阅读说明：本技术 负载Ru的In2O3纳米材料及其制备方法和应用 (In supporting Ru2O3Nano material and preparation method and application thereof ) 是由 杨明辉 张沈丹 曲奉东 于 2020-07-07 设计创作，主要内容包括：本发明公开了负载Ru的In<Sub>2</Sub>O<Sub>3</Sub>纳米材料及其制备方法和应用,所述In<Sub>2</Sub>O<Sub>3</Sub>纳米材料为形貌呈开裂状的立方块形,其平均粒径为1μm；所述In<Sub>2</Sub>O<Sub>3</Sub>纳米材料的表面负载有Ru纳米粒子。本发明负载Ru的In<Sub>2</Sub>O<Sub>3</Sub>纳米材料,具有高的比表面积,同时通过Ru的修饰In<Sub>2</Sub>O<Sub>3</Sub>对三甲苯气体的敏感性提高；此外本发明将上述负载Ru纳米粒子的立方块In<Sub>2</Sub>O<Sub>3</Sub>纳米材料涂覆于三甲苯气体传感器的敏感元件,具有制备方法简单,成本低廉,优秀的快速响应恢复特性、可大规模生产的特点,对三甲苯气体具有良好的检测性能。总体上本发明采用的工艺简单、制得的器件体积小、适于大批量生产,因而具有重要的应用价值。(The invention discloses In loaded with Ru 2 O 3 Nano material, its preparing process and application, said In 2 O 3 The nano material is in a shape of a cracked cube, and the average grain diameter of the nano material is 1 mu m; said In 2 O 3 The surface of the nano material is loaded with Ru nano particles. In carrying Ru In the invention 2 O 3 Nanomaterial with high specific surface area and In modified by Ru 2 O 3 The sensitivity to the trimethylbenzene gas is improved; in addition, the invention puts the cubic block In loaded with Ru nano particles 2 O 3 The nano material is coated on a sensitive element of the trimethylbenzene gas sensor, has the characteristics of simple preparation method, low cost, excellent quick response and recovery characteristic and large-scale production, and has good detection performance on the trimethylbenzene gas. The invention has simple process, small volume of the prepared device,Is suitable for mass production, thereby having important application value.)

1. In supporting Ru₂O₃Nanomaterial characterized In that In₂O₃The nano material is in a shape of a cracked cube, and the average grain diameter of the nano material is 1 mu m; said In₂O₃The surface of the nano material is loaded with Ru nano particles.

2. Ru-loaded In according to claim 1₂O₃Preparation method of nano materialThe method is characterized by comprising the following steps:

step one, preparing in (OH) by adopting a hydrothermal method₃Nano cubic block, and calcining to obtain cracked nano cubic block In₂O₃Is In₂O₃A white powder;

step two, loading Ru In₂O₃The preparation of the nano material comprises the following steps:

s21, taking the cracked nano cube In prepared In the step one₂O₃Adding 0.01-0.1g of white powder into 10-40ml of ethanol and uniformly dispersing;

s22, mixing RuCl with the concentration of 2-20mmol/L and the concentration of 20-200 mu L₃Adding the solution into the mixed solution prepared in the S21 and completely dissolving the solution;

s23, standing the solution prepared In the S22 In a vacuum drying oven at the temperature of 50-80 ℃ for 5-10 hours, completely evaporating the solution to obtain an off-white solid powder, and calcining the off-white solid powder In a muffle furnace at the temperature of 300 ℃ for 2 hours to obtain cubic In loaded with Ru nano particles₂O₃And (3) nano materials.

3. The method for preparing the alloy material according to claim 2, wherein the step one comprises the steps of:

s11, dissolving 0.1-0.2g of indium chloride tetrahydrate and 0.1-0.2g of urea in 50-100ml of water, and stirring for 10-30min to obtain a uniform solution;

s12, transferring the obtained uniform solution into a reaction kettle, placing the reaction kettle in a blowing oven at 90-100 ℃ for 8-12h, centrifuging and washing the mixed solution after the reaction is finished, drying the precipitate at 60-80 ℃ for 6-12 h, taking out and grinding to obtain nano cubic in (OH)₃A white powder;

s13 nanometer cubic in (OH)₃Calcining at 400 ℃ for 1h to obtain cracked nano cubic In₂O₃White powder.

4. The method according to claim 3, wherein the solvent water used in the first and second steps is deionized water or ultrapure water.

5. Ru-loaded In according to claim 1₂O₃Nanomaterial or Ru-supported In prepared by the preparation method of any one of claims 2 to 4₂O₃The application of the nano material in a trimethylbenzene gas sensor.

