CN114988460B - Indium oxide nano material and application thereof - Google Patents
Indium oxide nano material and application thereof Download PDFInfo
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- CN114988460B CN114988460B CN202210788814.0A CN202210788814A CN114988460B CN 114988460 B CN114988460 B CN 114988460B CN 202210788814 A CN202210788814 A CN 202210788814A CN 114988460 B CN114988460 B CN 114988460B
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 86
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 42
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 39
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 22
- ZYYDOSLSINDXIQ-UHFFFAOYSA-N O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZYYDOSLSINDXIQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 230000004044 response Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- 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
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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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
- 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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- 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
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Organic Chemistry (AREA)
- Pathology (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses an indium oxide nano material and application thereof, which takes indium nitrate tetrahydrate, cobalt salt, terephthalic acid and N-N Dimethylformamide (DMF) as raw materials, and obtains the indium oxide with a hexagonal box shape through solvothermal reaction and calcination treatment. The product prepared by the invention has a porous structure, has a larger specific surface area, can effectively adsorb more oxygen and target gas, and improves the sensing performance; the method disclosed by the invention has the advantages of no use of surfactant, low cost, simple preparation method, excellent gas sensitivity to hydrogen sulfide gas and application prospect in the aspect of hydrogen sulfide gas detection.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an indium oxide nano material and application thereof.
Background
Hydrogen sulfide (H) 2 S) is a by-product of various industries, such as petroleum refining, sewage systems, aquaculture and natural gas production, a colorless toxic gas, with a putrescive or malodorous smell, one of the most harmful gases, which can be harmful to the environment and to natural gasHuman health has a variety of effects. Whether in the detection of environmental pollution gas or the protection of human body safety, research and development of high-performance gas sensors have important significance. With the importance of environmental protection and the strict monitoring of the emission of toxic and harmful gases, the gas detection and early warning device is accompanied, and industrialization and commercialization are further achieved. The semiconductor gas sensor has the characteristics of high detection sensitivity, quick response recovery, low price and the like, and is widely applied to various gas detection fields.
Indium oxide is a typical n-type semiconductor, which is white or pale yellow powder at normal temperature, turns reddish brown at high temperature, is insoluble in water, is soluble in a hot inorganic acid, and has a melting point of 2000 ℃. Indium oxide has small resistivity, wide forbidden bandwidth, high catalytic activity and excellent photoelectric property, and is widely applied to various fields such as gas sensors, photoelectric fields, solar cells, field emission and the like. The main factor affecting the performance of indium oxide nanomaterials is their structural morphology, so many researchers are currently devoting their efforts to controlling the formation of morphology of indium oxide materials in order to improve their performance in all respects. However, in the process of preparing the indium oxide material, the reason that the morphology of the indium oxide material can be influenced is numerous, but in the prior art, the research on the morphology of the indium oxide material, especially the nanoscale structure of the indium oxide material, is in a starting stage, in order to obtain different morphologies of the indium oxide material, the preparation method often has strict requirements, such as the defects of complex operation, high production cost and the like, and the research result is difficult to be put into actual industrial production in a large range.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the indium oxide nanomaterial to solve the problems that the indium oxide nanomaterial prepared by the prior art is small in specific surface area, high in production cost and difficult to industrially apply.
In order to solve the technical problems, the invention adopts the following technical scheme:
an indium oxide nano material is prepared by the following method:
step 1: adding DMF into a container, adding cobalt salt and terephthalic acid, and uniformly stirring;
step 2: adding DMF, indium nitrate tetrahydrate and terephthalic acid into another container, and uniformly stirring;
step 3: adding the solution obtained in the step 1 into the solution obtained in the step 2, and uniformly stirring to obtain a reaction solution; wherein, in the reaction liquid, the molar concentration ratio of cobalt ions, indium nitrate tetrahydrate and terephthalic acid is 1: (1-5): (2-6);
step 4: transferring the reaction liquid obtained in the step 3 into a reaction kettle, heating to 120-180 ℃, preserving heat for 2-6 hours, and cooling to room temperature;
step 5: washing the reaction product obtained in the step 4, centrifugally separating, washing a solid product, and drying;
step 6: grinding the dried sample in the step 5, dispersing and placing the ground sample in a crucible, placing the crucible in a tube furnace for calcination, heating the crucible to 350-500 ℃ for 3-8 hours, keeping the temperature for 1-3 hours at a heating rate of not more than 5 ℃/min, and cooling the crucible to room temperature to obtain the light yellow indium oxide nano material.
