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Cobalt titanate gas-sensing material with high sensitivity to low-concentration ethyl alcohol and preparation method of cobalt titanate gas-sensing material

A low-concentration ethanol, high-sensitivity technology, applied in the field of cobalt titanate gas-sensing materials and their preparation, can solve the problems of difficult control of process parameters, easy environmental pollution in the preparation process, long response time, etc., and achieves high effective utilization of specific surface area. , The effect of easy gas diffusion and transportation and less equipment investment

Active Publication Date: 2019-08-09
SHENYANG POLYTECHNIC UNIV
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  • Application Information

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Problems solved by technology

[0003] The preparation methods of traditional cobalt titanate gas-sensing materials mainly include magnetron sputtering method, sol-gel method, hydrothermal method, etc. These methods have disadvantages such as high energy consumption, long time consumption, and expensive raw materials, and the prepared titanate The sensitivity of cobalt gas-sensing materials is not high enough, and the working temperature range needs to be further expanded; in order to improve the sensitivity of cobalt titanate gas-sensing materials, researchers have done a lot of work, such as ion doping, compounding with other metal oxides, and developing new materials; Doping cobalt titanate or compounding it with other substances complicates the preparation process, and the process parameters are difficult to control; it is necessary to fundamentally solve the poor sensitivity and response recovery of current cobalt titanate gas-sensitive materials. It is not fast enough and the working temperature range is narrow, and it is necessary to strengthen the development and research of new gas-sensitive materials
[0004] Chinese patent CN201610583835.3 discloses a new type of CoTiO 3 The preparation method and application of gas-sensitive materials, the method uses cobalt nitrate hexahydrate and tetra-n-butyl titanate as initial raw materials, ethylene glycol methyl ether as solvent, citric acid as complexing agent, and CoTiO is prepared by sol-gel method 3 Gas-sensitive materials; the preparation process of this method is complicated, and the obtained sol needs to be left for a long time, secondary drying and secondary calcination treatment, high energy consumption, long time consumption, easy to pollute the environment during the preparation process, and the obtained CoTiO 3 The response time of gas-sensing materials to ethanol gas is longer, which takes 15s; therefore, the key to research is to prepare gas-sensing materials with high sensitivity, fast response and wide operating temperature range by simple methods

Method used

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  • Cobalt titanate gas-sensing material with high sensitivity to low-concentration ethyl alcohol and preparation method of cobalt titanate gas-sensing material
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  • Cobalt titanate gas-sensing material with high sensitivity to low-concentration ethyl alcohol and preparation method of cobalt titanate gas-sensing material

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Experimental program
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Effect test

Embodiment 1

[0038] A mixture of ethylene glycol and 66mL of absolute ethanol is used as a solvent; the volume ratio of ethylene glycol to absolute ethanol in the solvent=0.1;

[0039] Add tetrabutyl titanate and cobalt nitrate to the solvent in turn, and stir and mix at room temperature to form a red clear mixed solution; add water to the red clear mixed solution to promote the hydrolysis and polycondensation reaction, the amount of water is 1.5mL; The molar ratio of tetrabutyl titanate to cobalt nitrate is 1:1, and the molar ratio of tetrabutyl titanate to absolute ethanol is 1:65;

[0040] Put the red clear mixed solution in a reaction kettle, heat it to 160°C under airtight conditions for solvothermal reaction, the reaction time is 18 hours, then cool it down to room temperature naturally, and centrifuge the reacted material to separate the precipitated solid phase;

[0041] After the solid phase of the precipitate is washed with absolute ethanol and dried, it is heated to 600°C in an ...

Embodiment 2

[0044] Method is with embodiment 1, and difference is:

[0045] (1) 100mL absolute ethanol is used as solvent;

[0046] (2) No water was added to the red clear mixed solution; the molar ratio of tetrabutyl titanate to absolute ethanol was 1:85;

[0047] (3) Solvothermal reaction was carried out at 170°C, and the reaction time was 16h;

[0048] (4) Roasting at 650°C for 2 hours;

[0049](5) Cobalt titanate gas-sensitive material with high sensitivity to low concentration of ethanol has an average mesopore diameter of 38.43nm and a pore volume of 0.3cm 3 / g, specific surface area 7.4m 2 / g.

Embodiment 3

[0051] Method is with embodiment 1, and difference is:

[0052] (1) The mixed solution of ethylene glycol and 48mL absolute ethanol is used as solvent; the volume ratio of ethylene glycol and absolute ethanol=0.5 in the solvent;

[0053] (2) Add 0.5 mL of water to the red clear mixed solution; the molar ratio of tetrabutyl titanate to absolute ethanol is 1:110;

[0054] (3) Solvothermal reaction was carried out at 200°C, and the reaction time was 18h;

[0055] (4) Roasting at 700°C for 2 hours;

[0056] (5) Electron microscope scanning results of cobalt titanate gas-sensitive materials with high sensitivity to low concentration ethanol are as follows figure 1 shown, from figure 1 It can be seen in (a) that the shape of the powder is irregular, which is caused by figure 1 (b) It can be seen that the three-dimensional structure formed by powder accumulation has a multi-scale mesopore structure, and the diameter of the large mesopore is 100-200nm; the crystal grains are mainl...

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Abstract

The invention provides a cobalt titanate gas-sensing material with high sensitivity to low-concentration ethyl alcohol and a preparation method of the cobalt titanate gas-sensing material. The grain diameter of the gas-sensing material is 25-100 nanometers, a three-dimensional structure formed by powder accumulation is provided with mesopores, wherein the average pore diameter of the mesopores is30-40 nanometers, the pore volume is 0.1-0.3 cm<3> / g, and the specific surface area is 5-21 m<2> / g. The preparation method comprises the steps that (1) anhydrous ethanol is taken as a solvent, or a mixed solution of ethylene glycol and absolute ethanol is taken as a solvent; 2) tetrabutyl titanate and cobalt nitrate are added into the solvent, stirring and mixing are carried out, and a red clear mixed solution is formed; (3) a solvothermal reaction is performed at 150-220 DEG C, and a solid phase is separated through centrifugation; (4) roasting is performed at 600-750 DEG C after drying. Theprepared product has the high sensitivity to low-concentration ethanol gas and short response time; the preparation process is simple, and the cost is low, and the method is suitable for popularization and application.

Description

technical field [0001] The invention belongs to the technical field of metal oxide semiconductor gas-sensitive materials, and in particular relates to a cobalt titanate gas-sensitive material with high sensitivity to low-concentration ethanol and a preparation method thereof. Background technique [0002] With the improvement of people's quality of life, health and safety issues are particularly important; ethanol is the main component of various alcohols, and it is flammable. It can cause combustion and explosion when exposed to open flames and high temperatures. Great health and safety hazards; cobalt titanate is a P-type semiconductor oxide with good chemical stability and low cost, and is widely used in the detection of ethanol gas; however, it has poor sensitivity to low-concentration ethanol gas, narrow operating temperature range, Long response recovery time has become a major obstacle in its practical application; since the sensitivity of the sensor depends on factor...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01G23/00G01N27/12
CPCC01G23/003C01P2004/64C01P2006/12C01P2006/14C01P2006/16G01N27/127
Inventor 李明春陶爱丽宋明高李胜飞
Owner SHENYANG POLYTECHNIC UNIV