WO2018103145A1 - Micro-porous hollow nickel oxide gas-sensitive material for selectively adsorbing formaldehyde as well as preparation and application thereof - Google Patents

Micro-porous hollow nickel oxide gas-sensitive material for selectively adsorbing formaldehyde as well as preparation and application thereof Download PDF

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WO2018103145A1
WO2018103145A1 PCT/CN2016/111648 CN2016111648W WO2018103145A1 WO 2018103145 A1 WO2018103145 A1 WO 2018103145A1 CN 2016111648 W CN2016111648 W CN 2016111648W WO 2018103145 A1 WO2018103145 A1 WO 2018103145A1
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nickel oxide
oxide gas
microporous hollow
formaldehyde
sensing material
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何丹农
张芳
林琳
葛美英
张春明
金彩虹
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上海纳米技术及应用国家工程研究中心有限公司
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    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • 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
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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  • the invention relates to a gas sensor device and a manufacturing method thereof, in particular to a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde, and preparation and application thereof.
  • the nickel oxide hollow sphere Due to the adjustable pore structure, high specific surface area and strong ion exchange performance, the nickel oxide hollow sphere is beneficial to the reaction of the reactants in the active site during the catalytic process, and shows the detection of gases such as ethanol, acetone and formaldehyde. Great application prospects, however, earlier studies were unsatisfactory in terms of operating temperature, detection limits, and anti-interference.
  • the porous hollow sphere structure has a larger specific surface area and more diffusion channels at the same volume than other nanostructures, resulting in higher sensitivity and rapid response.
  • the invention provides a NiO sensor which can selectively adsorb formaldehyde, and utilizes the characteristics that the size of formaldehyde gas in the air is lower than that of other interference gases, and effectively controls the indoor air by controlling the pore size of the surface of the NiO hollow sphere.
  • the new idea of screening provides the market with a high-quality and gas-selective gas sensor material and device.
  • the present invention provides a microporous hollow nickel oxide gas sensing sensing material for selective adsorption of formaldehyde, and preparation and application thereof.
  • Nickel oxide microporous hollow spheres use nanocellulose as a template, using a water-soluble nickel salt as a precursor, and Ni 2+ forms a coordination structure with a COO - based group. Under heating, hexamethylamide provides OH - and regulates The nickel oxide of the microporous hollow sphere is prepared under the conditions of the concentration, the ratio, the reaction temperature and the like of the precursor.
  • Method for preparing microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde characterized in Dissolving the nanocellulose in a mixed solution of deionized water and a dispersing agent, completely dispersing, adding a nickel precursor and a sustained-release precipitant hexamethyltetramine, and placing the beaker containing the solution in a drying oven for heating The green precipitate is obtained by washing and drying, and then calcined at a high temperature to obtain a microporous hollow nickel oxide gas sensing material.
  • the nanocellulose is 50 nm in diameter and length, added to deionized water, and then added with dispersant; the dispersant is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAC).
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • DMAC dimethylacetamide
  • the method of dispersion was stirred by a magnetic stirrer, the stirring time was 20 min, and the mass fraction of nanocellulose was 5%.
  • the green suspension was washed with alcohol and water for 3-5 times.
  • the precipitated green powder is placed in a muffle furnace, calcined under air for 2 to 10 hours, the heating rate is 3 to 10 ° C / min, and the heating range is 300 to 600 ° C to obtain a microporous hollow sphere nickel oxide powder. stand-by.
  • the nickel precursor is one of nickel sulfate, nickel chloride, nickel nitrate hexahydrate or nickel oxalate.
  • a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde which is prepared according to any of the methods described above.
  • microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde in the detection of formaldehyde gas in air.
  • the alumina ceramic tube is cleaned with deionized water, acetone and chloroform, and dried for use; the suspension of the prepared microporous hollow nickel oxide gas sensing material is evenly spread on the alumina ceramic tube, and the ceramic tube is packaged; The battery was aged for 5-10 days at 200 ° C - 300 ° C to prepare a gas sensor device for testing.
