-ray diffraction (XRD) spectra of cubic, spherical and rod-shaped gas-sensitive composite materials prepared in Examples 1-3.
图2实施例1-3制备的立方体、球形和棒状Pd/CeO2纳米复合材料形貌TEM图。Figure 2 TEM images of cubic, spherical and rod-shaped Pd/CeO2 nanocomposites prepared in Examples 1-3.
图3是实施例1-3制备的立方体、球形和棒状Pd/CeO2纳米复合材料在25℃工作温度时对1%氢气响应的重复图。FIG. 3 is a repeated graph of the cubic, spherical and rod-shaped Pd/CeO2 nanocomposites prepared in Examples 1-3 in response to 1% hydrogen at an operating temperature of 25° C.
图4是实施例1-3制备的立方体、球形和棒状Pd/CeO2纳米复合材料在25℃工作温度时对1%氢气响应和恢复时间。FIG. 4 shows the response and recovery time of cubic, spherical and rod-shaped Pd/CeO2 nanocomposites prepared in Examples 1-3 to 1% hydrogen at an operating temperature of 25° C.
图5是实施例1制备的立方体Pd/CeO2纳米复合材料在25℃工作温度时对不同浓度氢气响应时间的比较。FIG. 5 is a comparison of the response time of the cubic Pd/CeO2 nanocomposite prepared in Example 1 to different concentrations of hydrogen at an operating temperature of 25° C.
图6是实施例1-3制备的立方体、球形和棒状Pd/CeO2纳米复合材料对1%不同气体的选择性柱状图。FIG. 6 is a bar graph showing the selectivity of cubic, spherical and rod-shaped Pd/CeO2 nanocomposites prepared in Examples 1-3 to 1% of different gases.
具体实施方式Detailed ways
实施例1Example 1
1)溶液A：将1.911克Ce(NO3)3•6H2O溶于40毫升去离子水中。溶液B：将0.896克NaOH分散在去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟。然后加入到100mL高压釜中，在180℃下反应24小时。将水热反应后的产物离心分离，用乙醇洗涤3次后在80℃下干燥过夜；1) Solution A: Dissolve 1.911 g of Ce(NO3 )3 •6H2 O in 40 ml of deionized water. Solution B: Disperse 0.896 g of NaOH in deionized water. Slowly add solution B to solution A and stir for 30 minutes. Then add it to a 100 mL autoclave and react at 180°C for 24 hours. The product after the hydrothermal reaction is centrifuged, washed with ethanol three times and dried at 80°C overnight;
2)将步骤1）中的产物在马弗炉中以5℃/min的升温速率加热到500℃，并煅烧4小时；2) heating the product in step 1) to 500° C. in a muffle furnace at a heating rate of 5° C./min and calcining for 4 hours;
3)将60毫克步骤2）产物和适当浓度的PdCl2（0.6767M）分散在20毫升去离子水中，搅拌30分钟。然后，在磁力搅拌下加入0.2克抗坏血酸。陈化22小时后，将沉淀物离心，并用去离子水洗涤多次以去除杂质。最后，将离心后的产物在45℃的真空烘箱中干燥过夜。得立方体状Pd/CeO2纳米复合材料，如图2所示。3) 60 mg of the product of step 2) and an appropriate concentration of PdCl2 (0.6767M) were dispersed in 20 ml of deionized water and stirred for 30 minutes. Then, 0.2 g of ascorbic acid was added under magnetic stirring. After aging for 22 hours, the precipitate was centrifuged and washed with deionized water several times to remove impurities. Finally, the centrifuged product was dried in a vacuum oven at 45°C overnight. A cubic Pd/CeO2 nanocomposite material was obtained, as shown in Figure 2.
实施例2Example 2
本实施例的Pd/CeO2纳米复合材料，水热反应的温度按150℃进行制备，制备方法与实施例1的唯一区别在于：步骤1）溶液A：将1.911克Ce(NO3)3•6H2O溶于40毫升去离子水中。溶液B：将0.896克NaOH分散在去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟。然后加入到100mL高压釜中，在150℃下反应24小时；得到球形Pd/CeO2纳米复合材料，如图2所示。其他参数均与实施例1的相同，不再赘述。The Pd/CeO2 nanocomposite material of this embodiment is prepared at a hydrothermal reaction temperature of 150°C. The only difference between the preparation method and that of Example 1 is that: Step 1) Solution A: Dissolve 1.911 g of Ce(NO3 )3 •6H2 O in 40 ml of deionized water. Solution B: Disperse 0.896 g of NaOH in deionized water. Slowly add solution B to solution A and stir for 30 minutes. Then add to a 100 mL autoclave and react at 150°C for 24 hours; obtain a spherical Pd/CeO2 nanocomposite material, as shown in FIG2 . Other parameters are the same as those of Example 1 and will not be repeated.
