WO2017020859A1 - 锡掺杂的光催化甲醛传感材料及其制备方法和甲醛传感器 - Google Patents

锡掺杂的光催化甲醛传感材料及其制备方法和甲醛传感器 Download PDF

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WO2017020859A1
WO2017020859A1 PCT/CN2016/093563 CN2016093563W WO2017020859A1 WO 2017020859 A1 WO2017020859 A1 WO 2017020859A1 CN 2016093563 W CN2016093563 W CN 2016093563W WO 2017020859 A1 WO2017020859 A1 WO 2017020859A1
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formaldehyde
sensing material
tin
zinc oxide
solvent
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PCT/CN2016/093563
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French (fr)
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常兴华
刘宇
郑捷
李星国
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北京大学
夏普株式会社
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    • 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
    • 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

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  • the invention belongs to the field of formaldehyde gas monitoring technology and formaldehyde sensor technology, and particularly relates to a tin-doped photocatalytic formaldehyde sensing material, a preparation method thereof and a formaldehyde sensor.
  • sensor technology is very important because if consumers are not sure about the true role of air quality products, then they will be suspicious of related products.
  • Commercially available sensors are primarily based on electrochemical type sensors, which are very expensive due to the use of platinum electrodes, and the accuracy, stability and selectivity of such sensors are not satisfactory.
  • the patent application CN2007153341 (formaldehyde air sensing material and formaldehyde air sensing device preparation method) relates to a formaldehyde gas sensing material and a preparation method thereof, and also comprises a method for manufacturing a formaldehyde gas sensor device.
  • the sensing material is composed of SnO 2 -TiO 2 binary nano powder, the molar ratio of Ti/Sn is 0.2-0.5, and 2%-5% cadmium is incorporated, and the material is combined with absolute ethanol and polyethylene glycol.
  • the mixture is ground to a paste, and then uniformly applied to the electrode tube, and the electrode tube is annealed at 400 ° C for 2-4 hours, and then welded, aged, and sealed to obtain a formaldehyde gas sensor.
  • the sensor has low operating temperature, high sensitivity to formaldehyde and strong anti-interference ability to indoor polluting gases such as benzene, toluene, xylene and ammonia, and has a short response time and recovery time.
  • the sensor is mainly used to detect formaldehyde gas generated by interior decoration.
  • the operating temperature of the sensor is 260-300 ° C, at which almost all indoor organic pollutants can be oxidized on the surface of the sensing material, so the selectivity of the material is not satisfactory, especially the difference is not very good.
  • Ethanol and formaldehyde In addition, the detection limit of this technology is 20 ppm, which is two orders of magnitude higher than the safe concentration (0.06 ppm).
  • the present invention is directed to the above problems, and provides a low-cost, high-sensitivity, high-selective tin-doped photocatalytic formaldehyde sensing material, and a formaldehyde sensor using the same.
  • a photocatalytic formaldehyde sensing material comprising zinc oxide nanoparticles and a tin additive.
  • the zinc oxide nanoparticles have a particle diameter of 20 nm to 50 nm, and more preferably 30 nm.
  • the tin additive is tin oxide, and the tin oxide accounts for 0.3% to 5% of the total mass of the zinc oxide and the tin oxide, and more preferably 2%.
  • a method for synthesizing the above photocatalytic formaldehyde sensing material the steps of which include:
  • the method further comprises the step 4): grinding the product C, then uniformly dispersing in a solvent to form a slurry, and suspending the slurry onto the electrode, and drying to obtain a film sensing material.
  • the tin salt in the step 1) is preferably stannous sulfate (SnSO 4 ), and the other may also be tin chloride (SnCl 4 ), stannous oxalate (SnC 2 O 4 ), etc., wherein stannous sulfate is used.
  • SnSO 4 stannous sulfate
  • SnCl 4 tin chloride
  • SnC 2 O 4 stannous oxalate
  • the photocatalytic formaldehyde sensing material obtained has the best performance.
  • step 2) evaporates the solvent at 80-120 ° C, preferably at 80 ° C until the solvent is evaporated to dryness, and then dried at 80 ° C for 12 h, and dried at 120 ° C for 2 h to thoroughly dry the sample.
  • the calcination is carried out at 400 to 500 ° C in step 3), and the optimum temperature is 450 °C.
  • a formaldehyde sensor using the above photocatalytic formaldehyde sensing material comprising:
  • An ultraviolet light source for providing ultraviolet light to illuminate the electrode area during detection
  • the measuring circuit is connected to the electrode for detecting a photo-induced change of the formaldehyde sensing material when the ultraviolet light is irradiated to the electrode region, thereby measuring the formaldehyde content.