  • the obtained powder was dispersedly coated on a hexagonal ceramic tube gas sensing test element, and the response to different gases was tested using a WS-30A gas sensor test system.
  • the invention provides a simple and feasible gas sensor material with selective adsorption function and a preparation method of the device.
  • the preparation method is simple, and the response efficiency is improved by increasing the specific surface area and the surface active vacancy, and the response temperature is lowered to make the semiconductor
  • the application of materials in gas sensors is simpler.
  • the method of the invention utilizes the carboxyl group in the nanocellulose to coordinate with Ni 2+ to form a shell structure, which has higher selectivity by adjusting the pore size; adjusting the size of the hollow sphere to obtain a high specific surface area, and further
  • the surface active vacancy is regulated, the gas response rate is improved, and the gas sensing material is coated on the surface of the ceramic tube in the preparation of the device, and the preparation process is simple and the repeatability is good.
  • the invention has the advantages that the micropore size adjustment can selectively adsorb the gas and improve the anti-interference ability of the test; and the hollow oxide ball with a large specific surface area can greatly increase the active vacancy on the surface of the material. Make the most of both The advantage is to improve the response rate and response time of the gas sensor.
  • the gas sensor device of the invention has simple manufacture, stable performance and high sensitivity, and has high sensitivity to formaldehyde at working temperature, and can be used for detection of formaldehyde gas.
  • Figure 1 is a SEM image of a microporous hollow nickel oxide of the present invention.
  • Figure 2 is a graph showing the response of nickel oxide to different gases of the present invention.
  • microporous hollow sphere is placed in alcohol or water for use; the alumina ceramic tube is cleaned with deionized water, acetone, chloroform, dried, and the NiO paste is used.
  • the material was uniformly coated on the surface of the ceramic tube, welded to the electrode, and packaged, and aged at 200 ° C for 10 days to obtain a gas sensor.
  • the WS-30A gas sensor test system was used to test the response of different gases at 100 ppm, which has a significant response to formaldehyde gas, as shown in Figure 2.
  • Ball, hollow sphere diameter between 2-2.5 microns, the microporous hollow spheres are placed in alcohol or water for use; alumina ceramic tubes are cleaned with deionized water, acetone, chloroform, dried, and the NiO paste is evenly coated It was applied to the surface of the ceramic tube, welded to the electrode and package, and aged at 300 ° C for 5 days to obtain a gas sensor.
  • the WS-30A gas sensor test system was used to test the response of different gases at 1 ppm, which has a significant response to formaldehyde gas with a sensitivity of 7.6.
  • microporous hollow spheres are placed in alcohol or water for use; the alumina ceramic tubes are cleaned with deionized water, acetone and chloroform. The film was dried and dried, and the NiO paste was uniformly coated on the surface of the ceramic tube, and the electrode and the package were welded, and aged at 250 ° C for 7 days to obtain a gas sensor.
  • the WS-30A gas sensor test system was used to test the response of different gases at 1 ppm concentration, and the formaldehyde gas had a significant response with a sensitivity of 8.0.

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Abstract

A micro-porous hollow nickel oxide gas-sensitive material for selectively adsorbing formaldehyde as well as preparation and application thereof, the preparation comprising: dispersing nanocellulose into a mixed solution of de-ionized water and a dispersant; adding a nickel precursor and a slow-release precipitant hexamethyl tetramine after completely dispersing the nanocellulose; placing a beaker full of the solution into a drying oven to heat and carry out reacting so as to obtain a green precipitate; and placing the green precipitate into a crucible to carry out high-temperature calcination so as to obtain the micro-porous hollow nickel oxide gas-sensitive material after cleaning and drying the green precipitate. The prepared nickel oxide may be used for selective detection of formaldehyde gases in the air.

Description

一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料和器件及制备和应用Microporous hollow nickel oxide gas sensing sensing material and device for selective adsorption of formaldehyde, preparation and application thereof 技术领域Technical field
本发明涉及一种气敏传感器件及其制作方法，特别是涉及一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料及制备和应用。The invention relates to a gas sensor device and a manufacturing method thereof, in particular to a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde, and preparation and application thereof.
