CN113861600B - Bio-based porous material and preparation method and application thereof - Google Patents
Bio-based porous material and preparation method and application thereof Download PDFInfo
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- CN113861600B CN113861600B CN202111406064.8A CN202111406064A CN113861600B CN 113861600 B CN113861600 B CN 113861600B CN 202111406064 A CN202111406064 A CN 202111406064A CN 113861600 B CN113861600 B CN 113861600B
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- 239000011148 porous material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 72
- 229920002678 cellulose Polymers 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000004964 aerogel Substances 0.000 claims abstract description 27
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- -1 nitrogen-containing heterocyclic carboxylic acid Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000006557 surface reaction Methods 0.000 claims 1
- 239000002159 nanocrystal Substances 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000013291 MIL-100 Substances 0.000 description 20
- 239000000499 gel Substances 0.000 description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002707 nanocrystalline material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention relates to a bio-based porous material, a preparation method and application thereof, and belongs to the field of material preparation. The material comprises aerogel and a metal organic frame/cellulose nanocrystalline composite, wherein the metal organic frame/cellulose nanocrystalline composite is dispersed in the aerogel. According to the invention, the metal organic framework material with positive charges is grafted on the surface of the cellulose nanocrystal to form a metal organic framework/cellulose nanocrystal complex, and the overall charge quantity of the cellulose nanocrystal is reduced by constructing the complex, so that on one hand, the cellulose nanocrystal is promoted to self-assemble to form a stable microcosmic self-assembly structure, on the other hand, the aggregation of the cellulose nanocrystal is reduced, the porous structure of the tip part of the cellulose nanocrystal is utilized, and the adsorption effect of the material on gas/ions is further improved.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a bio-based porous material, and a preparation method and application thereof.
Background
Aerogel is a nano porous material with high specific surface area, is obtained by drying hydrogel or organic gel, and has the advantages of low density and high porosity. Cellulose nanocrystalline is a natural, renewable and abundant rod-like nanomaterial with high aspect ratio and chemical modification activity.
At present, a sol-gel method is generally adopted for preparing cellulose nanocrystalline aerogel, namely, gel is needed to be prepared firstly and then the aerogel is obtained by drying, and the pores in the aerogel are utilized to the maximum extent by introducing a metal organic framework/cellulose nanocrystalline into an aerogel structure, so that the gas adsorption rate is improved. The cellulose nanocrystalline aerogel prepared by the traditional method has brittleness due to the rigid structure of the cellulose nanocrystalline and a large number of hydrogen bonds existing in the cellulose nanocrystalline, and is difficult to be practically applied, so that the aerogel is required to be modified by adopting a high polymer material with a flexible long-chain structure, and further the available aerogel with proper mechanical properties is obtained.
Disclosure of Invention
Accordingly, one of the objects of the present invention is to provide a bio-based porous material.
The second object of the present invention is to provide a method for preparing a bio-based porous material.
It is a further object of the present invention to provide a use of a bio-based porous material as an ion or gas adsorbent.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a bio-based porous material comprising an aerogel, a metal-organic framework/cellulose nanocrystalline composite, the metal-organic framework/cellulose nanocrystalline composite dispersed in the aerogel.
Preferably, the aerogel is prepared by crosslinking any one of sodium alginate, polyvinyl alcohol and polyethylene glycol.
Preferably, the metal organic frame in the metal organic frame/cellulose nanocrystalline composite is one of metal organic frames containing carboxylic acid ligand, nitrogen-containing heterocyclic ligand and nitrogen-containing heterocyclic carboxylic acid ligand.
Preferably, the surface of the cellulose nanocrystal in the metal organic framework/cellulose nanocrystal complex is modified with any one of carboxyl, amino and aldehyde groups.
Preferably, the mass percentage of the metal organic frame/cellulose nanocrystalline composite in the bio-based porous material is 5% -20%, and the mass percentage of the metal organic frame material in the metal organic frame/cellulose nanocrystalline composite is 4% -40%.
A method for preparing a bio-based porous material, comprising the steps of:
(1) Adjusting the pH value of the surface functionalized modified cellulose nanocrystalline suspension to 6-7, adding an organic ligand until the organic ligand is completely dissolved to obtain a mixed solution A, adding a metal ion solution into the mixed solution A, stirring until the reaction is finished, taking a solid phase, washing, drying and grinding to obtain a metal organic frame/cellulose nanocrystalline complex;
(2) Adding the metal organic frame/cellulose nanocrystalline complex into a flexible chain polymer solution, uniformly mixing, adding a cross-linking agent, adjusting the pH value to 4-6, uniformly mixing again, vacuumizing for degassing, heating, and vacuum freeze-drying.
