CN109999757B - Cr-MOF/wood composite aerogel capable of capturing heavy metal ions and preparation method and application thereof - Google Patents
Cr-MOF/wood composite aerogel capable of capturing heavy metal ions and preparation method and application thereof Download PDFInfo
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- 239000002023 wood Substances 0.000 title claims abstract description 115
- 239000013087 chromium-based metal-organic framework Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000004964 aerogel Substances 0.000 title claims abstract description 62
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 33
- 150000002500 ions Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 230000020477 pH reduction Effects 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 7
- 229960002218 sodium chlorite Drugs 0.000 claims description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical group CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 241000219000 Populus Species 0.000 claims description 5
- 238000000352 supercritical drying Methods 0.000 claims description 5
- 240000007182 Ochroma pyramidale Species 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 3
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229960003975 potassium Drugs 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229960005076 sodium hypochlorite Drugs 0.000 claims description 3
- 229960001922 sodium perborate Drugs 0.000 claims description 3
- 229940045872 sodium percarbonate Drugs 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 241000218645 Cedrus Species 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 7
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000010875 treated wood Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 241000771208 Buchanania arborescens Species 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003113 alkalizing effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012777 commercial manufacturing Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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]
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- 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
- B01J20/28014—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 form
- B01J20/28047—Gels
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The invention belongs to the technical field of composite materials, and provides a preparation method of Cr-MOF/wood composite aerogel capable of capturing heavy metal ions, which comprises the following steps: step S1, preparing the dried wood into wood hydrogel; step S2, immersing the wood hydrogel into a solution containing Cr-MOF capable of being formed to perform hydrothermal reaction in a sealed reactor to form Cr-MOF/wood composite hydrogel; step S3, drying the Cr-MOF/wood composite hydrogel to obtain the Cr-MOF/wood composite aerogel. According to the preparation method of the Cr-MOF/wood composite aerogel capable of capturing the heavy metal ions, the Cr-MOF and the wood hydrogel are combined through a hydrothermal method to form the Cr-MOF/wood composite aerogel with the function of capturing the heavy metal ions, the process is simple, the reaction is carried out at a low temperature, and the operation is easy.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to Cr-MOF/wood composite aerogel capable of capturing heavy metal ions and a preparation method and application thereof.
Background
In recent years, with the rapid development of economic construction in China, the activities of mining, smelting, processing and commercial manufacturing of heavy metals are increasingly increased, so that a plurality of heavy metals (such as lead, cesium, strontium and the like) enter the atmosphere, water and soil, a series of serious pollution events are caused, and great harm is caused to the ecological environment. Acute poisoning caused by heavy metals and various chronic diseases of human bodies such as senile dementia threaten the health of human beings all the time. Some heavy metal ions have extremely strong toxicity to organisms at very low concentration, and unlike organic compounds, heavy metals have enrichment property and are difficult to degrade in natural environment. Due to the limitation of the production process, the waste generated in a series of production activities, such as industrial wastewater, contains a large amount of heavy metal ions, which can cause damage to the ecological environment and also cause high production cost.
Most of the materials developed at present with the function of capturing heavy metal ions in sewage are inorganic materials, and have the defects of single adsorption function, small capture amount, slow dynamics and hundreds of hours of deposition process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the Cr-MOF/wood composite aerogel capable of capturing heavy metal ions, so as to solve the problem of how to efficiently and simultaneously capture various heavy metal ions.
In a first aspect, the invention provides a preparation method of a Cr-MOF/wood composite aerogel capable of capturing heavy metal ions, which comprises the following steps:
step S1, preparing the dried wood into wood hydrogel;
step S2, immersing the wood hydrogel into a solution containing Cr-MOF capable of being formed to perform hydrothermal reaction in a sealed reactor to form Cr-MOF/wood composite hydrogel;
step S3, drying the Cr-MOF/wood composite hydrogel to obtain the Cr-MOF/wood composite aerogel.
Optionally, the specific steps of step S1 are as follows:
and sequentially carrying out acidification treatment on the dried wood by using an acidification oxidant and alkalizing by using alkali liquor.
Optionally, the water content of the dried wood in the step S1 is 0.1% to 30%, and the kind of the dried wood is poplar, birch, fir or balsa wood.
Optionally, the acidifying oxidant is hydrogen oxide, peracetic acid, sodium dichromate, ammonium persulfate, sodium chlorite, sodium hypochlorite, sodium percarbonate, sodium perborate or potassium perborate, the pH of the acidifying oxidant is 1.0-6.0, and the acidifying oxidant accounts for 0.1-30% by mass;
the temperature of the acidification treatment is 20-100 ℃, and the treatment time is 1-120 hours.