  • the invention provides a low-cost, high-sensitivity, high-selectivity photocatalytic formaldehyde sensing material.
  • the lower limit of detection of formaldehyde was successfully reduced to 0.1 ppm, and the selectivity of the material to ethanol was improved.
  • the present invention greatly reduces the cost, improves the selectivity, and significantly improves the detection limit.
  • Conventional semiconductor sensors also use zinc oxide and tin oxide as sensitive materials, but since the conventional heated semiconductor sensor and the photocatalytic sensor of the present invention have great differences in principle, the tin element plays a role in sensitive materials. The effect is also different.
  • tin oxide itself is used as a sensitive material, and VOC (volatile organic compound) can react with oxygen on the surface of tin oxide, thereby causing a change in resistance of tin oxide to achieve detection.
  • VOC volatile organic compound
  • tin oxide is used as an additive for a zinc oxide sensitive material, and tin oxide itself does not have a photocatalytic ability. The effect of tin oxide is to prolong the photo-generated carrier lifetime of zinc oxide and to enhance the photocatalytic ability of zinc oxide.
  • Figure 1 is a process flow diagram of a method of synthesizing a photocatalytic formaldehyde sensing material of the present invention.
  • Figure 2 is a graph comparing the response of different tin additive species samples to 1 ppm formaldehyde.
  • Figure 3 is a graph comparing the response of different tin doping samples to 1 ppm formaldehyde.
  • Figure 4 is a graph comparing the response of tin doped samples to 1 ppm formaldehyde at different calcination temperatures.
  • Figure 5 is a graph comparing the response of a tin-doped and cadmium-doped sample to 1 ppm formaldehyde and response time.
  • FIG. 1 is a flow chart showing the steps of a method for synthesizing a photocatalytic formaldehyde sensing material of the present invention, comprising the following steps:
  • tin salt solution such as SnSO 4 + deionized water
  • the solution is evaporated to dryness, preferably the solution is evaporated to dryness at 80-120 ° C, further preferably at 80 ° C until the solvent is evaporated to dryness, and then dried at 80 ° C for 12 h and then dried at 120 ° C for 2 h to make the sample. Thoroughly dry;
  • the resulting slurry is then suspended onto the finger electrode and the solvent is dried to obtain the formaldehyde sensor we need.
  • Zinc oxide nanoparticles (20-50 nm, optimal particle size 30 nm) have a large specific surface area, which is advantageous for the adsorption and photoconductive properties of formaldehyde.
  • Tin additives are very important for formaldehyde detection, and the amount of tin added is a key point of the present invention.
  • the mass ratio of tin (the ratio of tin oxide to the total mass of zinc oxide to tin oxide) is 0.3% to 5%, and the optimum ratio is 2%.
  • the anion of the tin additive is important and the sulfate is the best.
  • the sintering temperature is very important, 400-500 ° C, and the optimum temperature is 450 ° C.
  • the solvent for pre-pulping the electrode is very important, and it is preferred to use anhydrous ethanol.
  • Step 2 Adding tin elements
  • the solid product was ground to a fine powder, uniformly dispersed in absolute ethanol to prepare a slurry, and then the prepared slurry was sprayed onto an electrode, and the ethanol was blown dry (1 min) with a hair dryer to obtain a film sensing material.
  • a sensor electrode plate having a finger electrode pattern is prepared by a conventional PCB plate-making method, and the channel width of the finger electrode is 100 micrometers, and the electrode portion is gold-plated.
  • the sensitive material is dripped on the upper finger area, and the lower two larger electrodes are used for external measurement circuits.
  • the formaldehyde detection the 365nm UV lamp is directly inserted into the electrode part, and the external measuring circuit detects the photo-induced change of the ultraviolet light for the sensitive material.
  • the UV source produces a photocatalytic effect on sensitive materials for the detection of formaldehyde.
  • An ultraviolet lamp of 365 nm wavelength or an ultraviolet light emitting diode of 385 nm wavelength can be used as an ultraviolet light source.
  • the resistance of the sensor begins to decrease due to the photo-induced effect of the zinc oxide material. After a certain period of time (usually 5 minutes), the resistance value is stabilized. In clean air, the resistance is set to R 0 . When the sensor is transferred from clean air to air containing formaldehyde, the resistance of the sensor will decrease. After a certain period of time (usually 3 minutes), the resistance value is stabilized and set to R s .