实施例3Example 3
本实施例的Pd/CeO2纳米复合材料，水热反应的温度按100℃和Ce(NO3)3•6H2O与NaOH的质量比为1：9.6进行制备，制备方法与实施例1的区别在于：步骤1）溶液A：将1.76克Ce(NO3)3•6H2O溶于40毫升去离子水中，溶液B：将16.88克NaOH分散于去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟，然后加入100mL高压釜中，在100℃下反应24小时；得到棒状Pd/CeO2纳米复合材料，如图2所示。其他参数均与实施例1的相同，不再赘述。The Pd/CeO2 nanocomposite material of this embodiment is prepared at a hydrothermal reaction temperature of 100°C and a mass ratio of Ce(NO3 )3 •6H2 O to NaOH of 1:9.6. The preparation method is different from that of Example 1 in that: Step 1) Solution A: 1.76 g of Ce(NO3 )3 •6H2 O is dissolved in 40 ml of deionized water, Solution B: 16.88 g of NaOH is dispersed in deionized water. Solution B is slowly added to Solution A, stirred for 30 minutes, and then added to a 100 mL autoclave, and reacted at 100°C for 24 hours; a rod-shaped Pd/CeO2 nanocomposite material is obtained, as shown in FIG2 . Other parameters are the same as those of Example 1 and are not described in detail.
实施例4Example 4
本实施例的Pd/CeO2纳米复合材料，水热反应的温度按180℃和Ce(NO3)3•6H2O与NaOH的质量比为1：5进行制备，制备方法与实施例1的区别在于：步骤1）溶液A：将1.76克Ce(NO3)3•6H2O溶于40毫升去离子水中，溶液B：将8.8克NaOH分散于去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟，然后加入100mL高压釜中，在180℃下反应24小时。其他参数均与实施例1的相同，不再赘述。The Pd/CeO2 nanocomposite material of this embodiment is prepared at a hydrothermal reaction temperature of 180°C and a mass ratio of Ce(NO3 )3 •6H2 O to NaOH of 1:5. The preparation method is different from that of Example 1 in that: Step 1) Solution A: 1.76 g of Ce(NO3 )3 •6H2 O is dissolved in 40 ml of deionized water, Solution B: 8.8 g of NaOH is dispersed in deionized water. Solution B is slowly added to Solution A, stirred for 30 minutes, and then added to a 100 mL autoclave and reacted at 180°C for 24 hours. Other parameters are the same as those of Example 1 and are not repeated here.
实施例5Example 5
本实施例的Pd/CeO2纳米复合材料，水热反应的温度按180℃和Ce(NO3)3•6H2O与NaOH的质量比为1：2进行制备，制备方法与实施例1的区别在于：步骤1）溶液A：将1.76克Ce(NO3)3•6H2O溶于40毫升去离子水中，溶液B：将3.52克NaOH分散于去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟，然后加入100mL高压釜中，在180℃下反应24小时。其他参数均与实施例1的相同，不再赘述。The Pd/CeO2 nanocomposite material of this embodiment is prepared at a hydrothermal reaction temperature of 180°C and a mass ratio of Ce(NO3 )3 •6H2 O to NaOH of 1:2. The preparation method is different from that of Example 1 in that: Step 1) Solution A: 1.76 g of Ce(NO3 )3 •6H2 O is dissolved in 40 ml of deionized water, Solution B: 3.52 g of NaOH is dispersed in deionized water. Solution B is slowly added to Solution A, stirred for 30 minutes, and then added to a 100 mL autoclave and reacted at 180°C for 24 hours. Other parameters are the same as those of Example 1 and are not repeated here.
