CN110813202A - Co3O4Preparation method and application of @ ZIF-67 core-shell structure material - Google Patents

Co3O4Preparation method and application of @ ZIF-67 core-shell structure material Download PDF

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CN110813202A
CN110813202A CN201911171897.3A CN201911171897A CN110813202A CN 110813202 A CN110813202 A CN 110813202A CN 201911171897 A CN201911171897 A CN 201911171897A CN 110813202 A CN110813202 A CN 110813202A
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季澎
章伟
田仁兵
郑华
张耿
张绍强
胡君
刘敏霞
李仪
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Dongguan University of Technology
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Abstract

The invention relates to Co3O4The preparation of the material with the structure of @ ZIF-67 core-shell and the application of the material in a gas sensor are carried out by Co3O4A layer of ZIF-67 shell material grows on the surface of the nano-particles, and selective filtration of macromolecular gas is realized. Co prepared by the method3O4The material with the @ ZIF-67 core-shell structure can be used as a gas-sensitive sensing material, particularly shows good gas-sensitive selectivity for small-molecule gases such as hydrogen, methanol and the like, and hardly responds to large-molecule gases. Co of the invention3O4The synthesis of the material with the @ ZIF-67 core-shell structure is reported for the first time and is easy to implement.

Description

Co3O4Preparation method and application of @ ZIF-67 core-shell structure material
Technical Field
The invention discloses a Co3O4The preparation of the material with the @ ZIF-67 core-shell structure and the application of the gas sensor relate to the field of the preparation of sensing materials and the application of the gas sensor.
Background
The gas sensitivity selectivity of a semiconductor gas sensor is a very important indicator, since different gases may respond to the semiconductor sensing material, so that it is difficult to separate the signals of different gases. By utilizing the principle that different gas sizes are different, the porous materials with different apertures are coated on the surface of the sensing material to serve as the shell layer, so that the gas with the molecular size larger than the aperture of the shell layer can be selectively filtered, and the selective identification of the micromolecular gas is realized.
SnO2(Sensors and Actuators B:Chemical,1999,60,64-70)、ZnO(Sensors andActuators B:Chemical,2000,66,277-279)、Co3O4(Advanced Functional Materials,2005, 15, 851-. In which SnO is classified according to semiconductor2And ZnO or the like being n-type semiconductor, Co3O4And CuO, etc. are p-type semiconductors.
ZIF (fully-known as Zeolite Imidazolate Frameworks) materials are one type of metal organic framework Materials (MOFs) and have a porous structure similar to zeolite molecular sieves. In recent years, a core-shell structure material ZnO @ ZIF-8(ACS Sensors,2016,1, 243-. Peculiar to the aid of ZIF-8
Figure BDA0002288931090000011
The small pore diameter (PNAS,2006,103,10186-&Interfaces,2016,8,8323- > 8328; Chemistry-A European Journal,2017,23, 7969-7975; sensors and activators B,2008,258, 1099-. ZIF-67 is a Co-based ZIF material with the same topology as ZIF-8 (Science,2008,319, 939-.
Patent CN109019783A discloses a Co (OH)2The preparation method of the/ZIF-67 carbon-based catalytic electrode comprises the following steps: (1) co (OH) is loaded on the surface of the carbon-based electrode2A layer; (2) loading Co (OH) obtained in step (1)2The carbon-based electrode of the layer is placed in gas-phase 2-methylimidazole and reacts for 1-60 min at the temperature of 120-220 ℃ to obtain a ZIF-67 layer; (3) after the reaction is finished, washing and drying to obtain Co (OH)2a/ZIF-67 carbon-based catalytic electrode. The Co (OH)2the/ZIF-67 material can be used as a catalytic electrode. But can not be used as a core-shell structure material to be applied to a gas sensor.
Co3O4Growing ZIF-67 shell on the surface to prepare Co3O4The document of the @ ZIF-67 core-shell structure material is not reported yet.
Disclosure of Invention
It is an object of the present invention to provide a Co3O4A preparation method of @ ZIF-67 core-shell structure material.
Another object of the present invention is to provide Co3O4The application of the material with the @ ZIF-67 core-shell structure in the gas sensor.
The invention is realized by the following technical scheme:
co3O4The preparation method of the @ ZIF-67 core-shell structure material comprises the following steps:
mixing Co3O4Carrying out post-treatment on the matrix, adding an organic ligand and a solvent, and heating in a closed system to obtain Co3O4@ ZIF-67 core-shell structure material.
Co as described above3O4The preparation method of the @ ZIF-67 core-shell structure material comprises the following steps:
(1) preparation of Co3O4A parent body;
(2) the matrix Co3O4Adding the powder into a solvent containing an organic ligand, and heating and reacting in a closed system;
(3) filtering, washing and drying the mixture obtained after the reaction in the step 2 to obtain Co3O4@ ZIF-67 core-shell structure material.
Co as described above3O4In the preparation method of the @ ZIF-67 core-shell structure material, Co is adopted in the step (1)3O4The particle size range of the matrix is 50-80 nm.
Co as described above3O4In the preparation method of the @ ZIF-67 core-shell structure material, Co is adopted in the step (1)3O4The preparation method of the matrix comprises the following steps: placing cobalt acetate tetrahydrate in a crucible, heating to 500 deg.C at 2 deg.C per minute, maintaining for 1 hr, and cooling to obtain Co3O4And (4) a parent body.
Co as described above3O4In the preparation method of the @ ZIF-67 core-shell structure material, the ligand in the step (2) is 2-methylimidazole, and the molar ratio of the 2-methylimidazole to the cobalt atom is 0.5-3: 1.
Co as described above3O4In the preparation method of the @ ZIF-67 core-shell structure material, the reaction temperature in the step (2) is 130-170 ℃, and the reaction time is 1-3 days.
Co as described above3O4The preparation method of the @ ZIF-67 core-shell structure material comprises the following detailed steps:
(1) pyrolysis method for preparing Co with particle size of 50-80 nm3O4As a precursor, cobalt acetate tetrahydrate is put in a crucible, heated to 500 ℃ at the speed of 2 ℃ per minute, kept for 1 hour, and then cooled to obtain Co3O4A parent body;
(2) 0.1g of Co prepared in step 1 was weighed3O4Adding the mixture into 10g of methanol, keeping magnetic stirring, and then adding ligand 2-methylimidazole (the molar ratio of 2-methylimidazole/Co is 0.5-3:1) continuously stirring for 5 minutes, transferring the mixture into a 50mL tetrafluoroethylene lining with a stainless steel outer sleeve, screwing the mixture, transferring the mixture into a blast drying oven, and standing the mixture for 1 to 3 days at the temperature of between 130 and 170 ℃;
(3) step 2, cooling the kettle after the reaction is finished, filtering and washing the product, and drying the product at the temperature of 60 ℃ to obtain the Co of a thin shell layer3O4@ZIF-67。
Co as described above3O4The application of the material with the @ ZIF-67 core-shell structure in the gas sensor.
The invention has the beneficial effects that:
(1) the invention provides a new kind of Co3O4Preparation method of @ ZIF-67 core-shell structure material, and preparation method of Co3O4@ ZIF-67 core-shell structure material has not been reported in public.
(2) Seed Co of the invention3O4The preparation method of the @ ZIF-67 core-shell structure material comprises the steps of adding an organic ligand under the solvothermal condition, and etching the Co under the self-etching action of Co under the alkaline condition2+In Co3O4The surface of the catalyst is coordinated and assembled with an organic ligand to form a ZIF-67 shell, and etched Co3+Transferring the mixture into a solvent to successfully prepare Co3O4@ ZIF-67 core-shell structure material. The preparation method is convenient and feasible, is easy to amplify, and has certain industrial application prospect.
(3) Co prepared by the method of the invention3O4The material has a @ ZIF-67 core-shell structure, and a ZIF-67 shell layer can effectively block macromolecular gases such as toluene and acetone, so that the material can realize the directional sensing of small molecular gases such as hydrogen and methanol.
Drawings
FIG. 1 shows Co synthesized in example 13O4@ ZIF-67 and parent Co3O4Comparing XRD diffraction patterns of the components.
FIG. 2 shows the Co synthesized in example 13O4Scanning Electron microscopy of @ ZIF-67.
Detailed Description
The present invention will be described in further detail below with reference to specific examples.
Example 1 thin Shell Co3O4@ ZIF-67 synthesis, comprising the following steps:
step 1, firstly, we prepare Co with particle size of about 50nm by pyrolysis method3O4As a matrix, the specific operation is that cobalt acetate tetrahydrate is put in a crucible, heated to 500 ℃ at the speed of 2 ℃ per minute, kept for 1 hour, and then cooled to obtain black nano Co3O4。
