CN112479246B - Preparation of Ni-doped stannic oxide formaldehyde sensitive composite material based on ZIF-8 metal organic framework template, product and application - Google Patents
Preparation of Ni-doped stannic oxide formaldehyde sensitive composite material based on ZIF-8 metal organic framework template, product and application Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 45
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title abstract description 24
- 239000011206 ternary composite Substances 0.000 claims abstract description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000001276 controlling effect Effects 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 8
- -1 tin dioxide formaldehyde Chemical compound 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229910006404 SnO 2 Inorganic materials 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 8
- 238000004729 solvothermal method Methods 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 239000002086 nanomaterial Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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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Abstract
The invention discloses a preparation method of a Ni-doped stannic oxide formaldehyde sensitive ternary composite material based on a ZIF-8 metal organic framework template, and a product and application thereof, wherein the method utilizes ZIF-8 MOF material is used as a crystallization template, thiourea is decomposed under the condition of glycol solvothermal to provide S 2‑ Generating SnS 2 And NiS precursor, and preparing Ni-doped SnO based on ZIF-8 metal organic framework template by regulating and controlling conditions such as roasting temperature, roasting time and the like of the precursor 2 A formaldehyde-sensitive ternary composite material. The specific surface area of the prepared composite material can be greatly improved by taking ZIF-8 as a template, and the doping of Zn and Ni is beneficial to further improving SnO 2 Response value and selectivity to formaldehyde gas; the preparation method of the SnO prepared by the solvothermal method is simple, the reaction temperature is low, and the subsequent treatment is not needed 2 the/NiO @ ZIF-8 ternary composite material can be used for formaldehyde gas sensors and the like.
Description
Technical Field
The invention relates to a preparation technology of a metal oxide nano material, in particular to Ni-doped SnO based on a ZIF-8 metal organic framework template 2 A preparation method of formaldehyde-sensitive ternary composite material, and a product and application thereof.
Background
Formaldehyde is a carcinogenic gas, is commonly used in interior decoration materials such as interlayer glue, paint, plastic products and the like of new furniture, and is one of main indoor pollution gases harmful to human bodies. The latest standard established by the world health organization is that the content of formaldehyde exposed to human body for a long time should not exceed 0.08 ppm. However, low concentrations of formaldehyde are difficult to detect by the human olfactory system. Therefore, the developed formaldehyde gas sensing material has a far-reaching practical significance on high formaldehyde sensitivity, strong anti-interference capability of other gases and stable chemical properties.
Tin dioxide is an n-type semiconductor with a wide forbidden band, and has an adjustable pore structure and a high specific surface area, so that defects are easily generated to dope impurities, and meanwhile, the tin dioxide is low in price, easy to synthesize, non-toxic and harmless, so that the tin dioxide nano-structure material is widely applied to sensitive materials of gas sensors. However, the gas-sensitive property of a single tin dioxide material is controlled by the morphology, crystal form, specific surface area, energy band structure and the like of the material, and the defects of low sensitivity to formaldehyde, poor selectivity and the like still exist.
Metal-Organic Framework (MOF) is a new type of porous material formed by Metal ions and Organic ligands through coordination bonds. The nano material obtained by taking the MOF as the template has the characteristics of high porosity and large specific surface area, and has more active chemical properties. Meanwhile, the aggregation of the doped metal elements can be effectively prevented due to the existence of ligand molecules. Comparatively pure SnO 2 In terms of material, snO 2 the/NiO composite material is easier to generate electron-hole exchange due to the difference of energy levels of a conduction band and a valence band, and has better selectivity to formaldehyde. So that SnO synthesized by taking ZIF-8 as template 2 the/NiO @ ZIF-8 ternary composite material has better gas-sensitive property to formaldehyde. The invention takes ZIF-8 as a template and adopts a simple solvothermal method to prepare SnO 2 the/NiO @ ZIF-8 ternary composite nano material provides a high-quality gas-sensitive sensor material aiming at formaldehyde gas for the market.
Disclosure of Invention
The invention aims to provide Ni-doped SnO (SnO) based on ZIF-8 metal organic framework template 2 A preparation method of formaldehyde-sensitive ternary composite nano material.