The invention also provides application of the indium oxide nano material, and the indium oxide nano material is used as a gas-sensitive material for detecting hydrogen sulfide gas.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, indium nitrate tetrahydrate, cobalt salt and terephthalic acid are used as raw materials, DMF is used as a solvent, and solvothermal reaction and calcination treatment are combined to obtain indium oxide with a hexagonal box shape; the indium oxide material with the morphology has a larger specific surface area, can effectively adsorb more gases, and the prepared sensor has more excellent sensitivity to hydrogen sulfide, and improves the sensing performance.
2. The method disclosed by the invention does not use a surfactant at all, the raw material cost is low, the appearance of the indium oxide can be changed through cobalt salt, and the material preparation operation is simple.
3. The indium oxide nano material synthesized by the method has extremely high sensitivity to hydrogen sulfide gas, and can distinguish hydrogen sulfide from other toxic gases.
Drawings
Fig. 1 is an SEM image of the hexagonal box indium oxide nanomaterial prepared in example 1.
Fig. 2 is an SEM image of the hexagonal prism indium oxide material prepared in comparative example 1.
Fig. 3 is an XRD pattern of indium oxide prepared in example 1 and comparative example 1.
Fig. 4 is XPS graphs of indium oxide prepared in example 1 and comparative example 1.
Fig. 5 is a fine XPS spectrum of cobalt element of indium oxide prepared in example 1 and comparative example 1.
Fig. 6 is an SEM image of the hexagonal box indium oxide nanomaterial prepared in example 4.
FIG. 7 is a graph showing hydrogen sulfide gas-sensitive responses of the six-sided box indium oxide sensor device of example 1 and the six-sided prism indium oxide sensor device of comparative example 1 at different temperatures.
FIG. 8 is a graph showing the response of the six-sided box indium oxide sensor device of example 1 and the six-sided prism indium oxide sensor device of comparative example 1 to 2ppm hydrogen sulfide gas.
FIG. 9 is a bar graph of the response of example 1 hexagonal box indium oxide sensing device and comparative example 1 hexagonal prism indium oxide sensing device to 100ppm different gases.
Detailed Description
The invention will be further described with reference to the drawings and examples.
1. Examples
Example 1: an indium oxide nano material is prepared by the following method:
(1) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 1), puts into a clean magnetic rotor, accurately weighs 0.2mmol cobalt nitrate hexahydrate and 0.2mmol terephthalic acid with an electronic analytical balance, adds into the beaker (No. 1), puts into a magnetic stirrer and stirs for 30min;
(2) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 2), puts into a clean magnetic rotor, accurately weighs 0.6mmol indium nitrate tetrahydrate and 0.6mmol terephthalic acid in the beaker (No. 2) with an electronic analytical balance, puts into a magnetic stirrer and stirs for 30min;
(3) Taking all the solution in the beaker (No. 1) by a pipetting gun, adding the solution into the beaker (No. 2), and stirring the solution on a magnetic stirrer for 6 hours;
(4) Transferring the solution to a polytetrafluoroethylene lining, placing the lining into a reaction kettle, placing the reaction kettle into an oven, setting the condition to 160 ℃, preserving heat for 4 hours after the temperature is raised to 160 ℃, and naturally cooling to room temperature.
(5) Transferring the precipitate to a centrifuge tube, respectively washing with deionized water and absolute ethyl alcohol for three times by using a centrifuge to obtain powder, drying in a vacuum drying oven, heating to 60 ℃, and preserving heat for 12h.
(6) And (3) grinding the dried sample in a mortar uniformly, dispersing in a crucible, placing in a tube furnace for calcination, heating to 3-400 ℃, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a light yellow powder sample.