实施例6Example 6
本实施例的Pd/CeO2纳米复合材料，水热反应的温度按180℃和Ce(NO3)3•6H2O与NaOH的质量比为1：1进行制备，制备方法与实施例1的区别在于：步骤1）溶液A：将1.76克Ce(NO3)3•6H2O溶于40毫升去离子水中，溶液B：将1.76克NaOH分散于去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟，然后加入100mL高压釜中，在180℃下反应24小时。其他参数均与实施例1的相同，不再赘述。The Pd/CeO2 nanocomposite material of this embodiment is prepared at a hydrothermal reaction temperature of 180°C and a mass ratio of Ce(NO3 )3 •6H2 O to NaOH of 1:1. The preparation method is different from that of Example 1 in that: Step 1) Solution A: 1.76 g of Ce(NO3 )3 •6H2 O is dissolved in 40 ml of deionized water, Solution B: 1.76 g of NaOH is dispersed in deionized water. Solution B is slowly added to Solution A, stirred for 30 minutes, and then added to a 100 mL autoclave and reacted at 180°C for 24 hours. Other parameters are the same as those of Example 1 and are not repeated here.
实施例7Example 7
本实施例的Pd/CeO2纳米复合材料，水热反应的温度按150℃和Ce(NO3)3•6H2O与NaOH的质量比为1：1进行制备，制备方法与实施例1的区别在于：步骤1）溶液A：将1.76克Ce(NO3)3•6H2O溶于40毫升去离子水中，溶液B：将1.76克NaOH分散于去离子水中。将溶液B缓慢加入溶液A中，搅拌30分钟，然后加入100mL高压釜中，在150℃下反应24小时。其他参数均与实施例1的相同，不再赘述。The Pd/CeO2 nanocomposite material of this embodiment is prepared at a hydrothermal reaction temperature of 150°C and a mass ratio of Ce(NO3 )3 •6H2 O to NaOH of 1:1. The preparation method is different from that of Example 1 in that: Step 1) Solution A: 1.76 g of Ce(NO3 )3 •6H2 O is dissolved in 40 ml of deionized water, Solution B: 1.76 g of NaOH is dispersed in deionized water. Solution B is slowly added to Solution A, stirred for 30 minutes, and then added to a 100 mL autoclave and reacted at 150°C for 24 hours. Other parameters are the same as those of Example 1 and are not repeated here.
上述实施例的表征和性能测试结果如下所示：The characterization and performance test results of the above embodiments are as follows:
采用德国布鲁克公司的D8 Adcance X-射线衍射仪对制备的气敏复合材料进行物相测试，以Cu Kα1作为辐射源，扫描范围为10~80º，扫描速率为10º/min。图1是本发明实施例1~3的X射线衍射（XRD）谱图，由图1可知，CeO2与标准峰（PDF#89-8436）完全对应，Pd与标准峰（PDF#87-0643）完全对应。The prepared gas-sensitive composite material was tested for physical properties using a D8 Adcance X-ray diffractometer from Bruker, Germany, with Cu Kα1 as the radiation source, a scanning range of 10-80°, and a scanning rate of 10°/min. FIG1 is an X-ray diffraction (XRD) spectrum of Examples 1-3 of the present invention. As can be seen from FIG1, CeO2 completely corresponds to the standard peak (PDF#89-8436), and Pd completely corresponds to the standard peak (PDF#87-0643).
实施例1-3中制得的Pd/CeO2纳米复合材料表面形貌如图2所示，从微观结构可以看出该材料为立方体、球形和棒状结构。而立方体具有高比表面积，有利于表面气体吸附和脱附，获得良好的气体敏感特性。The surface morphology of the Pd/CeO2 nanocomposite materials prepared in Examples 1-3 is shown in Figure 2. From the microstructure, it can be seen that the material is a cubic, spherical and rod-shaped structure. The cube has a high specific surface area, which is conducive to surface gas adsorption and desorption, and obtains good gas sensitive properties.
在室温工作时，通过动态配气系统将1%氢气注入北京中聚高科科技有限公司生产的CGS-MT光电气综合测试平台的测试腔中，并实时记录气敏元件在150s内对不同浓度氢气的动态响应曲线。图3是本发明实施例1-3制备的立方体、球形和棒状Pd/CeO2气敏元件在室温对1%氢气的动态响应重复曲线图。由图3可知，立方体的Pd/CeO2检测1%的氢气表现出良好的重复性。When working at room temperature, 1% hydrogen is injected into the test chamber of the CGS-MT optoelectronic integrated test platform produced by Beijing Zhongju High-Tech Technology Co., Ltd. through the dynamic gas distribution system, and the dynamic response curve of the gas sensor to different concentrations of hydrogen within 150s is recorded in real time. Figure 3 is a repeated curve diagram of the dynamic response of the cubic, spherical and rod-shaped Pd/CeO2 gas sensors prepared in Examples 1-3 of the present invention to 1% hydrogen at room temperature. As shown in Figure 3, the cubic Pd/CeO2 shows good repeatability in detecting 1% hydrogen.