Preferably, the surface functionalized modified cellulose nanocrystal in the step (1) is any one of carboxyl, amino and aldehyde groups modified on the surface; the flexible chain polymer in the step (2) is one of sodium alginate, polyvinyl alcohol and polyethylene glycol.
Preferably, the organic ligand in the step (1) is one of trimesic acid, 2-methylimidazole or terephthalic acid, the metal ion in the metal ion solution in the step (1) is one of ferrous ion, zinc ion or zirconium ion, and the cross-linking agent in the step (2) is glutaraldehyde.
Preferably, the vacuum freeze drying after heating in the step (2) is specifically: heating at 75deg.C for 3 hr, and vacuum drying at-54 deg.C.
Use of a bio-based porous material as an ion or gas adsorbent.
The invention has the beneficial effects that: the material comprises aerogel and a metal organic framework/cellulose nanocrystalline composite, wherein the metal organic framework/cellulose nanocrystalline composite is dispersed in the aerogel. The adsorption of different target gases/ions is realized by dispersing the metal organic framework/cellulose nanocrystalline complex into aerogel to construct a multistage pore channel bio-based material. The cellulose nanocrystalline material is a rod-shaped material with negative charges, is difficult to assemble in a regular mode under a microscopic state due to self-charging, and the tip part of the cellulose nanocrystalline material is easy to guide the aggregation of the material, so that a large number of micropore structures of the tip cannot be fully utilized, and the adsorption effect of the cellulose nanocrystalline on gas/ions is greatly limited. According to the invention, the metal organic frame material with positive charges is grafted on the surface of the cellulose nanocrystal to form a metal organic frame/cellulose nanocrystal composite, the mass percentage of the metal organic frame material in the composite is further optimized, the overall charge amount of the cellulose nanocrystal is reduced by constructing the specific composite, on one hand, the cellulose nanocrystal is promoted to self-assemble to form a stable microcosmic self-assembly structure, the pore structure is improved, the specific surface area of the material is improved, meanwhile, the material has stable interaction under microcosmic conditions, the adsorption capacity, the functionality and the stability of the material are further improved, on the other hand, the aggregation of the cellulose nanocrystal is reduced, the porous structure of the tip part of the cellulose nanocrystal is utilized, and the adsorption effect of the material on gas/ions is further improved. The metal organic frame/cellulose nanocrystalline complex is dispersed into aerogel, a bio-based porous containing micropores, mesopores and macropores is constructed, and the adsorption performance of the metal organic frame/cellulose nanocrystalline complex on gas/ions is improved by using pore exposure. The metal organic frame/cellulose nanocrystalline composite is dispersed into aerogel to construct a bio-based porous material containing micropores, mesopores and macropores, and the pore condition in the porous material is regulated and controlled by controlling the mass percentage of the metal organic frame/cellulose nanocrystalline composite in the bio-based porous material, so that the pore exposure is fully utilized, and the adsorption performance of the metal organic frame/cellulose nanocrystalline composite on gas/ions is improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an SEM image of MIL-100 (Fe) @ OCN/PVA (10.0 wt% MIL-100 (Fe) @ OCN) bio-based porous material;
FIG. 2 is an SEM image of MIL-100 (Fe) @ OCN/PVA (5.0 wt% MIL-100 (Fe) @ OCN) bio-based porous material;
FIG. 3 is an SEM image of MIL-100 (Fe) @ OCN/PVA (20.0 wt% MIL-100 (Fe) @ OCN) bio-based porous material;
FIG. 4 is a graph showing pore size distribution of MIL-100 (Fe) @ OCN/PVA (10.0 wt% MIL-100 (Fe) @ OCN), OCN/PVA material in comparative example, and PVA aerogel.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Example 1
Weighing 2.00g of cellulose nanocrystalline (CNC for short), adding into distilled water, and performing ultrasonic treatment in an ultrasonic cleaner for 5 minutes to obtain CNC dispersion; 20mg of 2, 6-tetramethylpiperidine-1-oxyl (hereinafter referred to as TEMPO) and 0.42g of NaBr were weighed out and dissolved in distilled water to obtain a TEMPO/NaBr mixture. Adding a TEMPO/NaBr mixed solution into a CNC dispersion liquid at a speed of 5mL/min, dropwise adding a NaClO solution into the TEMPO/NaBr mixed solution after the TEMPO/NaBr solution is dropwise added, adjusting and maintaining the pH value to be 10.0+/-0.2, adding ethanol after reacting for 4 hours, ending the reaction, adjusting the pH value to 6-6.5, centrifuging, taking a solid phase, washing with distilled water, and obtaining carboxylated CNC, and marking as OCN.