背景技术Background technique
氧化镍空心球由于具有可调的孔道结构、高比表面积和较强的离子交换性能，有利于反应物在催化过程中在活性位进行反应，对乙醇、丙酮、甲醛等气体的探测方面显示了极大地应用前景，然而较早的研究在工作温度、检测限、抗干扰性方面都不如人意。多孔中空球结构与其它纳米结构相比，在相同体积下具有更大的比表面积和更多的扩散通道，从而拥有更高的敏感性和快速响应能力。另外，从分子筛和多孔膜的研究经验表明，当孔的直径处于某一范围时，可以对气体分子起到动力学筛分的作用，运动直径大的分子通过率要比小分子通过率要低。甲醛的动力学直径为0.243nm，较其它干扰气体如甲醇(0.36)、乙醇(0.45)、丙酮(0.469)、苯(0.585)等要小得多。理论上当孔径在0.24和0.36nm之间时将只允许甲醛分子通过从而实现100％的选择率，但制备难度很高，而且也非必要，控制在0.5-0.6nm(1nm以下微孔级别)即能对室内空气分子进行有效筛分。就我们所知目前还没有合成NiO多孔中空球结构的报导。Due to the adjustable pore structure, high specific surface area and strong ion exchange performance, the nickel oxide hollow sphere is beneficial to the reaction of the reactants in the active site during the catalytic process, and shows the detection of gases such as ethanol, acetone and formaldehyde. Great application prospects, however, earlier studies were unsatisfactory in terms of operating temperature, detection limits, and anti-interference. The porous hollow sphere structure has a larger specific surface area and more diffusion channels at the same volume than other nanostructures, resulting in higher sensitivity and rapid response. In addition, research experience from molecular sieves and porous membranes shows that when the diameter of the pores is within a certain range, it can act as a dynamic sieve for gas molecules, and the passage rate of molecules with large diameters is lower than that of small molecules. . The kinetic diameter of formaldehyde is 0.243 nm, which is much smaller than other interfering gases such as methanol (0.36), ethanol (0.45), acetone (0.469), benzene (0.585) and the like. Theoretically, when the pore size is between 0.24 and 0.36 nm, only formaldehyde molecules will be allowed to pass through to achieve 100% selectivity, but the preparation is very difficult, and it is not necessary, and it is controlled at 0.5-0.6 nm (microporous level below 1 nm). It can effectively screen indoor air molecules. As far as we know, there is currently no report on the synthesis of porous NiO hollow spheres.
本发明提出了一种可以对甲醛具有选择性吸附的NiO传感器，利用空气中甲醛气体尺寸低于其他干扰气体的尺寸的特点，通过对NiO空心球体表面气孔尺寸的控制，对室内空气进行有效的筛分的新思路，为市场提供一种优质并具有气体选择性的气敏传感器材料及器件。The invention provides a NiO sensor which can selectively adsorb formaldehyde, and utilizes the characteristics that the size of formaldehyde gas in the air is lower than that of other interference gases, and effectively controls the indoor air by controlling the pore size of the surface of the NiO hollow sphere. The new idea of screening provides the market with a high-quality and gas-selective gas sensor material and device.
发明内容Summary of the invention
为克服现有技术的不足，本发明提供一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料及制备和应用。In order to overcome the deficiencies of the prior art, the present invention provides a microporous hollow nickel oxide gas sensing sensing material for selective adsorption of formaldehyde, and preparation and application thereof.
氧化镍微孔空心球是利用纳米纤维素作为模板，利用易溶于水镍盐做前驱体，Ni2+与COO-基形成配位结构，加热条件下六甲基酰胺提供OH-，通过调控前驱体的浓度、比例、反应温度等条件，制备微孔空心球的氧化镍。Nickel oxide microporous hollow spheres use nanocellulose as a template, using a water-soluble nickel salt as a precursor, and Ni 2+ forms a coordination structure with a COO - based group. Under heating, hexamethylamide provides OH - and regulates The nickel oxide of the microporous hollow sphere is prepared under the conditions of the concentration, the ratio, the reaction temperature and the like of the precursor.