Example 2: an indium oxide nano material is prepared by the following method:
(1) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 1), puts into a clean magnetic rotor, accurately weighs 0.4mmol cobalt nitrate hexahydrate and 0.4mmol terephthalic acid with an electronic analytical balance, adds into the beaker (No. 1), puts into a magnetic stirrer and stirs for 30min;
(2) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 2), puts into a clean magnetic rotor, accurately weighs 0.4mmol indium nitrate tetrahydrate and 0.4mmol terephthalic acid in the beaker (No. 2) with an electronic analytical balance, puts into a magnetic stirrer and stirs for 30min;
(3) Taking all the solution in the beaker (No. 1) by a pipetting gun, adding the solution into the beaker (No. 2), and stirring the solution on a magnetic stirrer for 6 hours;
(4) Transferring the solution to a polytetrafluoroethylene lining, placing the lining into a reaction kettle, placing the reaction kettle into an oven, setting the condition to 160 ℃, preserving heat for 4 hours after the temperature is raised to 160 ℃, and naturally cooling to room temperature.
(5) Transferring the precipitate to a centrifuge tube, respectively washing with deionized water and absolute ethyl alcohol for three times by using a centrifuge to obtain powder, drying in a vacuum drying oven, heating to 60 ℃, and preserving heat for 12h.
(6) And (3) grinding the dried sample in a mortar uniformly, dispersing in a crucible, placing in a tube furnace for calcination, heating to 3-400 ℃, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a light yellow powder sample.
Example 3: an indium oxide nano material is prepared by the following method:
(1) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 1), puts into a clean magnetic rotor, accurately weighs 0.2mmol cobalt nitrate hexahydrate and 0.2mmol terephthalic acid with an electronic analytical balance, adds into the beaker (No. 1), puts into a magnetic stirrer and stirs for 30min;
(2) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 2), puts into a clean magnetic rotor, accurately weighs 0.6mmol indium nitrate tetrahydrate and 0.6mmol terephthalic acid in the beaker (No. 2) with an electronic analytical balance, puts into a magnetic stirrer and stirs for 30min;
(3) Taking all the solution in the beaker (No. 1) by a liquid-transferring gun, adding the solution into the beaker (No. 2), stirring the solution for 3 hours on a magnetic stirrer,
(4) Transferring the solution to a polytetrafluoroethylene lining, placing the lining into a reaction kettle, placing the reaction kettle into an oven, setting the condition to 160 ℃, preserving heat for 4 hours after the temperature is raised to 160 ℃, and naturally cooling to room temperature.
(5) Transferring the precipitate to a centrifuge tube, respectively washing with deionized water and absolute ethyl alcohol for three times by using a centrifuge to obtain powder, drying in a vacuum drying oven, heating to 60 ℃, and preserving heat for 12h.
(6) And (3) grinding the dried sample in a mortar uniformly, dispersing in a crucible, placing in a tube furnace for calcination, heating to 3-400 ℃, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a light yellow powder sample.
Example 4: an indium oxide nano material is prepared by the following method:
(1) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 1), puts into a clean magnetic rotor, accurately weighs 0.2mmol cobalt chloride hexahydrate and 0.2mmol terephthalic acid with an electronic analytical balance, adds into the beaker (No. 1), puts into a magnetic stirrer and stirs for 30min;
(2) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 2), puts into a clean magnetic rotor, accurately weighs 0.6mmol indium nitrate tetrahydrate and 0.6mmol terephthalic acid in the beaker (No. 2) with an electronic analytical balance, puts into a magnetic stirrer and stirs for 30min;
(3) Taking all the solution in the beaker (No. 1) by a liquid-transferring gun, adding the solution into the beaker (No. 2), stirring the solution for 6 hours on a magnetic stirrer,
(4) Transferring the solution to a polytetrafluoroethylene lining, placing the lining into a reaction kettle, placing the reaction kettle into an oven, setting the condition to 160 ℃, preserving heat for 4 hours after the temperature is raised to 160 ℃, and naturally cooling to room temperature.