Weighing 3.000g of OCN, adding water, performing ultrasonic dissolution to prepare an OCN suspension, adjusting the pH value of the OCN suspension to 6-7, adding 1.911g of trimesic acid into the suspension under the ultrasonic condition to obtain a mixed solution A, dripping ferrous chloride solution into the mixed solution A, wherein the amount of ferrous chloride substances is 14.4mmol, continuously stirring the mixed solution A at 35 ℃ for 24 hours until the reaction is finished, taking a solid phase, sequentially washing and precipitating the solid phase with distilled water and ethanol for 3 times, drying the solid phase at 55 ℃, and grinding to obtain a metal-organic frame/cellulose nanocrystalline composite, wherein the mass ratio of the metal-organic frame material in the metal-organic frame/cellulose nanocrystalline composite is 30%.
Adding 0.1g of metal organic frame/cellulose nanocrystalline composite into 100mL of polyvinyl alcohol solution with the concentration of 5wt%, stirring uniformly, adding 200 mu L of glutaraldehyde, regulating the pH to 4-6, uniformly mixing again, vacuumizing, degassing, reacting in a vacuum oven at 75 ℃ for 3 hours to obtain gel, and carrying out vacuum freeze-drying treatment on the gel at-54 ℃ for 48 hours to obtain the biological porous material, wherein the mass percentage of the metal organic frame/cellulose nanocrystalline composite in the biological porous material is 10%, and the biological porous material is marked as MIL-100 (Fe) @ OCN/PVA (10.0 wt% MIL-100 (Fe) @ OCN).
Examples 2 to 3
The bio-based porous materials having mass percentages of the metal organic framework/cellulose nanocrystalline composite in the bio-based porous materials of 5% and 20% were prepared by controlling the amounts of the metal organic framework/cellulose nanocrystalline composite in the aerogel under the conditions of example 1, respectively, and were marked as MILs-100 (Fe) @ OCN/PVA (5.0 wt% MILs-100 (Fe) @ OCN), MILs-100 (Fe) @ OCN/PVA (20.0 wt% MILs-100 (Fe) @ OCN) in sequence.
Example 4
Carboxylated CNC, designated OCN, was prepared as in example 1.
Weighing 0.490g of OCN, adding water, ultrasonically dissolving to obtain OCN suspension, regulating the pH value of the OCN suspension to 6-7, adding 0.4815 g of 2-methylimidazole into the suspension under ultrasonic condition to obtain a mixed solution A, and taking 0.891g of Zn (NO 3 ) 2 ·6H 2 O is added to the mixture A, wherein Zn (NO 3 ) 2 ·6H 2 The amount of the O substance is 3.00mmol, the mixed solution A is continuously stirred for 2 hours at normal temperature until the reaction is finished, then the solid phase is taken, distilled water and ethanol are used for washing and precipitating for 2 times in sequence, the solid phase is dried and ground at 60 ℃ to obtain the metal organic frame/cellulose nanocrystalline composite, wherein the mass ratio of the metal organic frame material in the metal organic frame/cellulose nanocrystalline composite is 4.16%.
Adding 0.1g of metal organic frame/cellulose nanocrystalline composite into 100mL of polyethylene glycol solution with the concentration of 5wt%, stirring uniformly, adding 200 mu L of glutaraldehyde, regulating the pH to 4-6, uniformly mixing again, vacuumizing for degassing, reacting in a vacuum oven at 75 ℃ for 3 hours after degassing to obtain gel, and carrying out vacuum freeze-drying treatment on the gel at-54 ℃ for 48 hours to obtain the biological porous material, wherein the mass percentage of the metal organic frame/cellulose nanocrystalline composite in the biological porous material is 10%.
Comparative example 1
Carboxylated CNC, designated OCN, was prepared as in example 1.
Adding 0.1g of OCN into 100mL of polyvinyl alcohol solution with the concentration of 5wt%, uniformly stirring, adding 200 mu L of glutaraldehyde solution with the concentration of 25wt%, regulating the pH to 4-6, uniformly mixing again, vacuumizing for degassing, reacting in a vacuum oven at 75 ℃ for 3 hours to obtain gel, and carrying out vacuum freeze-drying treatment on the gel at-54 ℃ for 48 hours to obtain the biological porous material, wherein the mass percentage of the OCN in the biological porous material is 10%, and the biological porous material is marked as the OCN/PVA material.
Comparative example 2
Taking 100mL of polyvinyl alcohol solution with the concentration of 5wt%, adding 200 mu L of glutaraldehyde solution with the concentration of 25wt%, regulating the pH to 4-6, uniformly mixing, vacuumizing for degassing, reacting in a vacuum oven at 75 ℃ for 3 hours after degassing to obtain gel, and performing vacuum freeze-drying treatment on the gel at-54 ℃ for 48 hours to obtain aerogel, which is marked as PVA aerogel.