6. Use according to claim 5, characterized In that In to be loaded with Ru₂O₃The nano material is coated on a sensitive element of the trimethyl benzene gas sensor.

7. Use according to claim 6, wherein In of the load Ru₂O₃The thickness of the sensitive layer formed by the nanometer material on the sensitive element is 20-40 μm.

8. Use according to claim 6, wherein the trimethylbenzene gas sensor comprises an explosion-proof cover, In coated with a load of Ru₂O₃A sensitive element made of nano material and a six-pin tube seat.

9. The use according to claim 8, wherein the preparation method of the trimethylbenzene gas sensor comprises the following steps:

(1) in to be loaded with Ru₂O₃The nano material is made into slurry and then evenly coated on Al with an annular Au electrode₂O₃Forming a sensitive layer with the thickness of 20-40 mu m on the outer surface of the ceramic tube, wherein the sensitive layer completely covers the annular Au electrode;

(2) drying the element obtained in the step (1) at the temperature of 60-80 ℃ for 1-3 hours;

(3) then the Ni-Cr alloy heating wire with the resistance value of 35-40 omega is penetrated through Al₂O₃The ceramic tube is used as a heating wire to obtain a sensitive element;

(4) and welding the sensitive element on a six-pin tube seat and packaging.

10. According to the claimsThe use according to claim 9, wherein the slurry In the step (1) is prepared by drying In loaded with Ru₂O₃Putting the nano material into a mortar, and grinding for 20-30 minutes; then dripping water into the mortar and continuing to grind for 20-30 minutes to obtain viscous slurry; in of the Ru load₂O₃The mass ratio of the nano material to the water is 5: 1-3.

Technical Field

The invention relates to the technical field of gas sensors, In particular to Ru (ruthenium) -loaded In₂O₃A nano material and a preparation method and application thereof.

Background

The mesitylene referred to in the present invention is mesitylene. The mesitylene is an important organic chemical raw material, and can be used for developing various dye intermediates such as trimesic acid, pyromellitic anhydride and the like, and also can be used for producing an antioxidant, a polyester resin curing agent, a stabilizer, an alkyd resin plasticizer and the like. As mesitylene is a good solvent, it is flammable, irritating and has a very low freezing point. In the electronics industry, it is used as a developer for silicone photosensitive sheets.

Mesitylene is also a common Volatile Organic Compound (VOC) in cities, mainly produced by combustion. It plays an important role in many atmospheric chemical reactions (including aerosol and tropospheric ozone generation). Mesitylene has about the same toxicity as xylene. Symptoms of acute toxicity are irritation of the mucosa and central nerves. Chronic poisoning causes central nervous system disorder, hemorrhagic anemia of skin, bronchitis, pulmonary edema, etc. Therefore, the rapid intelligent detection of the trimethylbenzene makes the development of a high-performance trimethylbenzene gas sensor necessary.

Among gas sensors, the metal oxide semiconductor type gas sensor has the advantages of high sensitivity, good selectivity, quick response recovery, low cost, convenience in carrying and the like, and is one of the most widely used gas sensors at present. The metal oxide semiconductor gas sensor directly adsorbs detection gas by using a sensitive material, so that the electrical property and the like of the material are changed, and the gas concentration is detected by detecting the change of an output signal of a sensitive element of a peripheral circuit. Oxide semiconductor sensitive materials with different morphologies have great influence on the gas-sensitive performance, so that the gas-sensitive performance is often improved by synthesizing the sensitive materials with different morphologies. In addition to this, the catalytic material has an influence on the gas-sensitive properties of the sensitive material.

Disclosure of Invention

To solve the above technical problems, the present invention provides an In loaded with Ru₂O₃And (3) nano materials.

Another object of the present invention is to provide In loaded with Ru₂O₃A method for preparing nano material.

It is still another object of the present invention to provide In loaded with Ru₂O₃The application of the nano material in a trimethylbenzene gas sensor.

In order to achieve the above purpose, the invention provides the following technical scheme: in supporting Ru₂O₃Nanomaterial of said In₂O₃The nano material is in a shape of a cracked cube, and the average grain diameter of the nano material is 1 mu m; said In₂O₃The surface of the nano material is loaded with Ru nano particles.

In of the above-mentioned Ru-supporting₂O₃The preparation method of the nano material comprises the following steps:

step one, preparing cubic In by using a hydrothermal method₂O₃Nanomaterial, comprising the following steps:

s11, dissolving 0.1-0.2g of indium chloride tetrahydrate and 0.1-0.2g of urea in 50-100ml of water, and stirring for 10-30min to obtain a uniform solution;

s12, transferring the obtained uniform solution into a reaction kettle, placing the reaction kettle in a blowing oven at 90-100 ℃ for 8-12h, centrifuging and washing the mixed solution after the reaction is finished, drying the precipitate at 60-80 ℃ for 6-12 h, taking out and grinding to obtain nano cubic in (OH)₃A white powder;

s13 nanometer cubic in (OH)₃Calcining at 400 ℃ for 1h to obtain cracked nano cubic In₂O₃White powder.