Step 2, weighing 0.1g of Co prepared in step 13O4Then, the mixture was added to 10g of methanol, magnetic stirring was maintained, then 0.01g of ligand 2-methylimidazole (2-methylimidazole/Co molar ratio 1:1) was added thereto, stirring was continued for 5 minutes, and then the mixture was transferred to 50mL of a tetrafluoroethylene inner liner with a stainless steel outer jacket, screwed down and transferred to an air-blowing dry box, and left to stand at 150 ℃ for 3 days.
Step 3, cooling the kettle after the reaction in the step 2, filtering the product, fully washing the product with water, and drying the product at the temperature of 60 ℃ to obtain the Co of the thin shell layer of the product3O4@ZIF-67。
Example 2 Co with Thick Shell3O4@ ZIF-67 synthesis, comprising the following steps:
step 1, nano Co as in example 13O4And (4) preparation.
Step 2, weighing 0.1g of Co prepared in step 13O4Then, the mixture was added to 10g of methanol, magnetic stirring was maintained, then 0.03g of ligand 2-methylimidazole (2-methylimidazole/Co molar ratio: 3:1) was added thereto, stirring was continued for 5 minutes, and then the mixture was transferred to 50mL of a tetrafluoroethylene inner liner with a stainless steel outer jacket, screwed down and transferred to an air-blowing dry oven, and left to stand at 140 ℃ for 2 days.
Step 3, cooling the kettle after the reaction in the step 2, filtering the product, fully washing the product with water, and drying the product at the temperature of 60 ℃ to obtain the Co with a thick shell layer3O4@ZIF-67。
Example 1 Co obtained by Synthesis3O4@ ZIF-67 and parent Co3O4The XRD diffraction pattern of the material is compared with that of the material shown in figure 1, and Co can be seen from figure 13O4@ ZIF-67 having attribute of Co at the same time3O4And the peak of crystal face of ZIF-67 (in which the crystal face of ZIF-67 is labeled in the figure), proving that Co obtained by synthesis3O4@ ZIF-67 is Co3O4A composite with ZIF-67.
Example 1 Co obtained by Synthesis3O4FIG. 2 is a scanning electron micrograph of @ ZIF-67, and it can be seen from FIG. 2 that Co3O4@ ZIF-67 has uniform nanometer morphology, no other impurity phase is seen, and crystal grains are slightly adhered to each other and are caused by the overlapping growth of adjacent ZIF-67 crystals of a shell layer.
Co synthesized in example 1 and example 23O4@ ZIF-67 core-shell structure material and parent Co3O4Ultrasonically dispersing in ethanol, uniformly coating on a gas-sensitive test electrode, drying at 60 ℃ for 30min, and respectively testing 100ppm of hydrogen, methanol, acetone and 10ppm of toluene, wherein the results are shown in Table 1.
TABLE 1 detection of the Performance of a gas sensor made of cobaltosic oxide synthesized by the solvent-free Process of the present invention
Gas sensitive response of hydrogen Gas sensitive response of methanol Acetone gas sensitive response Toluene gas sensitive response
Test voltage 2.5V 3.0V 3.0V 3.0V
Co3O4 2.7 1.9 8.9 5.4
Example 1 2.1 1.6 4.6 2.2
Example 2 1.7 1.4 2.5 1.4
Matrix Co3O4Has certain gas-sensitive response to hydrogen, methanol, acetone and toluene, and particularly has good gas-sensitive performance to macromolecular acetone and toluene. Examples 1 and 2 ratio of Co into thin shell and thick shell3O4@ ZIF-67 core-shell material, and is comparable to the parent Co3O4，Co3O4The response of @ ZIF-67 to the above four gases is reduced to some extent, and the thickness of Co of ZIF-67 shell is thick3O4The drop in response of @ ZIF-67 is more pronounced due to the non-conductivity of shell ZIF-67. Co3O4The gas-sensitive performance of the @ ZIF-67 to micromolecule hydrogen and methanol is reduced less, and the gas-sensitive performance to macromolecular acetone and toluene is reduced obviously, because the ZIF-67 can effectively block gas macromolecules and a nuclear layer sensing material Co3O4Thereby improving the contact to small molecule gasesGas sensitivity selectivity.
In summary, the present invention reports a Co3O4Preparation of @ ZIF-67 core-shell structure material and application of gas sensor, and Co is successfully prepared by solvothermal method for the first time3O4The material with the structure of @ ZIF-67 core-shell, ZIF-67 can effectively prevent macromolecular gases such as toluene, acetone and the like from entering and diffusing, and improve Co3O4@ ZIF-67 gas sensitivity selectivity to small molecule gases such as hydrogen, methanol, and the like.
The preparation method is convenient and feasible, is easy to amplify, and has certain industrial application prospect.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.

