CN111944162A - Preparation method of hyperbranched polyester modified silver ion-loaded diatomite - Google Patents
Preparation method of hyperbranched polyester modified silver ion-loaded diatomite Download PDFInfo
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- CN111944162A CN111944162A CN202010840596.1A CN202010840596A CN111944162A CN 111944162 A CN111944162 A CN 111944162A CN 202010840596 A CN202010840596 A CN 202010840596A CN 111944162 A CN111944162 A CN 111944162A
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- silver ion
- diatomite
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- hyperbranched polyester
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical class [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229920006150 hyperbranched polyester Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- -1 aminosilane modified silver ion Chemical class 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 101000775678 Burkholderia pseudomallei (strain K96243) Protein-glutamine deamidase Cif Proteins 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims 1
- 229910052621 halloysite Inorganic materials 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 7
- 229940043267 rhodamine b Drugs 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 238000004043 dyeing Methods 0.000 abstract description 5
- 238000007639 printing Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000007112 amidation reaction Methods 0.000 abstract 1
- 239000005909 Kieselgur Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a preparation method of hyperbranched polyester modified silver ion-loaded diatomite, which is characterized in that the silver ion-loaded diatomite is modified by aminosilane, and finally hyperbranched polyester is grafted by amidation reaction to obtain the hyperbranched polyester modified silver ion-loaded diatomite material. The material has strong adsorption capacity on heavy metal ions and organic pollutants in printing and dyeing wastewater, has the performance of photocatalytic degradation of organic pollutants, can realize enrichment and degradation of rhodamine B in polluted water, and has potential practical application value.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a preparation method of hyperbranched polyester modified negative-load silver ion diatomite.
Background
The dye organic pollutant is a common water environment pollutant and can be enriched in a human body through a biological chain, so that the health of the human body is influenced, and canceration is caused seriously. Therefore, the treatment of the dye organic pollutants in the printing and dyeing wastewater is urgent. The most common method for treating such contaminants is adsorption, but the adsorption and degradation capabilities are relatively weak. Therefore, the research and development of a high-efficiency, highly targeted and pollutant-degradable treatment technology becomes a current focus of attention.
The diatomite is a porous material formed by remains of the diatomite and has the advantages of large specific surface area, good corrosion resistance, greenness, no toxicity and the like. As an adsorption and catalysis carrier material with easily available raw materials and low price, the diatomite has wide application prospect in the aspect of water treatment. The natural diatomite contains metal oxide impurities in different proportions, so that the porosity of the diatomite is reduced, and the adsorption and catalytic activity of the diatomite are influenced. Therefore, the surface modification and composite modification for enhancing the adsorption and catalytic performance of the diatomite are the research focus in the water treatment direction of the diatomite material at present. There are many patents relating to the study of adsorption of pollutants by diatomite composite materials. For example, patent No. CN107486160A discloses a method for preparing a nanocellulose/diatomite composite adsorbing material. Patent No. 107376849a discloses an ethylenediaminetetraacetic acid modified diatomite adsorbent, a preparation method thereof and application of the ethylenediaminetetraacetic acid modified diatomite adsorbent in treating heavy metal ions in wastewater.
According to analysis in the prior art, most of the existing diatomite materials are complex to prepare, secondary pollution is easily caused, and reports are provided for diatomite materials with organic pollutant degradation functions. Therefore, the research on the composite diatomite material which takes natural mineral diatomite as a green raw material, efficiently adsorbs the natural mineral diatomite, aims at dye molecules as target pollutants and has a photocatalytic degradation function is very important.
Disclosure of Invention
In order to solve the problem of serious pollution of organic dye pollutants in printing and dyeing wastewater at present, the invention provides a preparation method of hyperbranched polyester modified negative-load silver ion diatomite with efficient adsorption and catalytic degradation functions, which can realize the purposes of enriching organic pollutants in printing and dyeing water and degrading the organic pollutants through photocatalysis and has potential application value.
