CN110342487B - Preparation method of polydopamine modified MOF derived carbon molecular sieve - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001690 polydopamine Polymers 0.000 title description 29
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 34
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229960003638 dopamine Drugs 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 239000012919 MOF-derived carbon material Substances 0.000 claims abstract description 7
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000013132 MOF-5 Substances 0.000 claims description 10
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 10
- 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 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 10
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000012922 MOF pore Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of preparing a polydopamine-modified MOF-derived carbon molecular sieve, the method comprising: preparing a trihydroxymethyl aminomethane aqueous solution, and adjusting the pH value to 8-9; preparing a dopamine aqueous solution, adding MOF, carrying out ultrasonic treatment at room temperature, and stirring; mixing the prepared two solutions, stirring at room temperature for 12-24 h, centrifuging, washing and drying to obtain a PDA/MOF precursor; placing the carbon material in nitrogen flow, heating to 600-1000 ℃, and keeping the temperature for 2-6 h to obtain a PDA/MOF derived carbon material; adding the mixture into an acid solution, stirring for 24 hours at room temperature, centrifuging, washing, and drying in vacuum to obtain a finished product; the preparation method is simple and convenient, economic and environment-friendly, and the dopamine modification can effectively reduce the structural damage of the MOF in the pyrolysis process and improve the carbon residue rate, thereby improving the yield.
Description
(I) technical field
The invention relates to a preparation method of a carbon molecular sieve, in particular to a preparation method of a Polydopamine (PDA) modified MOF derived carbon molecular sieve, belonging to the field of carbon material preparation.
(II) background of the invention
Carbon Molecular Sieve (CMS) is a nonpolar carbonaceous material having nano-scale ultra-fine micropores, and has a developed pore structure and unique surface new surface characteristics since it is composed of amorphous Carbon and crystalline Carbon. And has the advantages of strong acid resistance, strong alkali resistance, strong hydrophobicity, high hydrothermal stability and the like. Because the wedge-shaped micropores of the CMS are close to the diameter of the adsorbed molecules, most of the CMS are effective micropores, and the CMS has the characteristic of adjusting the pore size of the CMS according to the molecular size, thereby having the capability of screening the molecules. The unique pore structure and stable chemical properties of CMS make it widely used in chemical industry, and in addition, it is widely used in the fields of nitrogen-hydrogen production, wastewater treatment, environmental protection, military and national defense, gas masks, etc.
Metal Organic Frameworks (MOFs), as a novel crystalline porous material, have an ordered structure, a high surface area and a unique morphology, and have the characteristics of adjustable composition, various structures, controllable pore diameters and the like, and have attracted extensive attention in various aspects such as catalysis, energy storage and conversion, gas storage, environmental remediation and the like. The porous MOF has permanent nano-scale cavities and open channels, and provides an innate condition for the entry of small molecules, so that the porous MOF can be used as a template to synthesize a nano porous carbon material through pyrolysis under certain conditions. However, due to high temperature during pyrolysis, the pores in MOF shrink or collapse, so that the porosity is reduced, the effective micropores are reduced, and the entry of small molecules is not facilitated. At present, the literature reports that furfuryl alcohol is introduced as a second carbon source, and the furfuryl alcohol is polymerized inside the MOF pore channels, so that the shrinkage and collapse of the MOF pore channels in the pyrolysis process are reduced, and the inherent pore structure of the MOF is maintained. However, furfuryl alcohol is harmful to human body and environment, and belongs to class 2B carcinogens, so that a cleaner and more environment-friendly method is needed to solve the problem.
Disclosure of the invention
Aiming at the defects and shortcomings in the prior art, the invention provides a preparation method of a polydopamine modified MOF derived carbon molecular sieve. The carbon molecular sieve prepared by the invention has wide application prospect in the aspects of gas adsorption separation and gas purification.
The technical scheme of the invention is as follows:
a method of making a polydopamine-modified MOF-derived carbon molecular sieve, the method comprising the steps of:
(1) preparing a trihydroxymethyl aminomethane aqueous solution, and adjusting the pH value to 8-9 for later use;
the concentration of the trihydroxymethyl aminomethane water solution is 5-10 mmol/L;
the pH is adjusted by 5mol/L HCl aqueous solution;
(2) preparing a dopamine aqueous solution, adding MOF (powder), carrying out ultrasonic treatment (80-120W and 30min) at room temperature (20-30 ℃), and stirring (10min) for later use;
the concentration of the dopamine aqueous solution is 0.5-2 mg/mL;
the volume consumption of the dopamine aqueous solution is 100-300 mL/g based on the mass of the MOF;
the MOF is one or a mixture of more than two of MIL-96(Al), MOF-5 and ZIF-8 in any proportion;
(3) adding the solution prepared in the step (1) into the solution prepared in the step (2), stirring for 12-24 h at room temperature, centrifuging, washing (washing with deionized water and ethanol respectively for three times), and drying (80 ℃ and 12h) to obtain a PDA/MOF precursor;
specifically, the volume ratio of the solution in the step (1) to the solution in the step (2) is 1: 3;
(4) placing the PDA/MOF precursor obtained in the step (3) in nitrogen flow, heating to 600-1000 ℃ (preferably 800-1000 ℃) at the speed of 1-10 ℃/min (preferably 5-10 ℃/min), and keeping the temperature for 2-6 hours to obtain the PDA/MOF derived carbon material;
(5) adding the PDA/MOF derived carbon material obtained in the step (4) into an acid solution, stirring for 24h at room temperature (repeating the process for three times), centrifuging, washing (with deionized water), and drying in vacuum (100 ℃ for 12h) to obtain a finished product PDA/MOF derived carbon molecular sieve;
the acid solution is an HF or HCl aqueous solution, and the concentration of the acid solution is 20-30 wt%;
the volume usage amount of the acid solution is 200-300 mL/g based on the mass of the PDA/MOF derived carbon material.