一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在 于，将纳米纤维素分散于去离子水中与分散剂的混合溶液中，完全分散后加入镍前驱体和缓释沉淀剂六甲基四胺，将盛有溶液的烧杯放入干燥箱加热进行反应，得到绿色沉淀经清洗干燥后放入坩埚高温煅烧，得到微孔中空氧化镍气敏传感材料。Method for preparing microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde, characterized in Dissolving the nanocellulose in a mixed solution of deionized water and a dispersing agent, completely dispersing, adding a nickel precursor and a sustained-release precipitant hexamethyltetramine, and placing the beaker containing the solution in a drying oven for heating The green precipitate is obtained by washing and drying, and then calcined at a high temperature to obtain a microporous hollow nickel oxide gas sensing material.
纳米纤维素的直径和长度为50nm，加入去离子水中，再加入分散剂；分散剂是二甲基亚砜(DMSO)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAC)中的一种。The nanocellulose is 50 nm in diameter and length, added to deionized water, and then added with dispersant; the dispersant is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAC). One kind.
分散的方法为磁力搅拌器进行搅拌，搅拌时间为20min，纳米纤维素的质量分数5％。The method of dispersion was stirred by a magnetic stirrer, the stirring time was 20 min, and the mass fraction of nanocellulose was 5%.
在60-95℃温度下恒温加热，反应时间为5-24h。Heating at a constant temperature of 60-95 ° C, the reaction time is 5-24h.
待烧杯温度降至室温，将绿色悬浮液用酒精和水离心清洗3-5次。After the temperature of the beaker was lowered to room temperature, the green suspension was washed with alcohol and water for 3-5 times.
将沉淀的绿色粉体放入马弗炉中，在空气条件下煅烧2～10小时，升温速率为3～10℃/min，加热范围为300～600℃，得到微孔空心球氧化镍粉体待用。The precipitated green powder is placed in a muffle furnace, calcined under air for 2 to 10 hours, the heating rate is 3 to 10 ° C / min, and the heating range is 300 to 600 ° C to obtain a microporous hollow sphere nickel oxide powder. stand-by.
镍前驱体为硫酸镍、氯化镍、六水合硝酸镍或草酸镍的一种。The nickel precursor is one of nickel sulfate, nickel chloride, nickel nitrate hexahydrate or nickel oxalate.
在混合液中，按照摩尔比Ni：六亚甲基四胺(HMTA)＝(2-0.5)：1。In the mixed solution, Ni: hexamethylenetetramine (HMTA) = (2-0.5): 1 in terms of a molar ratio.
一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料，其特征在于，根据上述任一所述方法制备得到。A microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde, which is prepared according to any of the methods described above.
一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料在空气中甲醛气体的检测中的应用。The utility of a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde in the detection of formaldehyde gas in air.
氧化铝陶瓷管用去离子水、丙酮、氯仿清洗干净，烘干备用；将制备的微孔中空氧化镍气敏传感材料的悬浮液均匀涂抹在氧化铝陶瓷管上，将陶瓷管进行封装；在200℃-300℃下电老化5-10天，制成气敏传感器件，进行测试。The alumina ceramic tube is cleaned with deionized water, acetone and chloroform, and dried for use; the suspension of the prepared microporous hollow nickel oxide gas sensing material is evenly spread on the alumina ceramic tube, and the ceramic tube is packaged; The battery was aged for 5-10 days at 200 ° C - 300 ° C to prepare a gas sensor device for testing.
将得到的粉体分散涂于六角陶瓷管气敏测试元件上，采用WS-30A型气敏元件测试系统测试对不同气体的响应。The obtained powder was dispersedly coated on a hexagonal ceramic tube gas sensing test element, and the response to different gases was tested using a WS-30A gas sensor test system.