The invention is realized by the following technical scheme:
a preparation method of hyperbranched polyester modified negative-load silver ion diatomite comprises the following steps:
(1) preparation of silver ion-loaded diatomite (Ag @ DE)
The diatomite is completely wetted in an ascorbic acid solution, dried to constant weight, then completely wetted in a silver nitrate solution, and dried after standing for 24-32 hours to obtain the diatomite-loaded silver ion material (Ag @ DE), wherein the silver ion loading enables the diatomite material to have the performance of photocatalytic degradation of organic dyes, the concentration of the ascorbic acid solution is 0.20-0.25 mol/L, the concentration of the silver nitrate solution is 0.02-0.025 mol/L, and the drying temperature is preferably 100-110 ℃.
(2) Preparation of aminosilane modified silver ion-loaded diatomite (A-Ag @ DE)
Activating the silver-loaded diatomite material Ag @ DE prepared in the step (1) in a NaOH solution, ultrasonically dispersing activated diatomite powder in an ethanol solution for 30-60 min to prepare a diatomite suspension with good dispersibility, dropwise adding aminosilane into the suspension, adjusting the pH to 5.5-6 by using acetic acid, stirring in a water bath at 40-50 ℃ for 24-28 h, washing, and drying to prepare aminosilane modified silver ion-loaded diatomite marked as A-Ag @ DE. The mass ratio of the Ag @ DE to the NaOH of the silver ion-loaded diatomite material is 2.0-3.0: preferably, the molar concentration of the NaOH solution is 0.5-0.6 mol/L, and the mass ratio of the activated diatomite powder to the aminosilane is 1.4-1.6: 1. the aminosilane coupling agent is one or more of 3-aminopropyl-trimethoxy silane, 3-aminopropyl-triethoxy silane and N-beta-aminoethyl-gamma-aminopropyl-methyldimethoxy silane, and preferably, the mass fraction of acetic acid is 35-38%. Preferably, the drying temperature is 80-90 ℃.
(3) Preparation of hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE)
Dispersing the aminosilane modified silver ion-loaded diatomite powder prepared in the step (2) into an acetone solution, gradually adding hyperbranched polyester CHBP and p-toluenesulfonic acid, reacting for 40-60min, taking out, filtering, washing and drying to obtain the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) material.
The specific preparation route is as follows:
the mass-volume ratio of the aminosilane modified silver ion-loaded diatomite powder to the hyperbranched polyester CHBP to the p-toluenesulfonic acid to the acetone is 10 g: 4-4.5 g: 1-1.5 g: 25-30 mL.
The preferable hyperbranched polyester CHBP has the mass fraction of 5-6%, the washing is firstly carried out for 2-3 times by using methanol, then the washing is carried out to be neutral by using deionized water, and the preferable drying condition is vacuum drying for 12-15h at the temperature of 90-100 ℃.
The invention has the following beneficial effects:
1. the invention provides hyperbranched polyester modified silver ion-loaded diatomite with a photocatalytic degradation function
The organic dye in the printing and dyeing wastewater can be effectively adsorbed with high efficiency; the material adopts natural inorganic mineral diatomite as a substrate, is loaded with silver ions for hyperbranched modification, has the advantages of simple and convenient operation, high adsorption efficiency and catalytic degradation of organic pollutants, can be widely applied to the specific adsorption of a sewage system containing the organic pollutants, and has good development prospect.
2. The invention provides hyperbranched polyester modified silver ion-loaded diatomite with a photocatalytic degradation function
Has the advantages of cheap and easily obtained raw materials, wide application range, low production cost, environmental protection and the like.
Drawings
FIG. 1 is an SEM image of silver ion loaded diatomaceous earth (Ag @ DE) prepared in example 2;
FIG. 2 is an adsorption profile of the hyperbranched polyester modified silver ion loaded diatomaceous earth (CA-Ag @ DE) prepared in example 1;
FIG. 3 is a graph showing the photocatalytic degradation of rhodamine B by using the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) prepared in example 3.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
the preparation method of the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) comprises the following steps:
(1) preparation of silver ion-loaded diatomite (Ag @ DE)
Taking 15g of dried diatomite, adding 0.20mol/L ascorbic acid solution until the diatomite is completely wetted, drying at 105 ℃ to constant weight, then crushing the product, adding 0.02% silver nitrate solution until the diatomite is completely wetted, standing for 24h, and drying at 105 ℃ to obtain the silver ion-loaded diatomite (Ag @ DE).
