CN109575305B - Preparation method of Co-MOF gas-sensitive nano material, product and application thereof - Google Patents
Preparation method of Co-MOF gas-sensitive nano material, product and application thereof Download PDFInfo
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- CN109575305B CN109575305B CN201811560516.6A CN201811560516A CN109575305B CN 109575305 B CN109575305 B CN 109575305B CN 201811560516 A CN201811560516 A CN 201811560516A CN 109575305 B CN109575305 B CN 109575305B
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- 239000012921 cobalt-based metal-organic framework Substances 0.000 title claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012922 MOF pore Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/004—CO or CO2
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Combustion & Propulsion (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a preparation method of a Co-MOF gas-sensitive nano material, a product and application thereof. The content of the metal center is higher than that of other metal organic framework materials, and more gas-sensitive reaction active sites are provided; the Co-MOF gas-sensitive nano material prepared by the method has the advantages of high purity, uniform size, large specific surface area, low gas-sensitive response limit and short response recovery time.
Description
Technical Field
The invention belongs to the field of metal organic framework nano materials, and particularly relates to a preparation method of a Co-MOF gas-sensitive nano material, and a product and application thereof.
Background
Metal-organic frameworks (MOFs) are hollow network materials formed by self-assembling Metal ions and organic ligands (mostly aromatic polyacids and polybases), and compared with traditional porous materials, MOFs have the unique advantages of large specific surface area, rich pore channel structures, high porosity, stable structure, easiness in selecting different Metal ions and organic bridging ligands and the like, and attract considerable attention in recent 10 years. Currently, MOFs materials research is mainly focused on gas adsorption and gas separation. The gas-sensitive reaction usually occurs on the surface of a gas-sensitive material, so that the material is required to have larger specific surface area and higher porosity, and the gas-sensitive reaction also relates to a gas adsorption and desorption process, so that the MOFs material has wide application prospect in the field of gas sensitivity. Such porous MOFs are often converted into derivatized oxide materials by self-sacrifice methods to improve their gas-sensitive response properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a Co-MOF gas-sensitive nano material.
Yet another object of the present invention is to: provides a Co-MOF gas-sensitive nanometer material product prepared by the method.
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: a preparation method of a Co-MOF gas-sensitive nano material constructs a metal organic framework structure taking Co as a metal center, and prepares the Co-MOF gas-sensitive nano material by adjusting the concentration, the proportion, the reaction time and the reaction temperature conditions of precursors, and comprises the following steps:
(1) weighing 1.0-1.5g of cobalt acetate, dissolving in 35mL of deionized water, and uniformly stirring to obtain a solution 1;
(2) weighing 0.4-0.6g of 2, 5-dihydroxy terephthalic acid, dissolving in 35mL of tetrahydrofuran, and uniformly stirring to obtain a solution 2;
(3) quickly pouring the solution 2 into the solution 1, and uniformly stirring to obtain a solution 3;
(4) transferring the solution 3 into a reaction kettle, heating to 100-140 ℃, fully stirring for reaction, filtering the precipitate, washing and drying;
(5) the precipitate was then dispersed in 120mL ethanol for one day;
(6) and pouring out the ethanol solvent, and drying the solid in vacuum for 12 hours to obtain the Co-MOF gas-sensitive nano material.
Wherein the stirring reaction time is 1-4 days.
The vacuum drying temperature is 120-180 ℃.
The invention also provides a Co-MOF gas-sensitive nano material prepared by any one of the methods.
In addition, the invention also provides application of the Co-MOF gas-sensitive nano material in CO gas detection.
The cobalt-based MOF material is synthesized by a very simple method, and the stability of the material is improved by improving the synthesis process, so that the cobalt-based MOF material does not need to be converted into a corresponding oxide for application. The special appearance and huge specific surface area of the nano-particle are reserved, and the nano-particle shows a lower detection lower limit for CO gas.
The content of the metal center is higher than that of other metal organic framework materials, and more gas-sensitive reaction active sites are provided; the Co-MOF gas-sensitive nano material prepared by the method has the advantages of high purity, uniform size, large specific surface area, low gas-sensitive response limit and short response recovery time.
Drawings
FIG. 1 is a real-time response curve of Co-MOF gas-sensitive nanomaterial of the present invention to 200ppb CO gas.