本发明提供一种简单可行的具有选择吸附功能的气敏传感器材料及器件的制备方法，该方法制备工艺简单，通过提高材料比表面积和表面活性空位提高了响应效率，降低了响应温度，使半导体材料在气敏传感器方面的应用更简单。The invention provides a simple and feasible gas sensor material with selective adsorption function and a preparation method of the device. The preparation method is simple, and the response efficiency is improved by increasing the specific surface area and the surface active vacancy, and the response temperature is lowered to make the semiconductor The application of materials in gas sensors is simpler.
本发明的方法是利用纳米纤维素中的羧基与Ni2+配位形成壳层结构，通过微孔尺寸的调节，使其具有更高的选择性；调节空心球的尺寸获得高比表面积，进而调控其表面活性空位，提高气体响应率，器件制备方面，将气敏材料涂敷在陶瓷管表面，制备工艺简单，重复性好。The method of the invention utilizes the carboxyl group in the nanocellulose to coordinate with Ni 2+ to form a shell structure, which has higher selectivity by adjusting the pore size; adjusting the size of the hollow sphere to obtain a high specific surface area, and further The surface active vacancy is regulated, the gas response rate is improved, and the gas sensing material is coated on the surface of the ceramic tube in the preparation of the device, and the preparation process is simple and the repeatability is good.
本发明的优点在于：利用微孔尺寸调节，可选择性吸附气体，提高测试的抗干扰能力；比表面积大的中空属氧化物球，可大大增加材料表面的活性空位。充分利用这两种 优点，提高气敏传感器的响应率和响应时间。本发明气敏传感器件制作简单、性能稳定、灵敏度高，在工作温度下对甲醛有很高的灵敏性，可用于甲醛气体的检测。The invention has the advantages that the micropore size adjustment can selectively adsorb the gas and improve the anti-interference ability of the test; and the hollow oxide ball with a large specific surface area can greatly increase the active vacancy on the surface of the material. Make the most of both The advantage is to improve the response rate and response time of the gas sensor. The gas sensor device of the invention has simple manufacture, stable performance and high sensitivity, and has high sensitivity to formaldehyde at working temperature, and can be used for detection of formaldehyde gas.
附图说明DRAWINGS
图1为本发明的微孔中空氧化镍SEM图。Figure 1 is a SEM image of a microporous hollow nickel oxide of the present invention.
图2为本发明的氧化镍对不同气体的响应曲线。Figure 2 is a graph showing the response of nickel oxide to different gases of the present invention.
具体实施方式detailed description
实施例1：Example 1:
称取1g纳米纤维素溶于水中20ml放入去离子水和DMSO的混合溶液，室温下搅拌20min，加入0.0580g的硝酸镍和0.1402g的HMTA；将烧杯放入干燥箱在60℃反应24小时；待反应釜温度降至室温，将绿色悬浮液用酒精和水分别洗涤3-5次；放入马弗炉以5℃/min升温至300℃保温10小时，得到微孔中空的氧化镍球，空心球直径在1-2微米之间(图1)，将微孔空心球置于酒精或水中待用；氧化铝陶瓷管用去离子水、丙酮、氯仿清洗干净，烘干，将NiO糊状物均匀涂敷在陶瓷管表面，焊接电极、封装，在200℃老化10天，得到气敏传感器。采用WS-30A型气敏元件测试系统测试100ppm浓度不同气体的响应，对甲醛气体具有明显的响应，如图2所示。Weigh 1 g of nanocellulose dissolved in water and add 20 ml of a mixed solution of deionized water and DMSO. Stir at room temperature for 20 min, add 0.0580 g of nickel nitrate and 0.1402 g of HMTA; place the beaker in a dry box and react at 60 ° C for 24 hours. After the temperature of the reactor is lowered to room temperature, the green suspension is washed 3-5 times with alcohol and water respectively; placed in a muffle furnace and heated at 300 ° C for 5 hours at 5 ° C / min to obtain a microporous hollow nickel oxide ball. The diameter of the hollow sphere is between 1-2 microns (Fig. 1). The microporous hollow sphere is placed in alcohol or water for use; the alumina ceramic tube is cleaned with deionized water, acetone, chloroform, dried, and the NiO paste is used. The material was uniformly coated on the surface of the ceramic tube, welded to the electrode, and packaged, and aged at 200 ° C for 10 days to obtain a gas sensor. The WS-30A gas sensor test system was used to test the response of different gases at 100 ppm, which has a significant response to formaldehyde gas, as shown in Figure 2.