(2) Preparation of aminosilane modified silver ion-loaded diatomite (A-Ag @ DE)
Accurately weighing 10g of silver ion-loaded diatomite powder, putting the silver ion-loaded diatomite powder into 250mL of NaOH solution with the concentration of 0.5mol/L, stirring for 1h at normal temperature, carrying out suction filtration, washing and drying for later use.
Accurately weighing 1.5g of activated diatomite powder, putting the diatomite powder into a beaker filled with 30mL of ethanol solution, putting the beaker on a magnetic stirrer, stirring for 10min at room temperature, putting the beaker into an ultrasonic cleaner, and ultrasonically dispersing for 30min to prepare diatomite suspension with good dispersibility; weighing 0.8mL of 3-aminopropyltriethoxysilane, adding the 3-aminopropyltriethoxysilane into the diatomite suspension, adjusting the pH to 6 by adopting 36% acetic acid by mass fraction, stirring in a water bath at 40 ℃ for 24 hours, carrying out suction filtration, washing and drying to obtain the aminosilane modified silver ion-loaded diatomite.
(3) Preparation of hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE)
Taking acetone as a solvent, adding 1g of aminosilane modified silver ion-loaded diatomite (A-Ag @ DE), ultrasonically stirring for 30min to obtain a uniformly dispersed solution, then starting magnetic stirring, gradually adding 8mL of 5% CHBP and 0.1g of p-toluenesulfonic acid, taking out after 40min, filtering, washing for 2-3 times by using methanol, and then washing with deionized water to be neutral; drying for 12h at 90 ℃ to obtain the hyperbranched polyester modified silver ion loaded diatomite (CA-Ag @ DE) material.
Example 2:
the preparation of the silver ion-loaded diatomite (Ag @ DE) comprises the following steps:
adding 0.25mol/L ascorbic acid solution into 5g of dried diatomite until the diatomite is completely wetted, drying at 105 ℃ to constant weight, then crushing a product, adding 0.025% silver nitrate solution until the diatomite is completely wetted, standing for 30h, and drying at 105 ℃ to obtain the silver ion-loaded diatomite (Ag @ DE);
example 3:
the preparation method of the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) comprises the following steps:
(1) preparation of silver ion-loaded diatomite (Ag @ DE)
Taking 10g of dried diatomite, adding 0.20mol/L ascorbic acid solution until the diatomite is completely wetted, drying at 105 ℃ to constant weight, then mashing the product, adding 0.02% silver nitrate solution until the diatomite is completely wetted, standing for 24h, and drying at 105 ℃ to obtain the silver ion-loaded diatomite (Ag @ DE).
(2) Preparation of aminosilane modified silver ion-loaded diatomite (A-Ag @ DE)
Accurately weighing 10g of silver ion-loaded diatomite powder, putting the silver ion-loaded diatomite powder into 250mL of 0.5mol/L NaOH solution, stirring for 1h at normal temperature, performing suction filtration, washing and drying for later use.
Accurately weighing 3g of activated diatomite powder, putting the diatomite powder into a beaker filled with 60mL of ethanol solution, placing the beaker on a magnetic stirrer, stirring for 10min at room temperature, putting the beaker into an ultrasonic cleaner, ultrasonically dispersing for 30min to prepare a diatomite suspension with good dispersibility, weighing 1.6mL of 3-aminopropyl-trimethoxy silane, adding the 3-aminopropyl-trimethoxy silane into the diatomite suspension, adjusting the pH to 5.5 by adopting 38% acetic acid by mass fraction, stirring for 24h in water bath at 40 ℃, carrying out suction filtration, washing and drying to prepare the aminosilane modified silver ion-loaded diatomite (A-Ag @ DE).