(5) Transferring the precipitate to a centrifuge tube, respectively washing with deionized water and absolute ethyl alcohol for three times by using a centrifuge to obtain powder, drying in a vacuum drying oven, heating to 60 ℃, and preserving heat for 12h.
(6) And (3) grinding the dried sample in a mortar uniformly, dispersing in a crucible, placing in a tube furnace for calcination, heating to 3-400 ℃, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a light yellow powder sample.
Comparative example 1:
(1) The pipette takes 30 mL of DMF in a clean and dry 100mL beaker, places the beaker in a clean magnetic rotor, accurately weighs 0.8mmol of indium nitrate tetrahydrate and 0.8mmol of terephthalic acid with an electronic analytical balance into the beaker, and places the beaker on a magnetic stirrer to stir for 6 hours.
(2) Transferring the solution to a polytetrafluoroethylene lining, placing the lining into a reaction kettle, placing the reaction kettle into an oven, setting the condition to 160 ℃, preserving heat for 4 hours after the temperature is raised to 160 ℃, and naturally cooling to room temperature.
(3) Transferring the precipitate to a centrifuge tube, respectively washing with deionized water and absolute ethyl alcohol for three times by using a centrifuge to obtain powder, drying in a vacuum drying oven, heating to 60 ℃, and preserving heat for 12h.
(4) And (3) grinding the dried sample in a mortar uniformly, dispersing in a crucible, placing in a tube furnace for calcination, heating to 3-400 ℃, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a light yellow powder sample.
Comparative example 2:
(1) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 1), puts into a clean magnetic rotor, accurately weighs 0.2mmol cobalt nitrate hexahydrate and 0.2mmol terephthalic acid with an electronic analytical balance, adds into the beaker (No. 1), puts into a magnetic stirrer and stirs for 30min;
(2) The pipette takes 15 mL DMF in a clean and dry 100mL beaker (No. 2), puts into a clean magnetic rotor, accurately weighs 0.6mmol indium nitrate tetrahydrate and 0.6mmol terephthalic acid in the beaker (No. 2) with an electronic analytical balance, puts into a magnetic stirrer and stirs for 30min;
(3) Taking all the solution in the beaker (No. 1) by a pipetting gun, adding the solution into the beaker (No. 2), and stirring the solution on a magnetic stirrer for 30min;
(4) Transferring the solution to a polytetrafluoroethylene lining, placing the lining into a reaction kettle, placing the reaction kettle into an oven, setting the condition to 160 ℃, preserving heat for 4 hours after the temperature is raised to 160 ℃, and naturally cooling to room temperature.
(5) Transferring the precipitate to a centrifuge tube, respectively washing with deionized water and absolute ethyl alcohol for three times by using a centrifuge to obtain powder, drying in a vacuum drying oven, heating to 60 ℃, and preserving heat for 12h.
(6) And (3) grinding the dried sample in a mortar uniformly, dispersing in a crucible, placing in a tube furnace for calcination, heating to 3-400 ℃, preserving heat for 2 hours, and naturally cooling to room temperature to obtain a light yellow powder sample.
Comparative example 2 in step (3), the mixed solution was stirred on a magnetic stirrer for 30 minutes, at this time, the color of the reaction solution after stirring was a pink clear solution, whereas the color of the reaction solution after stirring was gray-black in example 1, because the stirring time of comparative example 2 was insufficient, the reaction in the reaction solution was not sufficiently progressed, the obtained product was extremely small, and the product rate was extremely low. After extensive studies of the reaction, it was found that the length of the stirring time affected the yield of the final product, and if the stirring time was less than 30 minutes, the yield of the product was less than one fifth of that of example 1. Therefore, in step (3), the stirring time should be not less than 30 minutes.