Optionally, the alkali liquor is lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water, and the mass percent of the alkali liquor is 1-20%;
the temperature of the alkalization treatment is 20-100 ℃, and the treatment time is 1-120 hours.
Optionally, the Cr-MOF-forming solution in the step S2 includes a molar ratio of 1:1:2, 2-amino terephthalic acid and sodium hydroxide.
Optionally, the temperature of the hydrothermal reaction in the step S2 is 50 to 200 ℃, and the treatment time is 1 to 120 hours.
Optionally, the drying process in step S3 is performed by vacuum freeze drying, critical point drying or supercritical drying.
In a second aspect, the invention provides a Cr-MOF/wood composite aerogel prepared by the preparation method of the Cr-MOF/wood composite aerogel capable of capturing heavy metal ions.
In a third aspect, the invention provides application of the Cr-MOF/wood composite aerogel in capturing heavy metal ions from sewage.
The invention has the beneficial effects that:
1. according to the preparation method of the Cr-MOF/wood composite aerogel capable of capturing the heavy metal ions, the Cr-MOF and the wood hydrogel are combined through a hydrothermal method to form the Cr-MOF/wood composite aerogel with the function of capturing the heavy metal ions, the process is simple, the reaction is carried out at a low temperature, and the operation is easy.
2. The Cr-MOF/wood composite aerogel capable of capturing heavy metal ions, which is prepared by the invention, has a good three-dimensional layered structure, can effectively capture heavy metal ions, and is a novel heavy metal ion capturing functional material.
3. The Cr-MOF/wood composite aerogel capable of capturing heavy metal ions shows strong balance capturing capacity in sewage and can be used for capturing Pb2+The maximum capture capacity of (2) is 3.64mmol/g, for Sr2+Has a maximum capture capacity of 1.61mmol/g for CS+The maximum capture capacity of (2) was 0.41 mmol/g.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is an XRD test pattern of Cr-MOF/wood composite aerogel provided in example 1 of the present invention;
FIG. 2 is an SEM image of a Cr-MOF/wood composite aerogel provided in example 1 of the present invention;
FIG. 3 is a view for capturing Pb2+XPS plot of post-Cr-MOF/wood composite aerogel;
FIG. 4 is a Cr-MOF/wood composite aerogel for capturing Pb2+The dynamic adsorption curve of (a);
FIG. 5 is a Cr-MOF/wood composite aerogel for capturing Sr2+The dynamic adsorption curve of (a);
FIG. 6 is a Cr-MOF/Wood composite aerogel Capture CS+Dynamic adsorption curve of (2).
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The invention provides a preparation method of Cr-MOF/wood composite aerogel capable of capturing heavy metal ions, which comprises the following steps:
step S1, sequentially carrying out acidification treatment on the dried wood by using an acidification oxidant and alkalization treatment by using alkali liquor to prepare wood hydrogel;
wherein the water content of the dried wood is 0.1-30%, and the dried wood is poplar, birch, fir or balsa wood.
The acidification oxidant is hydrogen oxide, peracetic acid, sodium dichromate, ammonium persulfate, sodium chlorite, sodium hypochlorite, sodium percarbonate, sodium perborate or potassium perborate, the pH of the acidification oxidant is 1.0-6.0, and the mass percent of the acidification oxidant is 0.1-30%;
the temperature of the acidification treatment is 20-100 ℃, and the treatment time is 1-120 hours.
The alkali liquor is lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water, and the mass percent of the alkali liquor is 1-20%;
the temperature of the alkalization treatment is 20-100 ℃, and the treatment time is 1-120 hours.
The wood mainly comprises cellulose, hemicellulose and lignin, and is subjected to acidification treatment to remove lignin components in the wood, then alkalization treatment to remove the hemicellulose in the wood, and finally the cellulose wood hydrogel is obtained.
Step S2, immersing the wood hydrogel into a solution containing Cr-MOF capable of being formed to perform hydrothermal reaction in a sealed reactor to form the Cr-MOF/wood composite hydrogel, wherein the solution containing Cr-MOF capable of being formed comprises the following components in a molar ratio of 1:1:2 chromium nitrate nonahydrate, 2-aminoterephthalic acid and sodium hydroxide;
the temperature of the hydrothermal reaction is 50-200 ℃, and the treatment time is 1-120 hours.
When the wood hydrogel is immersed in a solution containing Cr-MOF which can be formed3+Is combined in the wood hydrogel through the action of hydrogen bonds, and Cr is generated at high temperature provided by hydrothermal reaction3+Reacting the ions with 2-amino terephthalic acid under an alkaline condition to generate Cr-MOF; after several hours, the Cr-MOF attracts through hydrogen bonds and static electricityThe effect of the primer is to grow uniformly in the wood hydrogel.
And S3, drying the Cr-MOF/wood composite hydrogel to obtain the Cr-MOF/wood composite aerogel, wherein the drying treatment mode is vacuum freeze drying, critical point drying or supercritical drying.