(3) Preparation of hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE)
Adding 3g of aminosilane modified silver ion-loaded diatomite (A-Ag @ DE) into acetone serving as a solvent, performing ultrasonic stirring for 30min to obtain a uniformly dispersed solution, then starting magnetic stirring, gradually adding 24mL of 5% CHBP and 0.3g of p-toluenesulfonic acid, taking out after 40min, filtering, washing for 2-3 times by using methanol, and then washing with deionized water to be neutral; drying at 90 deg.C for 12 h. Obtaining the hyperbranched polyester modified silver ion loaded diatomite (CA-Ag @ DE) material.
Test example 1 structural characterization of silver ion-loaded diatomaceous earth (Ag @ DE)
Test samples: silver ion-loaded diatomaceous earth (Ag @ DE) prepared in example 2.
1. Analyzing the scanning electron microscope picture: scanning electron microscope analysis was performed on the silver ion loaded diatomaceous earth (Ag @ DE) prepared in example 2, and the electron microscope photograph is shown in the attached FIG. 1. It can be seen from the figure that the diatomite has a large cavity and a large number of shell holes (fig. 1A) for loading the nano-silver particles, the particle size of the nano-silver particles is about 30nm, and the diatomite has a large cavity for better loading the nano-silver particles. From fig. 1B, it can be seen that the nano silver is loaded on the diatomite, the active centers are uniformly distributed, and effective adsorption degradation can be performed.
Test example 2 adsorption Performance test of hyperbranched polyester-modified silver ion-loaded diatomaceous Earth (CA-Ag @ DE)
Test samples: the hyperbranched polyester prepared in example 1 is modified with silver ion-loaded diatomaceous earth (CA-Ag @ DE).
1g of the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) prepared in example 1 is taken to adsorb lead ions and dye rhodamine B respectively. Initial concentrations of 10, 20, 30, 50, 80, 100, 120, 150, 180, 200mg/L were selected and the adsorption content was determined as shown in FIG. 2. It can be seen that the adsorption content of the hyperbranched polyester modified silver ion-loaded diatomite is higher with the increase of the initial concentration of the pollutants. When the initial concentration is 120mg/L, the adsorption contents of the adsorption material on lead ions and rhodamine B reach 176.12 and 103.60mg/g respectively. The hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) is proved to have good adsorption performance.
Test example 3-photodegradability test of hyperbranched polyester-modified silver ion-loaded diatomaceous earth (CA-Ag @ DE).
Test samples: the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) prepared in example 3.
Under the condition of visible light irradiation, 1mg of CA-Ag @ DE prepared in example 3 is used for adsorbing rhodamine B, the content change of a pollutant rhodamine B in the solution is determined at time intervals of 0.25, 1.5, 2.5, 3.5, 4.5, 5.5 and 7 hours, and a curve of the degradation rate changing along with the time is made, as shown in an attached figure 3. It can be seen that along with the lapse of time, the longer the exposure time to visible light is, the lower the concentration of rhodamine B in the solution is, and the higher the degradation rate is, which proves that the photodegradability of the hyperbranched polyester modified silver ion-loaded diatomite (CA-Ag @ DE) is good.
Claims (8)
1. A preparation method of hyperbranched polyester modified silver ion-loaded diatomite is characterized by comprising the following steps:
(1) preparation of silver ion-loaded diatomite
Completely wetting kieselguhr in an ascorbic acid solution, drying to constant weight, completely wetting the kieselguhr in a silver nitrate solution, standing for 24-32 hours, and drying to obtain the kieselguhr-loaded silver ion material;
(2) preparation of aminosilane modified silver ion-loaded diatomite
Activating the silver ion-loaded diatomite material prepared in the step (1) in a NaOH solution, then ultrasonically dispersing activated diatomite powder in an ethanol solution for 30-60 min to prepare a diatomite suspension with good dispersibility, dropwise adding aminosilane into the suspension, adjusting the pH to 5.5-6 by using acetic acid, stirring in a water bath at 40-50 ℃ for 24-28 h, washing, and drying to prepare aminosilane modified silver ion-loaded diatomite;
(3) preparation of hyperbranched polyester modified silver ion-loaded diatomite
Dispersing the aminosilane modified silver ion-loaded diatomite powder prepared in the step (2) into acetone, gradually adding hyperbranched polyester CHBP and p-toluenesulfonic acid, reacting for 40-60min, taking out, filtering, washing and drying to obtain the hyperbranched polyester modified silver ion-loaded diatomite material.