  • the concentration of formaldehyde can be calculated from R s /R 0 .
  • the resistance value of the sensor can automatically return to R 0 .
  • Figure 2 shows the response of different tin additive species samples to 1 ppm formaldehyde. It can be seen that the detection of formaldehyde is best when using SnSO 4 , that is, the photocatalytic formaldehyde sensing material produced has the best performance.
  • Example 3 Different Sn contents, ie the mass ratio of tin oxide to (zinc oxide + tin oxide) (Fig. 3)
  • Figure 3 is the response of different tin doping samples to 1 ppm formaldehyde. It can be seen that when the mass ratio of tin oxide to (zinc oxide + tin oxide) is 1%, the response to formaldehyde is most significant and the effect is the best.
  • Figure 4 is the response of a tin doped sample to 1 ppm formaldehyde at different calcination temperatures. It can be seen that the optimum sintering temperature is 450 °C.
  • the SnSO 4 and 3CdSO 4 ⁇ 8H 2 O doped zinc oxide sensing materials are respectively ground for the same time, dispersed with an equal amount of absolute ethanol, sprayed onto the above-mentioned finger electrodes and dried to volatilize the solvent, and then added to the light source.
  • the formaldehyde sensor was then tested for response to the same concentration of formaldehyde and compared.
  • Figure 5 is a comparison of the size and response time of a tin-doped and cadmium-doped sample to 1 ppm formaldehyde. It can be seen that the tin-doped sample has better response to formaldehyde than the cadmium-doped sample.

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Abstract

一种锡掺杂的光催化甲醛传感材料及其制备方法和甲醛传感器。该光催化甲醛传感材料包含氧化锌纳米颗粒及锡添加剂。制备该材料时，首先将预先合成的氧化锌纳米颗粒均匀分散在锡盐溶液中，得到溶液A；然后搅拌溶液A并蒸干溶剂，得到沉淀物B；然后对沉淀物B进行高温煅烧处理，得到产物C，即为光催化甲醛传感材料。通过该方法制备了一种低成本、高灵敏度、高选择性的光催化甲醛传感材料，能够将甲醛的检测下限降到0.1ppm，并且提高了材料对乙醇的选择性。

Description

锡掺杂的光催化甲醛传感材料及其制备方法和甲醛传感器 技术领域
本发明属于甲醛气体监测技术、甲醛传感器技术领域，具体涉及一种锡掺杂的光催化甲醛传感材料及其制备方法和甲醛传感器。
背景技术
长期接触超过安全浓度限制的甲醛气体对人体健康非常有害，这可能会引起眼睛和喉咙的灼烧感，呼吸困难甚至会引起致命的疾病，例如鼻癌，骨髓性白血病等。目前在中国甲醛污染仍然非常严重，近70％新装修的房子都受到甲醛污染的困扰，因此在中国最令人担心的室内污染气体就是甲醛。
对于空气质量产品，传感器的技术是非常重要的，这是因为如果消费者不确定空气质量产品的真实作用，那么他们就会对相关产品产生怀疑。目前商业化的传感器主要是基于电化学类型传感器，这类传感器由于用到铂金电极而变得非常昂贵，此外这类传感器的精确度、稳定性以及选择性都不尽如人意。