The invention has the following beneficial effects:
1. the derivative carbon molecular sieve is prepared by using dopamine to replace the traditional toxic furfuryl alcohol modified MOF, so that the harm to human bodies and the environment is avoided, and the preparation method is simple and convenient, economic and environment-friendly.
2. The dopamine modification can effectively reduce the damage of the MOF in the pyrolysis process, and improve the carbon residue rate, thereby improving the yield.
(IV) description of the drawings
FIG. 1 is a PDA/MIL-96(Al) derived carbon molecular sieve prepared in example 1.
FIG. 2 is the PDA/MOF-5 derived carbon molecular sieve prepared in example 2.
FIG. 3 is the PDA/ZIF-8 derived carbon molecular sieve prepared in example 3.
(V) detailed description of the preferred embodiments
The present invention will be further described with reference to specific examples for better explaining the present invention, but the present invention is not limited to the following examples, and various modifications and implementations are included within the technical scope of the present invention without departing from the content and scope of the present invention.
Example 1
(1) Preparing 50mL of 5mmol/L trihydroxymethylaminomethane solution, and adjusting the pH value of the solution to 8.0 by using 5mol/L HCl;
(2) preparing 150mL of 0.5mg/mL dopamine aqueous solution, adding 0.5g MIL-96(Al) powder, performing ultrasonic treatment at room temperature for 30min, and stirring for 10 min;
(3) adding the solution in the step (1) into the solution in the step (2), stirring for 12h at room temperature, centrifuging, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 12h to obtain a PDA/MIL-96(Al) precursor;
(4) and (3) placing the PDA/MIL-96(Al) material in nitrogen flow, heating to 800 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2h to obtain the PDA/MIL-96(Al) derived carbon material.
(5) 0.1g of PDA/MIL-96(Al) derived carbon material is added into 20mL of 20% HF solution, stirred for 24h at room temperature, repeated for three times, centrifuged and repeatedly washed with deionized water, and then dried in an oven at 100 ℃ for 12h under vacuum to obtain the PDA/MIL-96(Al) derived carbon molecular sieve.
Comparative example 1
0.1g of MIL-96(Al) was directly carbonized without modification with dopamine and treated with HF, and a carbon molecular sieve was prepared in the same manner as in example 1.
Example 2
(1) Preparing 50mL of 10mmol/L trihydroxymethylaminomethane solution, and adjusting the pH value of the solution to 8.5 by using 5mol/L HCl;
(2) preparing 150mL of dopamine aqueous solution with the concentration of 1mg/mL, adding 1g of MOF-5 powder, performing ultrasonic treatment at room temperature for 30min, and then stirring for 10 min;
(3) adding the solution in the step (1) into the solution in the step (2), stirring for 12h at room temperature, centrifuging, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 12h to obtain a PDA/MOF-5 precursor;
(4) and (3) placing the PDA/MOF-5 material in nitrogen flow, heating to 1000 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 2h to obtain the PDA/MOF-5 derived carbon material.
(5) Adding 0.1g of PDA/MOF-5 derived carbon material into 30mL of 20% HCl solution, stirring for 24h at room temperature, repeating for three times, centrifuging, repeatedly washing with deionized water, and then drying in an oven at 100 ℃ for 12h in vacuum to obtain the PDA/MOF-5 derived carbon molecular sieve.
Comparative example 2
0.1g of MOF-5 was taken and carbonized directly without modification with dopamine and treated with HF, and a carbon molecular sieve was prepared in the same manner as in example 2.
Example 3
(1) Preparing 50mL of 8mmol/L trihydroxymethylaminomethane solution, and adjusting the pH value of the solution to 8.5 by using 5mol/L HCl;
(2) preparing 150mL of dopamine aqueous solution with the concentration of 2mg/mL, adding 1.5g of ZIF-8 powder, performing ultrasonic treatment at room temperature for 30min, and then stirring for 10 min;
(3) adding the solution in the step (1) into the solution in the step (2), stirring for 12h at room temperature, centrifuging, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 12h to obtain a PDA/ZIF-8 precursor;
(4) and (3) placing the PDA/ZIF-8 material in nitrogen flow, heating to 1000 ℃ at the heating rate of 5 ℃/min, and preserving heat for 4h to obtain the PDA/ZIF-8 derived carbon material.