2. Examples and comparative examples Performance analysis
FIG. 1 is an SEM topography of a hexagonal indium oxide nanomaterial obtained in the present invention (example 1), showing a box shape; as can be seen from FIG. 1, the indium oxide nanomaterial of the present invention has a hexagonal box morphology, a diameter of 1-2 μm and a length of 1-2 μm, and the porous structure has a relatively large specific Surface Area (BET Surface area= 57.38 m) 2 g -1 ) The gas attachment sites are increased, which is advantageous for Yu Qi-sensitive reactions. Meanwhile, according to the invention, through intensive researches, not only cobalt nitrate hexahydrate can influence the morphology of indium oxide, but also cobalt chloride hexahydrate is used in the preparation of indium oxide by using other cobalt salts, and the morphology of the product indium oxide is similarly changed as in the embodiment 4, and it is presumed that cobalt salts containing cobalt ions can have an advantageous effect on the morphology of indium oxide, and as can be seen from the comparison example 1, the morphology of indium oxide obtained without participation of cobalt ions is significantly different from the morphology of indium oxide obtained with participation of cobalt ions, and therefore, the cobalt salts added in the preparation process of indium oxide can have an advantageous effect on the morphology of indium oxide.
FIG. 2 is a SEM topography of a hexagonal prism indium oxide material obtained in comparative example 1 without cobalt ion participation, showing a hexagonal rod shape having a diameter of 1 to 2 μm and a length of 10 to 30 μm, which is longer than that of example 1, and a specific Surface Area (BET Surface area=32.73 m) 2 g -1 ) Smaller, unfavorable Yu Qi sensitive reactions. As can be seen by comparing fig. 1 and fig. 2, the presence of cobalt ions in the solution produces a very pronounced morphology for indium oxideThe influence of the indium oxide is very beneficial and positive, so that the indium oxide which originally presents a hexagonal rod-shaped structure is changed to form a hexagonal box shape, the specific surface area of the indium oxide is increased, and then the attachment sites of gas are increased; on the other hand, during the solution reaction, the existence of cobalt ions increases the number of oxygen vacancies in the hexagonal box indium oxide nanomaterial, and both aspects are beneficial to the gas-sensitive reaction.
Fig. 3, 4 and 5 show XRD, XPS spectrum and XPS spectrum of the material obtained in example 1 and comparative example 1, and it is clear from the figures that the material obtained in comparative example 1 and example 1 is indium oxide, but the cobalt element is present in the indium oxide obtained in example 1. Fig. 6 is a SEM morphology diagram of the indium oxide material obtained in the corresponding example 4, showing a box shape, and the synthesis of cobalt chloride hexahydrate instead of cobalt nitrate hexahydrate, illustrates that the morphology of indium oxide can be changed by other cobalt sources, and that the hexagonal rod-shaped indium oxide can be shortened to a box-shaped indium oxide nanomaterial.
From the results, the indium oxide nano material has a hexagonal box shape, and the porous structure has a larger specific Surface Area (BET Surface area= 57.38 m) 2 g -1 ) The existence of cobalt ions increases the oxygen vacancies of the obtained hexagonal box indium oxide nano material, thereby further enhancing the gas-sensitive performance; the preparation method does not use a surfactant, and has the characteristics of low cost, simple preparation method and the like.
3. Application of indium oxide nano material
The hexagonal box indium oxide nanomaterial prepared by the preparation method of the indium oxide nanomaterial can be used for hydrogen sulfide detection. And depositing the obtained hexagonal box indium oxide nanomaterial on the surface of an electrode to obtain a sensing device, and detecting hydrogen sulfide through the change of resistance before and after the sensor contacts hydrogen sulfide gas, wherein the sensitivity of the gas sensor is defined as Ra/Rg (Ra is the resistance value in air, and Rg is the resistance value in target hydrogen sulfide gas). Dispersing the prepared indium oxide material in absolute ethyl alcohol, taking concentrated slurry of the uniformly dispersed material by a liquid-transferring gun, dripping the concentrated slurry on an electrode, and aging for 24 hours in a vacuum environment to obtain the gas sensor.