The invention also provides examples 1-3 for the preparation process of the invention.
Example 1
1. Sequentially carrying out acidification treatment on a light wood with the size of 10mm x10mm x10mm and the water content of 8% in a sodium chlorite solution with the mass fraction of 1% and the pH value of 4.2 at 80 ℃ for 6 hours and alkalizing the light wood with the mass fraction of 10% in a sodium hydroxide solution with the mass fraction of 95 ℃ for 6 hours, and washing the treated wood in an alcohol-water solution for 3 times to obtain wood hydrogel;
2. putting the wood hydrogel into a solution of chromium nitrate nonahydrate, 2-amino terephthalic acid and sodium hydroxide in a molar ratio of 1:1:2, and carrying out hydrothermal reaction at 150 ℃ for 10 hours to obtain Cr-MOF/wood composite hydrogel;
3. and (3) freeze-drying the Cr-MOF/wood composite hydrogel to obtain the Cr-MOF/wood composite aerogel, and weighing to obtain 80 mgCr-MOF/wood composite aerogel.
FIG. 1 is an XRD pattern of Cr-MOF/wood composite aerogel provided in example 1 of the present invention. As shown in fig. 1, the diffraction peaks at 16 ° and 22 ° 2 θ values were attributed to the crystalline regions of cellulose in the wood hydrogel. In addition, other characteristic peaks are attributed to Cr-MOF. After the combination of the wood hydrogel and Cr-MOF, the characteristic peaks of cellulose and Cr-MOF remain in the XRD pattern of the Cr-MOF/wood composite aerogel. These results indicate that the Cr-MOF/wood composite aerogel was successfully synthesized.
FIG. 2 is an SEM image of a Cr-MOF/wood composite aerogel provided in example 1 of the present invention. As shown in figure 2, upon treatment of balsa with acidified sodium chlorite and sodium hydroxide solution, Cr-MOF/wood composite aerogels were observed to possess a layered structure, indicating the removal of hemicellulose and lignin. Cr (chromium) component3+First bound in the wood hydrogel by the action of hydrogen bonds. Thereafter, Cr is present during a heat treatment at 150 DEG C3+With 2-amino terephthalic acidThe reaction is carried out under the alkaline condition, the octahedron Cr-MOF grows in the layered wood hydrogel, and the Cr-MOF/wood composite aerogel is successfully synthesized.
Example 2
1. Sequentially carrying out acidification treatment on poplar with the size of 10mm x10mm x10mm and the water content of 1% in a sodium chlorite solution with the mass fraction of 5% and the pH value of 3.0 at 70 ℃ for 10 hours and alkalization treatment on the poplar in a sodium hydroxide solution with the mass fraction of 12% at 90 ℃ for 10 hours, and washing the treated wood in an alcohol-water solution for 3 times to obtain wood hydrogel;
2. putting the wood hydrogel into a solution of chromium nitrate nonahydrate, 2-amino terephthalic acid and sodium hydroxide in a molar ratio of 1:1:2, and carrying out hydrothermal reaction at 120 ℃ for 12 hours to obtain Cr-MOF/wood composite hydrogel;
3. and drying the critical point of the Cr-MOF/wood composite hydrogel to obtain the Cr-MOF/wood composite aerogel, and weighing to obtain 78 mgCr-MOF/wood composite aerogel.
Example 3
1. Sequentially carrying out acidification treatment on fir with the size of 10mm x10mm x10mm and the water content of 10% in a sodium chlorite solution with the mass fraction of 8% and the pH value of 5.0 at 85 ℃ for 8 hours and alkalization treatment on the fir with the mass fraction of 10% in a sodium hydroxide solution with the mass fraction of 90 ℃ for 12 hours, and washing the treated wood in an alcohol-water solution for 3 times to obtain wood hydrogel;
2. putting the wood hydrogel into a solution of chromium nitrate nonahydrate, 2-amino terephthalic acid and sodium hydroxide in a molar ratio of 1:1:2, and carrying out hydrothermal reaction at 180 ℃ for 6 hours to obtain Cr-MOF/wood composite hydrogel;
3. and (3) freeze-drying the Cr-MOF/wood composite hydrogel to obtain the Cr-MOF/wood composite aerogel, and weighing to obtain 77 mgCr-MOF/wood composite aerogel.
Example 4
This example is tested to determine whether the Cr-MOF/wood composite aerogel prepared in example 2 can adsorb heavy metal ions.