Claims (8)

1. Co3O4The preparation method of the @ ZIF-67 core-shell structure material is characterized by comprising the following steps of:
mixing Co3O4Carrying out post-treatment on the matrix, adding an organic ligand and a solvent, and heating in a closed system to obtain Co3O4@ ZIF-67 core-shell structure material.
2. Co according to claim 13O4The preparation method of the @ ZIF-67 core-shell structure material is characterized by comprising the following steps of:
(1) preparation of Co3O4A parent body;
(2) the matrix Co3O4Adding the powder into a solvent containing an organic ligand, and heating and reacting in a closed system;
(3) filtering, washing and drying the mixture obtained after the reaction in the step 2 to obtain Co3O4@ ZIF-67 core-shell structure material.
3. Co according to claim 23O4The preparation method of the @ ZIF-67 core-shell structure material is characterized in that Co in the step (1)3O4The particle size range of the matrix is 50-80 nm.
4. Co according to claim 33O4The preparation method of the @ ZIF-67 core-shell structure material is characterized in that Co in the step (1)3O4The preparation method of the matrix comprises the following steps: placing cobalt acetate tetrahydrate in a crucible, heating to 500 deg.C at 2 deg.C per minute, maintaining for 1 hr, and cooling to obtain Co3O4And (4) a parent body.
5. Co according to claim 23O4The preparation method of the @ ZIF-67 core-shell structure material is characterized in that a ligand in the step (2) is 2-methylimidazole, and the molar ratio of the 2-methylimidazole to a cobalt atom is 0.5-3: 1.
6. Co according to claim 23O4The preparation method of the @ ZIF-67 core-shell structure material is characterized in that the reaction temperature in the step (2) is 130-170 ℃, and the reaction time is 1-3 days.
7. Co according to claim 23O4The preparation method of the @ ZIF-67 core-shell structure material is characterized by comprising the following detailed steps:
(1) pyrolysis method for preparing Co with particle size of 50-80 nm3O4As a precursor, cobalt acetate tetrahydrate is put in a crucible, heated to 500 ℃ at the speed of 2 ℃ per minute, kept for 1 hour, and then cooled to obtain Co3O4A parent body;
(2) 0.1g of Co prepared in step 1 was weighed3O4Adding the mixture into 10g of methanol, keeping magnetic stirring, then adding ligand 2-methylimidazole (the molar ratio of 2-methylimidazole to Co is 0.5-3: 1, continuously stirring for 5 minutes, transferring the mixture into a 50mL tetrafluoroethylene lining with a stainless steel outer sleeve, screwing the lining, transferring the lining into a blast drying oven, and standing the lining for 1-3 days at 130-170 DEG C；
(3) And 2, cooling the kettle after the reaction is finished, filtering and washing the product, and drying the product at 50-80 ℃ to obtain Co of a thin shell layer3O4@ZIF-67。
8. Co according to any one of claims 1 to 73O4The application of the material with the @ ZIF-67 core-shell structure in the gas sensor.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004662A (en) * 2021-02-25 2021-06-22 安徽工业大学 PEDOT (PSS/ZIF-8) gas-sensitive material, gas-sensitive element, preparation method and application
CN113097490A (en) * 2021-04-02 2021-07-09 扬州大学 Dodecahedral ZIF-67/Co3O4Composite material, preparation method and application thereof
CN113092543A (en) * 2021-04-09 2021-07-09 中国科学院上海微系统与信息技术研究所 Gas sensing material and preparation method and application thereof
CN113447532A (en) * 2021-06-25 2021-09-28 杭州电子科技大学 Fe3O4Preparation method of @ UiO-66 structure gas sensor
CN114487020A (en) * 2022-02-08 2022-05-13 扬州大学 Gas-sensitive material for lung cancer breath marker gas methanol and preparation method thereof
CN115060767A (en) * 2022-07-13 2022-09-16 安徽维纳物联科技有限公司 Preparation method of gas-sensitive material for food safety detection, prepared gas-sensitive material and application thereof
CN117003293A (en) * 2023-07-31 2023-11-07 武汉理工大学 Modified Co 3 O 4 MOFs composite gas-sensitive material and preparation method and application thereof
CN117737887A (en) * 2024-02-16 2024-03-22 天津市计量监督检测科学研究院 Preparation method and application of composite nanofiber gas-sensitive material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130288892A1 (en) * 2012-04-03 2013-10-31 Jochen A. Lauterbach One-Step Synthesis of Monodisperse Transition Metal Core-Shell Nanoparticles with Solid Solution Shells
CN104549082A (en) * 2014-12-19 2015-04-29 安徽建筑大学 ZnO@ZIF-8 core-shell structure microsphere and preparation method thereof
CN109824093A (en) * 2019-04-12 2019-05-31 武夷学院 A kind of Co being layered porous hollow core-shell structure3O4High-efficiency synthesis method
CN110068599A (en) * 2019-05-31 2019-07-30 吉林大学 One kind being based on CoFe2O4/Co3O4The formaldehyde gas sensor and preparation method thereof of duplex shell structure cubic materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130288892A1 (en) * 2012-04-03 2013-10-31 Jochen A. Lauterbach One-Step Synthesis of Monodisperse Transition Metal Core-Shell Nanoparticles with Solid Solution Shells
CN104549082A (en) * 2014-12-19 2015-04-29 安徽建筑大学 ZnO@ZIF-8 core-shell structure microsphere and preparation method thereof
CN109824093A (en) * 2019-04-12 2019-05-31 武夷学院 A kind of Co being layered porous hollow core-shell structure3O4High-efficiency synthesis method
CN110068599A (en) * 2019-05-31 2019-07-30 吉林大学 One kind being based on CoFe2O4/Co3O4The formaldehyde gas sensor and preparation method thereof of duplex shell structure cubic materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YOUNG-MOO JO ET AL.: ""Metal-Organic Framework-Derived Hollow Hierarchical Co3O4 Nanocages with Tunable Size and Morphology: Ultrasensitive and Highly Selective Detection of Methylbenzenes"", 《ACS APPL. MATER. INTERFACES》 *