Yet another object of the present invention is to: the Ni-doped SnO prepared by the method based on the ZIF-8 metal organic framework template is provided 2 Formaldehyde-sensitive ternary composite nano-material products.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: preparation method of Ni-doped stannic oxide formaldehyde sensitive composite material based on ZIF-8 metal-organic framework template, which utilizes ZIF-8 metal-organic framework Material (MOF) as crystalTemplate, thioureolytic cleavage of ethylene glycol to provide S2-, snS formation 2 And NiS precursor, and preparing Ni-doped SnO based on ZIF-8 metal organic framework template by regulating and controlling conditions such as roasting temperature, roasting time and the like of the precursor 2 The formaldehyde-sensitive ternary composite material comprises the following steps:
(1) Pouring N-N Dimethylformamide (DMF) and methanol with the concentration of 2wt% into a flask according to the volume ratio of 1;
(2) 0.8 to 1.0g of zinc nitrate hexahydrate (Zn (NO) 3 ·6H 2 O) and 0.1 to 0.3g of 2-methylimidazole (2-MI) are put into a flask and fully stirred at room temperature;
(3) Transferring the solution in the flask to a beaker, completely reacting in an oven at 100 ℃, taking the precipitate, washing and drying to obtain ZIF-8 powder;
(4) 0.3g of the dried ZIF-8 powder was taken and put into 100mL of ethylene glycol ((CH) 2 OH) 2 ) 0.1 to 0.2g of nickel chloride hexahydrate (NiCl) is added into the mixture at the same time 2 ·6H 2 O), 1.0 to 2.0g of stannous chloride dihydrate and 1.0 to 1.5g of thiourea (NH) 2 CSNH 2 ) Or urea, and stirring uniformly;
(5) Transferring the solution after uniform stirring into a polytetrafluoroethylene reaction kettle, reacting in an oven at 150 to 180 ℃ for 24 hours, taking the precipitate, washing and drying to obtain a precursor;
(6) Putting the dried precursor into a crucible, putting the crucible into a muffle furnace, and roasting at 550-650 ℃ to obtain Ni-doped SnO based on a ZIF-8 metal organic framework template 2 A formaldehyde-sensitive ternary composite material.
The method has controllable Ni doping amount and uniform distribution of Ni and Zn elements, and provides a high-quality synthesis method of the gas-sensitive sensing material aiming at formaldehyde detection.
Wherein the volume of DMF in the step (1) is 40 to 50mL, and the volume of methanol is 80 to 100mL.
The rotation speed of the full stirring in the step (2) is 1000 revolutions per minute, and the stirring time is 20 to 30min.
The reaction time in the step (3) is 20 to 24h.
The thiourea described in step (4) may be replaced by an equimolar amount of urea.
The baking speed in the step (6) is 3 to 5 ℃/min, and the baking heat preservation time is 120 to 240min.
The invention also provides Ni-doped SnO based on the ZIF-8 metal organic framework template 2 The formaldehyde-sensitive ternary composite material is prepared by any one of the methods.
In addition, the invention also provides Ni-doped SnO based on the ZIF-8 metal organic framework template 2 The formaldehyde-sensitive ternary composite material is applied to a formaldehyde gas sensor.
A simple and feasible preparation method of a Ni-doped SnO2 formaldehyde sensitive ternary composite material based on a ZIF-8 metal organic framework template is characterized in that a ZIF-8 MOF material is used as the template, stannous chloride, nickel chloride and thiourea are used as reactants to synthesize a precursor SnS2/NiS @ ZIF-8 by a solvothermal method, and then the precursor is simply roasted to synthesize the SnO2/NiO @ ZIF-8 ternary composite nanomaterial.
The invention takes ZIF-8 as a template and adopts a simple solvothermal method to prepare SnO 2 the/NiO @ ZIF-8 ternary composite nano material provides a high-quality gas-sensitive sensor material aiming at formaldehyde gas for the market. The specific surface area of the prepared composite material can be greatly improved by taking ZIF-8 as a template, and the doping of Zn and Ni is beneficial to further improving SnO 2 Response value and selectivity to formaldehyde gas; the preparation method of the SnO prepared by the solvothermal method is simple, the reaction temperature is low, and the subsequent treatment is not needed 2 the/NiO @ ZIF-8 ternary composite material can be used for formaldehyde gas sensors and the like.
The invention has the advantages that: the doping amount of Ni and Zn is controllable, the doping elements are uniformly distributed, and the ternary composite nano material has high purity, uniform size, sensitivity and selectivity to formaldehyde and pure SnO 2 Compared with the nanometer materials, the nanometer material is greatly improved.