在室温工作时，通过动态配气系统将不同浓度的氢气注入测试腔中，并实时记录气敏元件在150s内对氢气的动态电阻曲线。图4是本发明实施例1-3制备的立方体、球形和棒状Pd/CeO2气敏材料在室温对1%氢气检测的响应图。由图4可知，立方体Pd/CeO2气敏元件在室温工作时，表现出最快的响应时间和最大的响应值。而球形和棒状Pd/CeO2气敏材料的响应时间和响应值均小于立方体结构。其中，响应时间定义为待测气体开始接触气敏元件到元件电阻下降到稳定电阻的90%所需时间。When working at room temperature, hydrogen of different concentrations is injected into the test chamber through the dynamic gas distribution system, and the dynamic resistance curve of the gas sensor to hydrogen within 150s is recorded in real time. Figure 4 is a response diagram of cubic, spherical and rod-shaped Pd/CeO2 gas-sensitive materials prepared in Examples 1-3 of the present invention to 1% hydrogen detection at room temperature. As can be seen from Figure 4, the cubic Pd/CeO2 gas-sensitive element shows the fastest response time and the largest response value when working at room temperature. The response time and response value of the spherical and rod-shaped Pd/CeO2 gas-sensitive materials are both smaller than those of the cubic structure. Among them, the response time is defined as the time required from the gas to be tested starting to contact the gas-sensitive element to the time when the element resistance drops to 90% of the stable resistance.
在室温工作时，通过动态配气系统将不同浓度的氢气注入测试腔中，并实时记录气敏元件在150s内对氢气的动态电阻曲线。图5是本发明实施例1-3制备的立方体、球形和棒状Pd/CeO2气敏材料在对不同浓度氢气检测的响应时间图。由图5可知，立方体Pd/CeO2气敏元件在室温工作时，随着氢气的浓度增加响应时间大幅度降低。对1%氢气的响应时间为3s，对3%氢气的响应时间仅为2s，超快的响应速率可以实现室温下对氢气泄漏的快速检测。When working at room temperature, hydrogen of different concentrations is injected into the test chamber through the dynamic gas distribution system, and the dynamic resistance curve of the gas sensor to hydrogen within 150 seconds is recorded in real time. Figure 5 is a response time diagram of the cubic, spherical and rod-shaped Pd/CeO2 gas-sensitive materials prepared in Examples 1-3 of the present invention to the detection of hydrogen of different concentrations. As can be seen from Figure 5, when the cubic Pd/CeO2 gas-sensitive element works at room temperature, the response time is greatly reduced as the concentration of hydrogen increases. The response time to 1% hydrogen is 3s, and the response time to 3% hydrogen is only 2s. The ultra-fast response rate can realize the rapid detection of hydrogen leaks at room temperature.
为探究实施例对氢气的选择性，分别将甲烷（CH4）、丙烷（C3H8）、二氧化碳（CO2）、一氧化碳（CO）、二氧化氮（NO2）和乙醇注入测试腔中，在150s后记录气敏材料对不同气体的响应。图6是本发明实施例1~3制备的气敏材料在室温工作时对1%不同气体的选择性柱状图。由图6可知，立方体Pd/CeO2气敏材料对氢气具有最高的响应，而对其他气体的响应较低，表明立方体Pd/CeO2气敏材料对氢气具有最好的选择性。In order to explore the selectivity of the embodiment to hydrogen, methane (CH4 ), propane (C3 H8 ), carbon dioxide (CO2 ), carbon monoxide (CO), nitrogen dioxide (NO2 ) and ethanol were injected into the test chamber, and the response of the gas-sensitive material to different gases was recorded after 150 seconds. FIG6 is a bar graph of the selectivity of the gas-sensitive materials prepared in Examples 1 to 3 of the present invention to 1% different gases when working at room temperature. As shown in FIG6 , the cubic Pd/CeO2 gas-sensitive material has the highest response to hydrogen, while the response to other gases is lower, indicating that the cubic Pd/CeO2 gas-sensitive material has the best selectivity to hydrogen.