Detailed Description
Example 1:
a preparation method of a Co-MOF gas-sensitive nano material constructs a metal organic framework structure taking Co as a metal center, and prepares the Co-MOF gas-sensitive nano material by adjusting the concentration, the proportion, the reaction time and the reaction temperature conditions of precursors, and comprises the following steps:
(1) weighing 1.0g of cobalt acetate, dissolving in 35mL of deionized water, and uniformly stirring to obtain a solution 1;
(2) weighing 0.4g of 2, 5-dihydroxy terephthalic acid, dissolving in 35mL of tetrahydrofuran, and uniformly stirring to obtain a solution 2;
(3) quickly pouring the solution 2 into the solution 1, and uniformly stirring to obtain a solution 3;
(4) transferring the solution 3 into a reaction kettle, heating to 120 ℃ and reacting for 2 day; filtering the precipitate, washing and drying;
(5) the precipitate was then dispersed in 120mL ethanol for one day;
(6) and (3) pouring out the ethanol solvent, and drying the solid for 12h at the temperature of 150 ℃ in vacuum to obtain the Co-MOF gas-sensitive nano material.
FIG. 1 is a real-time response curve of the Co-MOF gas-sensitive nanomaterial of the invention to 200ppb CO gas, and the working temperature is 200 ℃, wherein the sensitivity is about 1.836, which shows that the material has good response to the ppb level CO gas.
Example 2:
a preparation method of a Co-MOF gas-sensitive nano material is similar to that of example 1, and comprises the following steps:
(1) weighing 1.5g of cobalt acetate, dissolving in 35mL of deionized water, and uniformly stirring to obtain a solution 1;
(2) weighing 0.5g of 2, 5-dihydroxy terephthalic acid, dissolving in 35mL of tetrahydrofuran, and uniformly stirring to obtain a solution 2;
(3) quickly pouring the solution 2 into the solution 1, and uniformly stirring to obtain a solution 3;
(4) transferring the solution 3 into a reaction kettle, heating to 130 ℃ and reacting for 3 day; filtering the precipitate, washing and drying;
(5) the precipitate was then dispersed in 120mL ethanol for one day;
(6) and (3) pouring out the ethanol solvent, and drying the solid for 12h at 180 ℃ in vacuum to obtain the Co-MOF gas-sensitive nano material.
Example 3:
a preparation method of a Co-MOF gas-sensitive nano material is similar to that of example 1, and comprises the following steps:
(1) weighing 1.3g of cobalt acetate, dissolving in 35mL of deionized water, and uniformly stirring to obtain a solution 1;
(2) weighing 0.6g of 2, 5-dihydroxy terephthalic acid, dissolving in 35mL of tetrahydrofuran, and uniformly stirring to obtain a solution 2;
(3) quickly pouring the solution 2 into the solution 1, and uniformly stirring to obtain a solution 3;
(4) transferring the solution 3 into a reaction kettle, heating to 100 ℃ and reacting for 4 day; filtering the precipitate, washing and drying;
(5) the precipitate was then dispersed in 120mL ethanol for one day;
(6) and (3) pouring out the ethanol solvent, and drying the solid for 12h at 130 ℃ in vacuum to obtain the Co-MOF gas-sensitive nano material.
Claims (2)
1. The application of the Co-MOF gas-sensitive nano material in CO gas detection is characterized in that the Co-MOF gas-sensitive nano material is obtained by a preparation method, wherein a metal organic framework structure taking Co as a metal center is constructed by the method, and the Co-MOF gas-sensitive nano material is prepared by adjusting the concentration, the proportion, the reaction time and the reaction temperature conditions of a precursor, and the preparation method comprises the following steps:
(1) weighing 1.0-1.5g of cobalt acetate, dissolving in 35mL of deionized water, and uniformly stirring to obtain a solution 1;
(2) weighing 0.4-0.6g of 2, 5-dihydroxy terephthalic acid, dissolving in 35mL of tetrahydrofuran, and uniformly stirring to obtain a solution 2;
(3) quickly pouring the solution 2 into the solution 1, and uniformly stirring to obtain a solution 3;
(4) transferring the solution 3 into a reaction kettle, heating to 100-140 ℃, and fully stirring for reaction; filtering the generated precipitate, washing and drying;
(5) the precipitate was then dispersed in 120mL ethanol for one day;
(6) pouring out the ethanol solvent, and vacuum-drying the solid for 12h to obtain a Co-MOF gas-sensitive nano material; wherein,
the stirring reaction time is 1-4 days.
2. The use as claimed in claim 1, wherein the temperature of the vacuum drying is 120-180 ℃.
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| CN110026242A (en) * | 2019-05-10 | 2019-07-19 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of Co/Ce bimetallic MOF base ozone catalyst and products thereof and application |
| CN115651258B (en) * | 2022-10-27 | 2024-03-05 | 陕西科技大学 | A Co-BPDC/MXene composite material, preparation method and application |
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