和电化学传感器相比，半导体传感器有其特殊的优势，包括成本低、寿命长等，并且具有巨大的提升空间。目前的商用传感器都需要在200℃以上工作，而在此温度上几乎所有的有机污染物都可以反应和探测，所以这类传感器的选择性非常差。为了提高对气体的选择性，部分科研工作者也做出除了室温下工作的光催化半导体甲醛传感器，不过对于应用而言这些传感器的检测下限(大于1ppm)仍然非常高。表1列举了一些现有的传感材料的以及其存在的问题。
表1.现有的传感材料
Figure PCTCN2016093563-appb-000001
专利申请CN2007153341(甲醛空气传感材料及甲醛空气传感设备制备方法)涉及到甲醛气体传感材料及其制备方法，还包括甲醛气体传感器件的制作方法。该传感材料是由SnO2-TiO2二元纳米粉末组成，Ti/Sn的摩尔比为0.2-0.5，并掺入2％-5％的镉，将材料与无水乙醇和聚乙二醇共同研磨至糊状，而后将其均匀的涂到电极管上，将电极管在400℃退火2-4小时后通过焊接、老化、密封即可得到甲醛气体传感器。该传感器操作温度低、对甲醛的灵敏度高并且对于苯、甲苯、二甲苯、氨等室内污染气体具有很强的抗干扰能力，并且具有很短的响应时间和回复时间的特点。该传感器主要用于探测室内装修产生的甲醛气体。但该传感器的工作温度为260-300℃，在该温度下几乎所有的室内有机污染物都可以在传感材料表面被氧化，所以材料的选择性不尽如人意，特别是不能很好的区分乙醇和甲醛。此外该技术的探测下限为20ppm，这比安全浓度(0.06ppm)高出两个数量级。
发明内容
本发明针对上述问题，提供一种低成本、高灵敏度、高选择性的锡掺杂的光催化甲醛传感材料，以及应用该材料的的甲醛传感器。
本发明采用的技术方案如下：
一种光催化甲醛传感材料，包含氧化锌纳米颗粒及锡添加剂。
进一步地，所述氧化锌纳米颗粒的粒径为20nm～50nm，进一步优选为30nm。
进一步地，所述锡添加剂为氧化锡，氧化锡占氧化锌与氧化锡总质量的0.3％～5％，进一步优选为2％。
一种合成上述光催化甲醛传感材料的方法，其步骤包括：
1)将预先合成的氧化锌纳米颗粒均匀分散在锡盐溶液中，得到溶液A；
2)搅拌溶液A并蒸干溶剂，得到沉淀物B；
3)对沉淀物B进行高温煅烧处理，得到产物C，即为光催化甲醛传感材料。
进一步地，还包括步骤4)：对产物C进行研磨，然后均匀分散在溶剂中形成浆料，再将所述浆料悬涂到电极上，干燥后即得到薄膜传感材料。
进一步地，步骤1)所述锡盐优选为硫酸亚锡(SnSO4)，其它还可以采用氯化锡(SnCl4)、草酸亚锡(SnC2O4)等，其中采用硫酸亚锡是制得的光催化甲醛传感材料的性能最好。
进一步地，步骤2)在80-120℃下蒸干溶剂，优选在80℃下搅拌直至溶剂蒸干，而后分别在80℃下烘干12h，在120℃下烘干2h使样品彻底干燥。
进一步地，步骤3)在400-500℃进行所述煅烧，最佳温度为450℃。
一种采用上述光催化甲醛传感材料的甲醛传感器，其包括：
电极，其上涂敷所述光催化甲醛传感材料；
紫外光源，用于提供紫外光以在检测时对电极区域进行照射；
测量电路，连接所述电极，用于检测紫外光照射电极区域时甲醛传感材料所产生的光致电导变化，进而测得甲醛含量。
本发明提供了一种低成本、高灵敏度、高选择性的光催化甲醛传感材料。通过优化锡在氧化锌中的掺入量，成功地将甲醛的检测下限降到了0.1ppm，并且提高了材料对乙醇的选择性。相比于现有技术，本发明大大降低了成本，提高了选择性，并显著改善了检出限。
传统的半导体传感器也有的采用氧化锌和氧化锡作为敏感材料，但是由于传统加热式半导体传感器与本发明的光催化式传感器原理上具有很大的差别，因此锡元素在敏感材料中所起到的作用也不同。在传统加热式半导体传感器中，氧化锡本身作为敏感材料，VOC(挥发性有机化合物)能够与氧化锡表面的氧气发生反应，从而导致氧化锡的电阻变化，实现检测。而在本发明的光催化式传感器中，氧化锡作为氧化锌敏感材料的添加剂，而氧化锡本身不具备光催化能力。氧化锡所产生的作用是延长氧化锌的光生载流子寿命，起到增强氧化锌光催化能力的作用。
附图说明
图1是本发明的光催化甲醛传感材料的合成方法的工艺流程图。
图2是不同锡添加剂种类样品对1ppm甲醛的响应大小的对比图。
图3是不同锡掺杂比例样品对1ppm甲醛的响应大小的对比图。
图4是不同煅烧温度下锡掺杂样品对1ppm甲醛的响应大小的对比图。
图5是锡掺杂与镉掺杂样品对1ppm甲醛响应大小以及响应时间的对比图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面通过具体实施例和附图，对本发明做进一步说明。
图1是本发明的光催化甲醛传感材料的合成方法的步骤流程图，包括如下步骤：
1)将预先合成的氧化锌纳米颗粒分散到锡盐溶液(如SnSO4+去离子水)；
2)将溶液蒸干，优选在80-120℃下将溶液蒸干，进一步优选在80℃下搅拌直至溶剂蒸干，而后分别在80℃下烘干12h，在120℃下烘干2h使样品彻底干燥；
3)将所得沉淀物在400-500℃(最佳煅烧温度为450℃)下煅烧一定时间，煅烧后原来的锡盐生成氧化锡；