The Cr-MOF/wood composite aerogel prepared in example 2 was placed in a container containing only Pb at a concentration of 8mmol/L2+In the solution of (a) to (b),to be treated for Pb in the solution2+Until no change occurs, taking out the Cr-MOF/wood composite aerogel, and carrying out XPS analysis on the Cr-MOF/wood composite aerogel. FIG. 3 is a view for capturing Pb2+XPS plot of post-Cr-MOF/wood composite aerogel. As can be seen from FIG. 3, adsorption of Pb2+The post-Cr-MOF/wood composite aerogel mainly consists of Cr, O, N, C and Pb elements. Cr 2P, O1 s, N1 s and C1 s are classified into Cr-MOF/wood composite aerogels, where N is a-NH 2 functional group grafted to Cr-MOF. The appearance of Pb 4f peak indicates that the Cr-MOF/wood composite aerogel successfully captures heavy metal ions Pb2+。
Example 5
This example uses a dynamic adsorption test to test the adsorption capacity of the Cr-MOF/wood composite aerogel prepared in example 1 for heavy metal ions.
The test was carried out at 20 ℃. Prior to the test, 100mL of a test solution containing Pb at an initial concentration of 8mmol/L was prepared2+、Sr2+And Cs+. Putting 80mg of Cr-MOF/wood composite aerogel into a test solution, and detecting Pb in the test solution at regular intervals2+、Sr2+And Cs+And recording.
Pb was calculated by the following formula2+、Sr2+And Cs+The capture capacity of (a).
Capture capacity
Wherein, C0(mmol·L-1) Is the initial concentration of the ion; ce(mmol·L-1) Is the equilibrium concentration of the ion; m is the relative atomic mass of the ion; m (g) is the mass of the Cr-MOF/wood composite aerogel; v (L) is the volume of the test solution.
FIG. 4 is a Cr-MOF/wood composite aerogel for capturing Pb2+Dynamic adsorption curve of (2). As can be seen from FIG. 4, Cr-MOF/Wood composite aerogel is aligned to Pb2+The equilibrium capture capacity of (a) increases rapidly in a short time and then slowly, ultimately achieving maximum equilibrium capture capacity. Cr-MOF/Wood composite aerogel vs. Pb2+The maximum capture capacity of (2) is 3.64 mmol/g.
FIG. 5 is a Cr-MOF/wood composite aerogel for capturing Sr2+Dynamic adsorption curve of (2). Cr-MOF/wood composite aerogel pair Sr2+The maximum capture capacity of (2) was 1.61 mmol/g.
FIG. 6 is a Cr-MOF/Wood composite aerogel Capture CS+Dynamic adsorption curve of (2). Cr-MOF/Wood composite aerogel Pair CS+The maximum capture capacity of (2) was 0.41 mmol/g.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (5)
1. A preparation method of Cr-MOF/wood composite aerogel capable of capturing heavy metal ions is characterized by comprising the following steps:
step S1, preparing the dried wood into wood hydrogel;
step S2, immersing the wood hydrogel into a solution containing Cr-MOF capable of being formed to perform hydrothermal reaction in a sealed reactor to form Cr-MOF/wood composite hydrogel;
step S3, drying the Cr-MOF/wood composite hydrogel to obtain Cr-MOF/wood composite aerogel;
the solution capable of forming Cr-MOF in the step S2 comprises a mixture of Cr and MOF in a molar ratio of 1:1:2, the temperature of the hydrothermal reaction is 50-200 ℃, the treatment time is 1-120 hours,
the specific steps of step S1 are as follows:
sequentially carrying out acidification treatment on the dried wood by using an acidification oxidant and alkalifying by using alkali liquor, wherein the acidification oxidant is peracetic acid, sodium dichromate, ammonium persulfate, sodium chlorite, sodium hypochlorite, sodium percarbonate, sodium perborate or potassium perborate, the pH of the acidification oxidant is 1.0-6.0, and the mass percentage of the acidification oxidant is 0.1-30%; the temperature of the acidification treatment is 20-100 ℃, and the treatment time is 1-120 hours;
the alkali liquor is lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia water, and the mass percent of the alkali liquor is 1% -20%; the temperature of the alkalization treatment is 20-100 ℃, and the treatment time is 1-120 hours.
2. The preparation method of the Cr-MOF/wood composite aerogel capable of capturing heavy metal ions according to claim 1, wherein the water content of the dried wood in the step S1 is 0.1% -30%, and the dried wood is poplar, birch, cedar or balsa wood.
3. The preparation method of the Cr-MOF/wood composite aerogel capable of capturing heavy metal ions according to claim 1, wherein the drying treatment in the step S3 is vacuum freeze drying and critical point drying.
4. The Cr-MOF/wood composite aerogel prepared by the preparation method of the Cr-MOF/wood composite aerogel capable of capturing heavy metal ions, according to any one of claims 1 to 3.
5. Use of the Cr-MOF/wood composite aerogel of claim 4 for capturing heavy metal ions from wastewater.
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