The gas sensors prepared In example 1 and comparative example 1 were prepared by the above-described method, and the hexagonal box indium oxide nanomaterial (Co-In) prepared In example 1 2 O 3 ) Sensor and hexagonal prism indium oxide material (In 2 O 3 ) The sensor performs performance test comparison:
FIG. 7 shows that the devices prepared in example 1 and comparative example 1 all operate at 225 degrees Celsius;
FIG. 8 is a graph of the gas-sensitive response to 2ppm hydrogen sulfide gas at 225℃for the devices prepared in example 1 and comparative example 1, illustrating that the device prepared in example 1 has a better gas-sensitive response than the device prepared in comparative example 1;
FIG. 9 is a bar graph of the gas response from tests conducted on 100ppm of different gases at 225℃for the devices prepared in example 1 and comparative example 1, showing that example 1 has an extremely high response to hydrogen sulfide and is able to effectively distinguish it from other gases.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (8)
1. The indium oxide nano material is characterized by being prepared by the following steps:
step 1: adding DMF into a container, adding cobalt salt and terephthalic acid, and uniformly stirring;
step 2: adding DMF, indium nitrate tetrahydrate and terephthalic acid into another container, and uniformly stirring;
step 3: adding the solution obtained in the step 1 into the solution obtained in the step 2, and uniformly stirring to obtain a reaction solution; wherein, in the reaction liquid, the molar concentration ratio of cobalt ions, indium nitrate tetrahydrate and terephthalic acid is 1: (1-5): (2-6); in the step 3, the stirring time is more than 30min;
step 4: transferring the reaction liquid obtained in the step 3 into a reaction kettle, heating to 120-180 ℃, preserving heat for 2-6 hours, and cooling to room temperature;
step 5: washing the reaction product obtained in the step 4, centrifugally separating, washing a solid product, and drying;
step 6: grinding the dried sample in the step 5, dispersing and placing the ground sample in a crucible, placing the crucible in a tube furnace for calcination, heating the crucible to 350-500 ℃ for 3-8 hours, keeping the temperature for 1-3 hours at a heating rate of not more than 5 ℃/min, and cooling the crucible to room temperature to obtain the light yellow indium oxide nano material.
2. The indium oxide nanomaterial of claim 1, wherein in step 3, the molar concentration ratio of cobalt ions, indium nitrate tetrahydrate, and terephthalic acid is 1: (2-4): (3-5).
3. The indium oxide nanomaterial of claim 1, wherein in step 4, the reaction temperature is 150 ℃ to 170 ℃.
4. The indium oxide nanomaterial of claim 1, wherein in step 4, the holding time is 3h to 5h.
5. The indium oxide nanomaterial of claim 1, wherein in step 6, the temperature is raised to 400 ℃ to 450 ℃ by 3 hours to 4 hours, the temperature raising rate is not more than 3 ℃/min, and the temperature is kept for 1 hour to 2 hours.
6. An application of an indium oxide nanomaterial, which is characterized in that the indium oxide nanomaterial according to any one of claims 1 to 5 is used as a gas-sensitive material for detecting hydrogen sulfide gas.
7. The application of the indium oxide nanomaterial according to claim 6, characterized in that the indium oxide nanomaterial according to any one of claims 1 to 5 is dissolved in absolute ethyl alcohol to prepare a solution with a concentration of 25g/L, the solution is uniformly dispersed to form thick slurry, the thick slurry is dripped on the surface of an interdigital electrode, and aging is carried out for 24 hours in a vacuum environment, so that a gas-sensitive device for detecting hydrogen sulfide gas is obtained.
8. The use of indium oxide nanomaterial according to claim 7, characterized in that the indium oxide nanosensor detects hydrogen sulfide gas comprising the steps of:
(1) Obtaining stable resistance value R of indium oxide sensing device under dry air a ；
(2) Introducing hydrogen sulfide to enable the hydrogen sulfide to act on the indium oxide sensing device;
(3) Stable resistance value R of indium oxide sensing device under action of hydrogen sulfide g ；
(4) And calculating a response value of the indium oxide sensing device according to the relative change of the resistance, wherein the calculation formula is as follows: r is R a /R g Wherein R is a And R is g The stable resistance values of the sensing device under the action of dry air and hydrogen sulfide are respectively shown.
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