4)将所得固体产物研磨成粉末并分散在乙醇溶液中形成浆料。
然后将所得的浆料悬涂到插指电极上，烘干溶剂即可得到我们所需的甲醛传感器。
氧化锌纳米颗粒(20-50nm,最佳粒径30nm)具有较大的比表面积，这有利于甲醛的吸附以及光电导特性。锡添加剂对甲醛探测非常重要，锡元素的添加量是本发明的关键点。锡的质量比(氧化锡占氧化锌与氧化锡总质量的比例)为0.3％-5％，最佳比例为2％。锡添加剂的阴离子很重要，硫酸根为最佳。烧结温度非常重要，为400-500℃，最佳温度为450℃。悬涂电极前制浆的溶剂非常重要，优选采用无水乙醇。
实施例1：材料的合成及测试
步骤一：氧化锌纳米颗粒的合成
将10.77g ZnSO4·7H2O(375mmol)溶解在25mL去离子水中。将溶液逐滴加入到50mL100g/L(1.36mmol/L)NH4HCO3溶液中，在40℃水浴下搅拌1h。去掉上清液，每次用15mL去离子水洗涤沉淀，共洗涤三次，然后将沉淀在80℃干燥12h，在120℃干燥2h。烘完后将样品放入马弗炉中500℃煅烧2h。
步骤二：锡元素的添加
称取0.4g预先制备的氧化锌纳米颗粒并将其分散在60mL锡盐溶液中(SnSO40.007g)，溶液在80℃搅拌并蒸干溶剂，而后将沉淀在80℃干燥12h，在120℃干燥2h。在此之后将沉淀在450℃下煅烧。
步骤三：传感器制备
将固体产物研磨至微粉后均匀分散在无水乙醇中制成浆料，而后将所制备的浆料喷涂到电极上，用电吹风将乙醇吹干(1min)从而得到薄膜传感材料。
传感器电极制作方法：本实施例利用常规PCB制板方法制作具有插指电极图案的传感器电极板，插指电极沟道宽度为100微米，电极部分做镀金处理。敏感材料滴涂在上部的插指区，下部的两块较大电极用于外接测量电路。在进行甲醛检测时，365nm紫外灯直射插指电极部位，外接测量电路检测紫外光对于敏感材料所产生的光致电导变化。
步骤四：甲醛检测
紫外光源对于敏感材料产生光催化效应，用于甲醛的检测。365nm波长的紫外灯管或385nm波长的紫外发光二极管可以用来作为紫外光源。当紫外光源开启时，由于氧化锌材料的光致电导效应，传感器的电阻开始降低。经过一定时间后(通常是5分钟)，电阻值达到稳 定。在清洁的空气中时，该电阻值设为R0。当传感器从清洁的空气中转移到含有甲醛的空气中时，传感器的电阻值会出现降低。在一定的时间(通常是3分钟)之后，电阻值达到稳定，并设为Rs。根据预先确定的关系，甲醛的浓度可以由Rs/R0进行计算得出。检测完成之后，由于光催化效果对于传感器材料上吸附的甲醛具有分解清洁效果，该传感器的电阻值能够自动回复至R0。
实施例2：不同锡源的引入(图2)
a)SnCl4·5H2O
称取合成的ZnO颗粒0.400g溶于110ml去离子水中，并向其中加入0.009g SnCl4·5H2O，然后将溶液超声5min，用磁力搅拌机搅拌并加热，直至蒸干溶剂，将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
b)SnC2O4
称取合成的ZnO颗粒0.400g溶于110ml去离子水中，并向其中加入0.0056g SnC2O4，然后将溶液超声5min，用磁力搅拌机搅拌并加热，直至蒸干溶剂，将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
c)SnSO4
称取合成的ZnO颗粒0.400g溶于80ml去离子水中，并向其中加入0.007g SnSO4，然后将溶液超声5min，用磁力搅拌机搅拌并加热，直至蒸干溶剂，将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
图2是不同锡添加剂种类样品对1ppm甲醛的响应大小。可以看出，采用SnSO4时对甲醛的检测效果最好，即制得的光催化甲醛传感材料的性能最好。
实施例3：不同Sn含量，即氧化锡与(氧化锌+氧化锡)的质量比(图3)
a)0.3％
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.002g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
b)1％
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.007g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放 入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
c)3％
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.021g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
d)5％
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.030g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，而后置于450℃的马弗炉中煅烧4小时。