Drawings
FIG. 1 is SnO of example 1 of the present invention 2 The real-time response curve of the/NiO @ ZIF-8 ternary composite nano material to 200ppm formaldehyde gas;
FIG. 2 is SnO of example 2 of the present invention 2 The response value of the/NiO @ ZIF-8 ternary composite nano material to different gases of 200ppm of formaldehyde, methanol, ethanol, acetone and ammonia gas.
Detailed Description
Example 1:
a ZIF-8 metal-organic framework template-based Ni-doped stannic oxide formaldehyde sensitive composite material is prepared by taking a ZIF-8 metal-organic framework material as a crystallization template, decomposing thiourea under the solvothermal condition of ethylene glycol to provide S2-, and generating SnS 2 And NiS precursor, and preparing Ni-doped SnO based on ZIF-8 metal organic framework template by regulating and controlling the roasting temperature and roasting time of the precursor 2 The formaldehyde-sensitive ternary composite material is prepared by the following steps:
(1) 50mL of N-N Dimethylformamide (DMF) and 100mL of methanol with the concentration of 2wt% are weighed and poured into a flask, and the mixture is stirred uniformly;
(2) 0.8g of zinc nitrate hexahydrate (Zn (NO) 3 ·6H 2 O) and 0.1g of 2-methylimidazole (2-MI) were placed in a flask and sufficiently stirred at room temperature;
(3) Transferring the solution in the flask to a beaker, completely reacting in an oven at 100 ℃, taking the precipitate, washing and drying to obtain ZIF-8 powder;
(4) 0.3g of the dried ZIF-8 powder was taken and put into 100mL of ethylene glycol ((CH) 2 OH) 2 ) In (1), 0.1g of nickel chloride hexahydrate (NiCl) was added simultaneously 2 ·6H 2 O), 1.0g stannous chloride dihydrate and 1.1g thiourea (NH) 2 CSNH 2 ) Stirring uniformly;
(5) Transferring the uniformly stirred solution into a polytetrafluoroethylene reaction kettle, reacting in an oven at 150 ℃ for 24 hours, taking the precipitate, washing and drying to obtain a precursor;
(6) Putting the dried precursor into a crucible, putting the crucible into a muffle furnace, and roasting the precursor for 2 hours at 550 ℃ to obtain Ni-doped SnO based on a ZIF-8 metal organic framework template 2 A formaldehyde-sensitive ternary composite material.
FIG. 1 shows the SnO 2 The gas-sensitive sensing device made of the/NiO @ ZIF-8 ternary composite nano material has a real-time response curve to 200ppm of formaldehyde gas at 230 ℃. It can be seen that the material produces very high response values to formaldehyde.
Example 2:
an Ni-doped stannic oxide formaldehyde sensitive composite material based on a ZIF-8 metal organic framework template is similar to that in the embodiment 1, and is prepared by the following steps:
(1) 30mL of N-N Dimethylformamide (DMF) and 60mL of methanol with the concentration of 2wt% are weighed and poured into a flask, and the mixture is uniformly stirred;
(2) 0.9g of zinc nitrate hexahydrate (Zn (NO) 3 ·6H 2 O) and 0.2g of 2-methylimidazole (2-MI) were put into a flask and sufficiently stirred at room temperature;
(3) Transferring the solution in the flask to a beaker, completely reacting in an oven at 100 ℃, taking the precipitate, washing and drying to obtain ZIF-8 powder;
(4) 0.3g of the dried ZIF-8 powder was taken and put into 100mL of ethylene glycol ((CH) 2 OH) 2 ) In the meantime, 0.15g of nickel chloride hexahydrate (NiCl) was added 2 ·6H 2 O), 1.5g stannous chloride dihydrate and 1.3g thiourea (NH) 2 CSNH 2 ) Stirring uniformly;
(5) Transferring the solution after uniform stirring to a polytetrafluoroethylene reaction kettle, reacting for 24 hours in an oven at 160 ℃, taking the precipitate, washing and drying to obtain a precursor;
(6) Putting the dried precursor into a crucible, putting the crucible into a muffle furnace, and roasting the precursor for 2 hours at 600 ℃ to obtain Ni-doped SnO based on a ZIF-8 metal organic framework template 2 Formaldehyde sensitive ternary composite material.
FIG. 2 is the SnO 2 And a sensing device made of the/NiO @ ZIF-8 ternary composite nano material has a histogram of response values to various gases of 200ppm of formaldehyde, methanol, ethanol, acetone and ammonia gas at 230 ℃. The response value of the material to formaldehyde is far higher than that of other gases, which shows that the material has good selectivity and can effectively avoid the interference of other gases to the detection result.