实施例2：Example 2:
称取1g纳米纤维素溶于水中20ml放入去离子水和DMSO的混合溶液，室温下搅拌20min，加入0.0518g的氯化镍和0.1402g的HMTA；将烧杯放入干燥箱在95℃反应5小时；待反应釜温度降至室温，将绿色悬浮液用酒精和水分别洗涤3-5次；放入马弗炉以10℃/min升温至600℃保温2小时，得到微孔中空的氧化镍球，空心球直径在2-2.5微米之间，将微孔空心球置于酒精或水中待用；氧化铝陶瓷管用去离子水、丙酮、氯仿清洗干净，烘干，将NiO糊状物均匀涂敷在陶瓷管表面，焊接电极、封装，在300℃老化5天，得到气敏传感器。采用WS-30A型气敏元件测试系统测试1ppm浓度不同气体的响应，对甲醛气体具有明显的响应，灵敏度达到7.6。Weigh 1 g of nanocellulose dissolved in water and add 20 ml of water to a mixed solution of deionized water and DMSO. Stir at room temperature for 20 min, add 0.0518 g of nickel chloride and 0.1402 g of HMTA; place the beaker in a dry box at 95 ° C. Hours; when the temperature of the reactor is lowered to room temperature, the green suspension is washed 3-5 times with alcohol and water respectively; placed in a muffle furnace and heated at 600 ° C for 2 hours at 10 ° C / min to obtain a microporous hollow nickel oxide. Ball, hollow sphere diameter between 2-2.5 microns, the microporous hollow spheres are placed in alcohol or water for use; alumina ceramic tubes are cleaned with deionized water, acetone, chloroform, dried, and the NiO paste is evenly coated It was applied to the surface of the ceramic tube, welded to the electrode and package, and aged at 300 ° C for 5 days to obtain a gas sensor. The WS-30A gas sensor test system was used to test the response of different gases at 1 ppm, which has a significant response to formaldehyde gas with a sensitivity of 7.6.
实施例3：Example 3:
称取1g纳米纤维素溶于水中20ml放入去离子水和DMSO的混合溶液，室温下搅拌20min，0.1467g的草酸镍和0.5608g的HMTA；将烧杯放入干燥箱在75℃反应12小时；待反应釜温度降至室温，将绿色悬浮液用酒精和水分别洗涤3-5次；放入马弗炉以3℃/min升温至450℃保温6小时，得到微孔中空的氧化镍球，空心球直径在2-2.5微米之间，将微孔空心球置于酒精或水中待用；氧化铝陶瓷管用去离子水、丙酮、氯仿清洗干 净，烘干，将NiO糊状物均匀涂敷在陶瓷管表面，焊接电极、封装，在250℃老化7天，得到气敏传感器。采用WS-30A型气敏元件测试系统测试1ppm浓度不同气体的响应，对甲醛气体具有明显的响应，灵敏度达到8.0。 Weigh 1g of nanocellulose dissolved in water 20ml into a mixed solution of deionized water and DMSO, stir at room temperature for 20min, 0.1467g of nickel oxalate and 0.5608g of HMTA; put the beaker into a dry box and react at 75 ° C for 12 hours; The temperature of the reaction kettle was lowered to room temperature, and the green suspension was washed 3-5 times with alcohol and water respectively; the temperature was raised to 450 ° C for 3 hours at 3 ° C / min in a muffle furnace to obtain a microporous hollow nickel oxide ball. The hollow spheres are between 2 and 2.5 microns in diameter. The microporous hollow spheres are placed in alcohol or water for use; the alumina ceramic tubes are cleaned with deionized water, acetone and chloroform. The film was dried and dried, and the NiO paste was uniformly coated on the surface of the ceramic tube, and the electrode and the package were welded, and aged at 250 ° C for 7 days to obtain a gas sensor. The WS-30A gas sensor test system was used to test the response of different gases at 1 ppm concentration, and the formaldehyde gas had a significant response with a sensitivity of 8.0.