图3是不同锡掺杂比例样品对1ppm甲醛的响应大小。可以看出，氧化锡与(氧化锌+氧化锡)的质量比为1％时对甲醛的响应最显著，效果最好。
实施例4：样品的不同烧结温度(图4)
a)350℃
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.007g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，然后将样品分别置于350℃下煅烧4小时。
b)400℃
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.007g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，然后将样品分别置于400℃下煅烧4小时。
c)450℃
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.007g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，然后将样品分别置于450℃下煅烧4小时。
d)500℃
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.007g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，然后将样品分别置于500℃下煅烧4小时。
图4是不同煅烧温度下锡掺杂样品对1ppm甲醛的响应大小。可以看出，最佳烧结温度温度为450℃。
实施例5：锡添加剂与镉添加剂对比(图5)
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.007g SnSO4，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，然后将样品分别置于450℃下煅烧4小时。
称取先前合成的ZnO纳米颗粒0.400g，将其溶于110ml去离子水中，并向溶液中加入0.016g 3CdSO4·8H2O，超声5min，用磁力搅拌器搅拌并加热溶液，直至将溶剂蒸干后将所得固体放入80℃的烘箱中干燥8小时，再将烘箱温度调到120℃干燥2小时，然后将样品分别置于450℃下煅烧4小时。
将SnSO4与3CdSO4·8H2O掺杂的氧化锌传感材料分别研磨相同时间后用等量无水乙醇分散后喷涂到前述插指电极上并烘干使溶剂挥发，而后增加光源制成甲醛传感器，而后测试两者对相同浓度甲醛的响应，并进行比较。图5是锡掺杂与镉掺杂样品对1ppm甲醛响应大小以及响应时间的对比。可以看出，锡掺杂样品对甲醛的响应效果优于镉掺杂样品对甲醛的响应效果。
以上实施例仅用以说明本发明的技术方案而非对其进行限制，本领域的普通技术人员可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明的精神和范围，本发明的保护范围应以权利要求书所述为准。

Claims (10)

  1. 一种光催化甲醛传感材料，其特征在于，包含氧化锌纳米颗粒及锡添加剂。
  2. 如权利要求1所述的光催化甲醛传感材料，其特征在于：所述氧化锌纳米颗粒的粒径为20nm～50nm；所述锡添加剂为氧化锡，氧化锡占氧化锌与氧化锡总质量的0.3％～5％。
  3. 如权利要求2所述的光催化甲醛传感材料，其特征在于：所述氧化锌纳米颗粒的粒径为30nm，所述氧化锡占氧化锌与氧化锡总质量的2％。
  4. 一种合成权利要求1所述光催化甲醛传感材料的方法，其特征在于，包括如下步骤：
    1)将预先合成的氧化锌纳米颗粒均匀分散在锡盐溶液中，得到溶液A；
    2)搅拌溶液A并蒸干溶剂，得到沉淀物B；
    3)对沉淀物B进行高温煅烧处理，得到产物C，即为光催化甲醛传感材料。
  5. 如权利要求4所述的方法，其特征在于：步骤1)所述锡盐为SnSO4、SnCl4或SnC2O4。
  6. 如权利要求4所述的方法，其特征在于：步骤2)在80-120℃下蒸干溶剂。
  7. 如权利要求4所述的方法，其特征在于：步骤3)在400-500℃进行所述煅烧。
  8. 如权利要求4所述的方法，其特征在于：步骤1)所述锡盐为SnSO4；步骤2)在80℃下搅拌直至溶剂蒸干，而后分别在80℃下烘干12h和在120℃下烘干2h使样品彻底干燥；步骤3)在450℃进行所述煅烧。
  9. 如权利要求4-8中任一项所述的方法，其特征在于：将产物C研磨至微粉后均匀分散在溶剂中制成浆料，然后将该浆料喷涂到电极上，干燥后得到薄膜传感材料。
  10. 一种采用权利要求1所述光催化甲醛传感材料的甲醛传感器，其特征在于，包括：
    电极，其上涂敷所述光催化甲醛传感材料；
    紫外光源，用于提供紫外光以在检测时对电极区域进行照射；
    测量电路，连接所述电极，用于检测紫外光照射电极区域时甲醛传感材料所产生的光致电导变化，进而测得甲醛含量。
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