Example 3:
a ZIF-8 metal organic framework template-based Ni-doped tin dioxide formaldehyde sensitive composite material is similar to that in example 1 and is prepared by the following steps:
(1) Weighing 40mL of N-N Dimethylformamide (DMF) and 80mL of methanol with the concentration of 2wt%, pouring into a flask, and uniformly stirring;
(2) 1.0g of zinc nitrate hexahydrate (Zn (NO) 3 ·6H 2 O) and 0.3g of 2-methylimidazole (2-MI) were placed in a flask and sufficiently stirred at room temperature;
(3) Transferring the solution in the flask to a beaker, completely reacting in an oven at 100 ℃, taking the precipitate, washing and drying to obtain ZIF-8 powder;
(4) 0.3g of dried ZIF-8 powder was put into 100mL of ethylene glycol ((CH) 2 OH) 2 ) In (1), 0.2g of nickel chloride hexahydrate (NiCl) was added simultaneously 2 ·6H 2 O), 2.0g stannous chloride dihydrate and 1.5g thiourea (NH) 2 CSNH 2 ) Stirring uniformly;
(5) Transferring the uniformly stirred solution into a polytetrafluoroethylene reaction kettle, reacting for 24 hours in an oven at 180 ℃, taking the precipitate, washing and drying to obtain a precursor;
(6) Putting the dried precursor into a crucible, putting the crucible into a muffle furnace, and roasting at 650 ℃ for 2 hours to obtain Ni-doped SnO (SnO) based on a ZIF-8 metal organic framework template 2 Formaldehyde sensitive ternary composite material.
Claims (5)
1. A preparation method of a Ni-doped tin dioxide formaldehyde sensitive composite material based on a ZIF-8 metal-organic framework template is characterized in that a ZIF-8 metal-organic framework material is used as a crystallization template, and thiourea is decomposed under the thermal condition of an ethylene glycol solvent to provide S 2- Generating SnS 2 And NiS precursor, and preparing Ni-doped SnO based on ZIF-8 metal organic framework template by regulating and controlling roasting temperature and roasting time of the precursor 2 The formaldehyde-sensitive ternary composite material comprises the following steps:
(1) Pouring N, N-Dimethylformamide (DMF) and methanol with the concentration of 2wt% into a flask according to the volume ratio of 1;
(2) 0.8 to 1.0g of zinc nitrate hexahydrate (Zn (NO) 3 ·6H 2 O) and 0.1 to 0.3g of 2-methylimidazole (2-MI) are put into a flask and fully stirred at room temperature;
(3) Transferring the solution in the flask to a beaker, completely reacting in an oven at 100 ℃, taking the precipitate, washing and drying to obtain ZIF-8 powder;
(4) 0.3g of dried ZIF-8 powder was put into 100mL of ethylene glycol ((CH) 2 OH) 2 ) 0.1 to 0.2g of nickel chloride hexahydrate (NiCl) is added into the mixture at the same time 2 ·6H 2 O), 1.0 to 2.0g of stannous chloride dihydrate and 1.0 to 1.5g of thiourea (NH) 2 CSNH 2 ) Stirring uniformly;
(5) Transferring the solution after uniform stirring to a polytetrafluoroethylene reaction kettle, reacting for 24 hours in an oven at 150 to 180 ℃, taking the precipitate, washing and drying to obtain a precursor;
(6) Putting the dried precursor into a crucible, putting the crucible into a muffle furnace, and roasting at 550-650 ℃ to obtain Ni-doped SnO based on a ZIF-8 metal organic framework template 2 Formaldehyde-sensitive ternary composites; wherein,
in the step (1), the volume of DMF is 40 to 50mL, and the volume of methanol is 80 to 100mL;
in the step (2), the rotation speed of the full stirring is 1000 revolutions per minute, and the stirring time is 20 to 30min.
2. The method of claim 1, wherein: in the step (3), the reaction time is 20 to 24h.
3. The production method according to claim 1, characterized in that: in the step (6), the temperature rising speed of the roasting is 3 to 5 ℃/min, and the heat preservation time of the roasting is 120 to 240min.
4. Ni-doped SnO (SnO) based on ZIF-8 metal organic framework template 2 Formaldehyde-sensitive composite material, characterized in that it is prepared according to any one of claims 1 to 3.
5. The ZIF-8 metal organic framework template-based Ni-doped SnO according to claim 4 2 The formaldehyde sensitive composite material is applied as a gas sensor material.
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