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CN113004662B (en) * 2021-02-25 2023-04-25 安徽工业大学 PEDOT (polyether-ether-ketone) PSS/ZIF-8 gas-sensitive material, gas-sensitive element, preparation method and application
CN113004662A (en) * 2021-02-25 2021-06-22 安徽工业大学 PEDOT (PSS/ZIF-8) gas-sensitive material, gas-sensitive element, preparation method and application
CN113097490A (en) * 2021-04-02 2021-07-09 扬州大学 Dodecahedral ZIF-67/Co3O4Composite material, preparation method and application thereof
CN113092543A (en) * 2021-04-09 2021-07-09 中国科学院上海微系统与信息技术研究所 Gas sensing material and preparation method and application thereof
CN113447532A (en) * 2021-06-25 2021-09-28 杭州电子科技大学 Fe3O4Preparation method of @ UiO-66 structure gas sensor
CN114487020A (en) * 2022-02-08 2022-05-13 扬州大学 Gas-sensitive material for lung cancer breath marker gas methanol and preparation method thereof
CN114487020B (en) * 2022-02-08 2023-12-22 扬州大学 Gas-sensitive material for lung cancer breathing mark gas methanol and preparation method thereof
CN115060767A (en) * 2022-07-13 2022-09-16 安徽维纳物联科技有限公司 Preparation method of gas-sensitive material for food safety detection, prepared gas-sensitive material and application thereof
CN115060767B (en) * 2022-07-13 2024-05-28 安徽维纳物联科技有限公司 Preparation method of gas-sensitive material for food safety detection, prepared gas-sensitive material and application of gas-sensitive material
CN117003293A (en) * 2023-07-31 2023-11-07 武汉理工大学 Modified Co 3 O 4 MOFs composite gas-sensitive material and preparation method and application thereof
CN117003293B (en) * 2023-07-31 2024-04-05 武汉理工大学 Modified Co 3 O 4 MOFs composite gas-sensitive material and preparation method and application thereof
CN117737887A (en) * 2024-02-16 2024-03-22 天津市计量监督检测科学研究院 Preparation method and application of composite nanofiber gas-sensitive material
CN117737887B (en) * 2024-02-16 2024-05-10 天津市计量监督检测科学研究院 Preparation method and application of composite nanofiber gas-sensitive material

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