Claims (10)

  1. 一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，将纳米纤维素分散于去离子水中与分散剂的混合溶液中，完全分散后加入镍前驱体和缓释沉淀剂六甲基四胺，将盛有溶液的烧杯放入干燥箱加热进行反应，得到绿色沉淀经清洗干燥后放入坩埚高温煅烧，得到微孔中空氧化镍气敏传感材料。Method for preparing microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde, characterized in that nano cellulose is dispersed in a mixed solution of deionized water and dispersing agent, completely dispersed and then added with nickel precursor The body and the slow-release precipitant hexamethyltetramine, the beaker containing the solution is placed in a drying oven for heating, and the green precipitate is washed and dried, and then placed in a high temperature calcination to obtain a microporous hollow nickel oxide gas sensing material. .
  2. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，纳米纤维素的直径和长度为50nm，加入去离子水中，再加入分散剂；分散剂是二甲基亚砜(DMSO)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAC)中的一种。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, wherein the nanocellulose has a diameter and a length of 50 nm, and is added to deionized water. A dispersing agent is added; the dispersing agent is one of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and dimethylacetamide (DMAC).
  3. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，分散的方法为磁力搅拌器进行搅拌，搅拌时间为20min，纳米纤维素的质量分数5％。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, wherein the method of dispersing is stirring by a magnetic stirrer, and the stirring time is 20 min, nanometer The mass fraction of cellulose is 5%.
  4. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，在60-95℃温度下恒温加热，反应时间为5-24h。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, characterized in that the temperature is heated at a temperature of 60-95 ° C for 5-24 hours. .
  5. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，待烧杯温度降至室温，将绿色悬浮液用酒精和水离心清洗3-5次。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, wherein the temperature of the beaker is lowered to room temperature, and the green suspension is centrifuged with alcohol and water. Wash 3-5 times.
  6. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，将沉淀的绿色粉体放入马弗炉中，在空气条件下煅烧2～10小时，升温速率为3～10℃/min，加热范围为300～600℃，得到微孔空心球氧化镍粉体待用。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, wherein the precipitated green powder is placed in a muffle furnace under air conditions The lower calcination is carried out for 2 to 10 hours, the heating rate is 3 to 10 ° C / min, and the heating range is 300 to 600 ° C to obtain a microporous hollow sphere nickel oxide powder to be used.
  7. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，镍前驱体为硫酸镍、氯化镍、六水合硝酸镍或草酸镍的一种。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, wherein the nickel precursor is nickel sulfate, nickel chloride, nickel nitrate hexahydrate or A type of nickel oxalate.
  8. 根据权利要求1所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料的制备方法，其特征在于，在混合液中，按照摩尔比Ni：六亚甲基四胺(HMTA)＝(2-0.5)：1。The method for preparing a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 1, wherein in the mixed solution, according to a molar ratio of Ni: hexamethylenetetramine (HMTA) = (2-0.5): 1.
  9. 一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料，其特征在于，根据权利要求1-8任一所述方法制备得到。 A microporous hollow nickel oxide gas sensing sensing material for selective adsorption of formaldehyde, which is prepared by the method according to any one of claims 1-8.
  10. 根据权利要求9所述的一种用于甲醛选择性吸附的微孔中空氧化镍气敏传感材料在空气中甲醛气体的检测中的应用。 The use of a microporous hollow nickel oxide gas sensing material for selective adsorption of formaldehyde according to claim 9 for detecting formaldehyde gas in air.
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