上述具体实施方式用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明做出的任何修改和改变，都落入本发明的保护范围。The above specific implementation modes are used to explain the present invention rather than to limit the present invention. Any modification and change made to the present invention within the spirit of the present invention and the protection scope of the claims shall fall within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410487055.3ACN118090837A (en) | 2024-04-23 | 2024-04-23 | Room-temperature hydrogen-sensitive cube material and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410487055.3ACN118090837A (en) | 2024-04-23 | 2024-04-23 | Room-temperature hydrogen-sensitive cube material and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN118090837Atrue CN118090837A (en) | 2024-05-28 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410487055.3APendingCN118090837A (en) | 2024-04-23 | 2024-04-23 | Room-temperature hydrogen-sensitive cube material and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN118090837A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009008476A (en)* | 2007-06-27 | 2009-01-15 | Kyushu Univ | Hydrogen gas sensor and method for manufacturing hydrogen gas sensor |
| WO2010044935A2 (en)* | 2008-10-16 | 2010-04-22 | Apollo, Inc. | Sensitive materials for gas sensing and method of making same |
| CN101968461A (en)* | 2010-09-26 | 2011-02-09 | 浙江大学 | Room temperature hydrogen sensor based on palladium-nanometer-scale stannic oxide film type electrode |
| CN103558261A (en)* | 2013-11-20 | 2014-02-05 | 厦门大学 | Preparation method of room-temperature hydrogen sensor |
| CN104569051A (en)* | 2014-11-13 | 2015-04-29 | 无锡信大气象传感网科技有限公司 | Method for manufacturing hydrogen sensor |
| JP2018124211A (en)* | 2017-02-02 | 2018-08-09 | 日立化成株式会社 | Hydrogen detection method and hydrogen detection device |
| CN109813769A (en)* | 2019-03-13 | 2019-05-28 | 郑州大学 | A kind of indium oxide-based hydrogen sensor and preparation method thereof |
| CN113219008A (en)* | 2021-04-26 | 2021-08-06 | 浙江大学 | Porous nanocomposite material for high-selectivity hydrogen gas sensor and preparation method thereof |
| CN115724462A (en)* | 2022-11-23 | 2023-03-03 | 江苏大学 | CeO (CeO) 2 Composite TiO 2 Hydrogen sensitive material and preparation method thereof |
| CN116794118A (en)* | 2023-06-25 | 2023-09-22 | 太原理工大学 | A NO2 sensor based on In2O3/ZIF-8 core-shell nanocube composite material and its preparation method |
| CN117054492A (en)* | 2023-06-27 | 2023-11-14 | 大连理工大学 | PdPt/SnO 2 Preparation method of @ ZIF-8 gas-sensitive composite material and hydrogen sensing application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009008476A (en)* | 2007-06-27 | 2009-01-15 | Kyushu Univ | Hydrogen gas sensor and method for manufacturing hydrogen gas sensor |
| WO2010044935A2 (en)* | 2008-10-16 | 2010-04-22 | Apollo, Inc. | Sensitive materials for gas sensing and method of making same |
| CN101968461A (en)* | 2010-09-26 | 2011-02-09 | 浙江大学 | Room temperature hydrogen sensor based on palladium-nanometer-scale stannic oxide film type electrode |
| CN103558261A (en)* | 2013-11-20 | 2014-02-05 | 厦门大学 | Preparation method of room-temperature hydrogen sensor |
| CN104569051A (en)* | 2014-11-13 | 2015-04-29 | 无锡信大气象传感网科技有限公司 | Method for manufacturing hydrogen sensor |
| JP2018124211A (en)* | 2017-02-02 | 2018-08-09 | 日立化成株式会社 | Hydrogen detection method and hydrogen detection device |
| CN109813769A (en)* | 2019-03-13 | 2019-05-28 | 郑州大学 | A kind of indium oxide-based hydrogen sensor and preparation method thereof |
| CN113219008A (en)* | 2021-04-26 | 2021-08-06 | 浙江大学 | Porous nanocomposite material for high-selectivity hydrogen gas sensor and preparation method thereof |
| CN115724462A (en)* | 2022-11-23 | 2023-03-03 | 江苏大学 | CeO (CeO) 2 Composite TiO 2 Hydrogen sensitive material and preparation method thereof |
| CN116794118A (en)* | 2023-06-25 | 2023-09-22 | 太原理工大学 | A NO2 sensor based on In2O3/ZIF-8 core-shell nanocube composite material and its preparation method |