(5) And adding 0.1g of PDA/ZIF-8 derived carbon material into 20mL of 30% HCl solution, stirring at room temperature for 24h, repeating for three times, centrifuging, repeatedly washing with deionized water, and then drying in an oven at 100 ℃ for 12h in vacuum to obtain the PDA/ZIF-8 derived carbon molecular sieve.
Comparative example 3
0.1g of ZIF-8 was taken and carbonized directly without modification with dopamine and treated with HF, and a carbon molecular sieve was prepared in the same manner as in example 3.
CO was conducted for each of examples and comparative examples2The adsorption test comprises the following operation steps: the carbon molecular sieves prepared in each example and comparative example were vacuum-degassed at 200 ℃ for 6h, and then tested for CO using an Autosorb-iQ (Quantachrome, USA) physical adsorption apparatus at 25 ℃ and 1bar2And N2The results of the adsorption and desorption of (2) are shown in Table 2.
TABLE 1 parameters of specific surface area and pore structure of PDA/MOF-derived carbon molecular sieves obtained in examples 1-3
TABLE 2 gas adsorption Properties of carbon molecular sieves prepared in examples 1 to 3 and comparative examples 1 to 3
Claims (8)
1. A method of making a polydopamine-modified MOF-derived carbon molecular sieve, comprising the steps of:
(1) preparing a trihydroxymethyl aminomethane aqueous solution, and adjusting the pH value to 8-9 for later use;
(2) preparing a dopamine aqueous solution, adding MOF, performing ultrasound at room temperature, and stirring for later use;
(3) adding the solution prepared in the step (1) into the solution prepared in the step (2), stirring at room temperature for 12-24 h, centrifuging, washing, and drying to obtain a PDA/MOF precursor;
(4) placing the PDA/MOF precursor obtained in the step (3) in nitrogen flow, heating to 600-1000 ℃ at the speed of 1-10 ℃/min, and preserving heat for 2-6 h to obtain a PDA/MOF derived carbon material;
(5) adding the PDA/MOF derived carbon material obtained in the step (4) into an acid solution, stirring for 24 hours at room temperature, centrifuging, washing, and drying in vacuum to obtain a finished product PDA/MOF derived carbon molecular sieve;
the acid solution is HF or HCl water solution, and the concentration is 20-30 wt%.
2. The method for preparing the polydopamine-modified MOF-derived carbon molecular sieve according to claim 1, wherein in the step (1), the concentration of the aqueous solution of tris (hydroxymethyl) aminomethane is 5-10 mmol/L.
3. The method of preparing a polydopamine-modified MOF-derived carbon molecular sieve according to claim 1, wherein in step (1), the pH is adjusted with 5mol/L aqueous HCl.
4. The method for preparing the polydopamine-modified MOF-derived carbon molecular sieve according to claim 1, wherein in the step (2), the concentration of the dopamine aqueous solution is 0.5-2 mg/mL.
5. The method for preparing the polydopamine-modified MOF-derived carbon molecular sieve of claim 1, wherein in the step (2), the volume dosage of the dopamine aqueous solution is 100-300 mL/g based on the mass of the MOF.
6. The method for preparing the polydopamine-modified MOF-derived carbon molecular sieve according to claim 1, wherein in the step (2), the MOF is one or a mixture of more than two of MIL-96(Al), MOF-5 and ZIF-8 in any proportion.
7. The method of preparing a polydopamine-modified MOF-derived carbon molecular sieve of claim 1, wherein in step (3), the volume ratio of the solution of step (1) to the solution of step (2) is 1: 3.
8. the method for preparing the polydopamine-modified MOF-derived carbon molecular sieve according to claim 1, wherein in the step (5), the volume dosage of the acid solution is 200-300 mL/g based on the mass of the PDA/MOF-derived carbon material.
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|---|---|---|---|---|
| US5385876A (en) * | 1993-01-27 | 1995-01-31 | Syracuse University | Activated carbons molecularly engineered |
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN106340399A (en) * | 2016-08-27 | 2017-01-18 | 大连理工大学 | Functionalized polydopamine derived carbon layer coated carbon substrate preparation method and application |
| CN106512965A (en) * | 2016-11-28 | 2017-03-22 | 复旦大学 | Synthetic method and application of metal-organic framework composite nanomaterial |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5385876A (en) * | 1993-01-27 | 1995-01-31 | Syracuse University | Activated carbons molecularly engineered |
| CN104925783A (en) * | 2015-06-24 | 2015-09-23 | 上海大学 | Production method of core-shell hierarchical structure porous carbon |
| CN106340399A (en) * | 2016-08-27 | 2017-01-18 | 大连理工大学 | Functionalized polydopamine derived carbon layer coated carbon substrate preparation method and application |
| CN106512965A (en) * | 2016-11-28 | 2017-03-22 | 复旦大学 | Synthetic method and application of metal-organic framework composite nanomaterial |
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