Step two, loading Ru In₂O₃The preparation of the nano material comprises the following steps:

s21, taking the cracked nano cube In prepared In the step one₂O₃Adding 0.01-0.1g of white powder into 10-40ml of ethanol and uniformly dispersing;

s22, mixing RuCl with the concentration of 2-20mmol/L and the concentration of 20-200 mu L₃Adding the solution into the mixed solution prepared in the S21 and completely dissolving the solution;

s23, standing the solution prepared in the S22 in a vacuum drying oven at the temperature of 50-80 ℃ for 5-10 hours, completely evaporating the solution to obtain an off-white solid powder, and adding the off-white solid powder into the solutionCalcining the mixture In a muffle furnace at 300 ℃ for 2 hours to obtain cubic In loaded with Ru nano particles₂O₃And (3) nano materials.

Further, the solvent water used in the first step and the second step is deionized water or ultrapure water.

In of the above-mentioned Ru-supporting₂O₃The nano material can be applied to a trimethylbenzene gas sensor.

Further, In to be loaded with Ru₂O₃The nano material is coated on a sensitive element of the trimethyl benzene gas sensor.

Further, In of the load Ru₂O₃The thickness of the sensitive layer formed by the nanometer material on the sensitive element is 20-40 μm.

Further, the trimethylbenzene gas sensor comprises an explosion-proof cover and In coated with Ru₂O₃A sensitive element made of nano material and a six-pin tube seat.

Further, the preparation method of the trimethylbenzene gas sensor comprises the following steps:

(1) in to be loaded with Ru₂O₃The nano material is made into slurry and then evenly coated on Al with an annular Au electrode₂O₃Forming a sensitive layer with the thickness of 20-40 mu m on the outer surface of the ceramic tube, wherein the sensitive layer completely covers the annular Au electrode;

(2) drying the element obtained in the step (1) at the temperature of 60-80 ℃ for 1-3 hours;

(3) then the Ni-Cr alloy heating wire with the resistance value of 35-40 omega is penetrated through Al₂O₃The ceramic tube is used as a heating wire to obtain a sensitive element;

(4) and welding the sensitive element on a six-pin tube seat and packaging.

Further, the slurry In the step (1) is prepared by drying the Ru-loaded In₂O₃Putting the nano material into a mortar, and grinding for 20-30 minutes; then dripping water into the mortar and continuing to grind for 20-30 minutes to obtain viscous slurry; in of the Ru load₂O₃The mass ratio of the nano material to the water is 5: 1-3.

Advantages of the inventionHas the advantages that: in carrying Ru In the invention₂O₃Nanomaterial with high specific surface area and In modified by Ru₂O₃The sensitivity to the trimethylbenzene gas is improved, so that cubic In loaded with Ru nano particles is adopted₂O₃The nanometer material is used as sensitive material, has high specific surface area, and can utilize Ru to In effectively₂O₃The catalytic action of the surface and the trimethylbenzene gas improves the gas-sensitive response; in addition, the trimethylbenzene gas sensor of the invention is an improvement of the existing structure, and the cubic In loaded with Ru nano particles₂O₃The nano material is coated on a sensitive element, and the method has the characteristics of simple preparation method, low cost, excellent quick response and recovery characteristics and large-scale production, and has good detection performance on trimethylbenzene gas. Generally, the invention has simple process, small volume of the manufactured device and suitability for mass production, thereby having important application value.

Drawings

FIG. 1 shows In loaded with Ru In accordance with the invention₂O₃SEM (a) and TEM (b) morphology of nanomaterials;

FIG. 2 is a schematic diagram of the device structure of a trimethylbenzene sensor prepared according to the present invention;

FIG. 3 shows In supporting Ru prepared according to the present invention₂O₃XRD pattern of the nanomaterial;

FIG. 4 is a sensitivity-operating temperature characteristic curve of the device of the trimethylbenzene sensor of the present invention at a gas concentration of 100 ppm;

FIG. 5 is a response recovery curve of the trimethylbenzene sensor of the present invention at an operating temperature of 255 ℃ and a trimethylbenzene concentration of 100 ppm;

FIG. 6 shows the selective characteristics of the trimethylbenzene sensor of the present invention at an operating temperature of 255 ℃ and a gas concentration of 100 ppm.

Detailed Description

The present invention will be further described with reference to the following embodiments.