| CN117054492A (en)* | 2023-06-27 | 2023-11-14 | 大连理工大学 | PdPt/SnO 2 Preparation method of @ ZIF-8 gas-sensitive composite material and hydrogen sensing application thereof |
| Title |
|---|
| YIJU SONG 等: "Conductometric H2 sensors at room temperature based on palladium nanoparticles on ceria", 《SENSORS &ACTUATORS》, 31 December 2022 (2022-12-31)* |
| YIJU SONG 等: "Effect of hydroxyl groups on the oxygen vacancy and hydrogen-sensitive properties of CeO2 in different morphologies", 《INTERNATIONAL JOURNAL O F HYDROGEN ENERGY》, 15 June 2022 (2022-06-15), pages 25444 - 25445* |
| 瞿昀昊: "CeO2基纳米材料的制备及其氢气传感性能研究", 《CNKI》, 31 December 2021 (2021-12-31)* |
| 赵兵建 等: "以SnO2纳米颗粒为敏感电极的阻抗型氢气传感器的研究", 《功能材料》, 31 December 2011 (2011-12-31)* |
| Publication | Publication Date | Title |
|---|---|---|
| Xia et al. | Localized π-conjugated structure and EPR investigation of g-C3N4 photocatalyst | |
| Zhang et al. | Interfacial energy barrier tuning of hierarchical Bi2O3/WO3 heterojunctions for advanced triethylamine sensor | |
| Ma et al. | Enhanced formaldehyde sensing performance at ppb level with Pt-doped nanosheet-assembled In2O3 hollow microspheres | |
| CN113219008B (en) | Porous nanocomposite material for high-selectivity hydrogen gas sensor and preparation method thereof | |
| Wang et al. | An isopropanol sensor based on MOF-derived NiO/NiCoxFe2− xO4 porous nanocube with improved response and selectivity | |
| Zhang et al. | High sensitivity and surface mechanism of MOFs-derived metal oxide Co3O4-SnO2 hollow spheres to ethanol | |
| CN103831077B (en) | Ceramic material, carbon dioxide adsorption method and carbon dioxide conversion method | |
| CN110687170A (en) | A kind of TiO2/SnO2 gas sensor and preparation method based on ultraviolet light band | |
| CN107966479A (en) | A kind of Pd/W for improving hydrogen gas sensor performance18O49The preparation method of composite material | |
| Duan et al. | Ultra-effective room temperature gas discrimination based on monolithic Pd@ MOF-derived porous nanocomposites: an exclusive scheme with photoexcitation | |
| CN113791123A (en) | Tin oxide and noble metal based double-nanoparticle lattice hydrogen sensor and preparation method thereof | |
| CN112076757A (en) | A method for preparing porous LaCoO3 perovskite catalyst by acetic acid etching | |
| CN108956708A (en) | A kind of alcohol gas sensor and preparation method thereof based on zinc ferrite nano sensitive material | |
| Gao et al. | In2O3 sensing electrode prepared by salt melt method for impedancemetric-type NH3 sensor | |
| CN115463667B (en) | Preparation method of composite photocatalytic nitrogen fixation material with iridium loaded by cuprous oxide of different crystal planes | |
| CN114506873B (en) | Metal organic framework derived CuO/ZnO nano material and preparation method and application thereof | |
| Jin et al. | Anchoring Ni atomic clusters on yolk-shell In2O3 microspheres for highly sensitive, ultra-rapid responding/recovering ppb-level NO2 detections | |
| CN115193438B (en) | A kind of indium oxide composite material with surface modified nickel nanoparticles and its preparation method and application | |
| Wang et al. | Construction of ZnCo 2 O 4 decorated ZnO heterostructure materials for sensing triethylamine with dramatically enhanced performance | |
| Kang et al. | Fabrication and application of ZIF-8 derived In2O3-ZnO nanocomposites for ultra-sensitive NO2 sensing under UV irradiation at room temperature | |
| Ding et al. | Fast response triethylamine sensor based on MOF-derived coral flower-like Fe-doped Co3O4 | |
| Zhang et al. | High-Throughput Experimental Technology: Rapid Identification of the Precious Metal Modified In 2 O 3 for NO 2 Low-Temperature Sensing | |
| CN118090837A (en) | Room-temperature hydrogen-sensitive cube material and preparation method thereof | |
| CN115893476B (en) | Preparation method and application of indium oxide hollow tube derived from indium MOFs coated with Pd nanoparticles | |
| CN107117645B (en) | Metal-doped porous SnO is obtained by containing Sn intermetallic compound2The preparation method of material |
| 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 |