The materials prepared in examples 1 to 3 and the OCN/PVA material prepared in comparative example 1 were taken to measure specific surface areas, respectively, to obtain the following table:
it can be seen from the table that the metal organic framework material with positive charges is grafted on the surface of the cellulose nanocrystal to form a metal organic framework/cellulose nanocrystal complex, the complex is dispersed in the aerogel, the whole charge quantity of the cellulose nanocrystal is reduced by constructing the complex, the cellulose nanocrystal is promoted to self-assemble, a stable microscopic self-assembled structure is formed, the pore structure is improved, and the specific surface area of the bio-based porous material is increased.
FIG. 1 is an SEM image of MIL-100 (Fe) @ OCN/PVA (10.0 wt% MIL-100 (Fe) @ OCN) bio-based porous material.
FIG. 2 is an SEM image of MIL-100 (Fe) @ OCN/PVA (5.0 wt% MIL-100 (Fe) @ OCN) bio-based porous material.
FIG. 3 is an SEM image of MIL-100 (Fe) @ OCN/PVA (20.0 wt% MIL-100 (Fe) @ OCN) bio-based porous material.
As can be seen from FIGS. 1-3, the bio-based porous material prepared by the invention has better multi-order pore distribution and larger specific surface area.
FIG. 4 shows pore size distribution patterns of MIL-100 (Fe) @ OCN/PVA (10.0 wt% MIL-100 (Fe) @ OCN) in example 1, OCN/PVA material in comparative example 1, and PVA aerogel in comparative example 2, and it is understood that MIL-100 (Fe) @ OCN/PVA (10.0 wt% MIL-100 (Fe) @ OCN) has a wide pore size distribution range, and a bio-based porous material having micropores, mesopores, and macropores is formed.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (8)
1. A bio-based porous material, characterized in that: the material comprises aerogel and a metal organic frame/cellulose nanocrystalline composite, wherein the metal organic frame/cellulose nanocrystalline composite is dispersed in the aerogel; the mass percentage of the metal organic frame/cellulose nanocrystalline composite in the biological base porous material is 5% -20%, and the mass percentage of the metal organic frame material in the metal organic frame/cellulose nanocrystalline composite is 4.16% or 30%; the aerogel is prepared by crosslinking any one of sodium alginate, polyvinyl alcohol and polyethylene glycol; the metal organic framework/cellulose nanocrystalline composite is prepared according to the following method:
adjusting the pH value of the surface functionalized modified cellulose nanocrystalline suspension to 6-7, adding an organic ligand until the organic ligand is completely dissolved to obtain a mixed solution A, adding a metal ion solution into the mixed solution A, stirring until the reaction is finished, taking a solid phase, washing, drying and grinding to obtain the metal organic frame/cellulose nanocrystalline complex.
2. The material of claim 1, wherein: the metal organic frame in the metal organic frame/cellulose nanocrystalline composite is one of a carboxylic acid ligand-containing metal organic frame, a nitrogen-containing heterocyclic ligand metal organic frame and a nitrogen-containing heterocyclic carboxylic acid ligand metal organic frame.
3. The material of claim 1, wherein: the surface of the cellulose nanocrystalline in the metal organic framework/cellulose nanocrystalline complex is modified with any one group of carboxyl, amino and aldehyde groups.
4. A method for preparing a bio-based porous material according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) Adjusting the pH value of the surface functionalized modified cellulose nanocrystalline suspension to 6-7, adding an organic ligand until the organic ligand is completely dissolved to obtain a mixed solution A, adding a metal ion solution into the mixed solution A, stirring until the reaction is finished, taking a solid phase, washing, drying and grinding to obtain a metal organic frame/cellulose nanocrystalline complex;
(2) Adding the metal organic frame/cellulose nanocrystalline complex into a flexible chain polymer solution, uniformly mixing, adding a cross-linking agent, adjusting the pH value to 4-6, uniformly mixing again, vacuumizing for degassing, heating, and vacuum freeze-drying to obtain the metal organic frame/cellulose nanocrystalline composite; the flexible chain polymer is one of sodium alginate, polyvinyl alcohol and polyethylene glycol.
5. The method of manufacturing according to claim 4, wherein: the cellulose nanocrystalline modified by surface functionalization in the step (1) is any one group selected from carboxyl, amino and aldehyde groups modified on the surface.
6. The method of manufacturing according to claim 4, wherein: the organic ligand in the step (1) is one of trimesic acid, 2-methylimidazole or terephthalic acid, the metal ion in the metal ion solution in the step (1) is one of ferrous ion, zinc ion or zirconium ion, and the cross-linking agent in the step (2) is glutaraldehyde.
7. The method of manufacturing according to claim 4, wherein: the vacuum freeze drying after heating in the step (2) is specifically as follows: after heating at 75℃for 3h, vacuum drying was performed at-54 ℃.
8. Use of a bio-based porous material according to any of claims 1-3 as an ion or gas adsorbent.
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