2. The preparation method of the hyperbranched polyester modified silver ion-loaded diatomite as claimed in claim 1, wherein the concentration of the ascorbic acid solution in the step (1) is 0.20-0.25 mol/L.
3. The preparation method of the hyperbranched polyester modified silver ion-loaded diatomite as claimed in claim 1, wherein the concentration of the silver nitrate solution in the step (1) is 0.02-0.025 mol/L.
4. The preparation method of the hyperbranched polyester modified silver ion-loaded diatomite as claimed in claim 1, wherein the mass ratio of the silver ion-loaded diatomite material to NaOH in the step (2) is 2.0-3.0: 1, wherein the molar concentration of the NaOH solution is 0.5-0.6 mol/L.
5. The preparation method of the halloysite-based molecularly imprinted nanomaterial according to claim 1, wherein the mass ratio of the activated diatomite powder to the activated aminosilane in the step (2) is 1.4-1.6: 1.
6. the method for preparing hyperbranched polyester modified silver ion-loaded diatomite as claimed in claim 1, wherein the aminosilane in step (2) is one or more selected from 3-aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, and N-beta-aminoethyl-gamma-aminopropyl-methyldimethoxysilane.
7. The preparation method of the hyperbranched polyester modified silver ion-loaded diatomite as claimed in claim 1, wherein the mass-to-volume ratio of the aminosilane-modified silver ion-loaded diatomite powder, the hyperbranched polyester CHBP, the p-toluenesulfonic acid and the acetone in the step (3) is 10 g: (4-4.5 g): (1-1.5 g): 25-30 mL.
8. The preparation method of the hyperbranched polyester modified silver ion-loaded diatomite as claimed in claim 1, wherein the washing in the step (3) is performed by washing with methanol for 2-3 times, and then washing with deionized water until the washing is neutral.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978987A (en) * | 2021-02-19 | 2021-06-18 | 北京九泉科技有限公司 | Novel water purification unit made of environment-friendly materials |
| CN114717118A (en) * | 2022-05-19 | 2022-07-08 | 中南大学 | Silver-loaded diatom material and preparation method and application thereof |
| CN115215411A (en) * | 2022-08-05 | 2022-10-21 | 东莞理工学院 | MOF-Ti doped with rare earth metal 4 O 7 Preparation method of composite electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1960948A (en) * | 2004-03-24 | 2007-05-09 | 3M创新有限公司 | Anti-microbial filter media and methods for making and utilizing the same |
| US20090275680A1 (en) * | 2004-06-01 | 2009-11-05 | Basf Aktiengesellschaft | Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same |
| CN111250047A (en) * | 2020-01-21 | 2020-06-09 | 北京工业大学 | Heavy metal ion adsorbent and preparation method and application thereof |
| CN112962157A (en) * | 2021-02-19 | 2021-06-15 | 上海水星家用纺织品股份有限公司 | Modified diatomite powder loaded with antiviral material, preparation method and application |
| WO2021151850A1 (en) * | 2020-01-27 | 2021-08-05 | Basf Se | Thermoplastic polyamide molding compositions that resist heat |
-
2020
- 2020-08-20 CN CN202010840596.1A patent/CN111944162A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1960948A (en) * | 2004-03-24 | 2007-05-09 | 3M创新有限公司 | Anti-microbial filter media and methods for making and utilizing the same |
| US20090275680A1 (en) * | 2004-06-01 | 2009-11-05 | Basf Aktiengesellschaft | Highly functional, highly branched or hyperbranched polyesters, the production thereof and the use of the same |
| CN111250047A (en) * | 2020-01-21 | 2020-06-09 | 北京工业大学 | Heavy metal ion adsorbent and preparation method and application thereof |
| WO2021151850A1 (en) * | 2020-01-27 | 2021-08-05 | Basf Se | Thermoplastic polyamide molding compositions that resist heat |
| CN112962157A (en) * | 2021-02-19 | 2021-06-15 | 上海水星家用纺织品股份有限公司 | Modified diatomite powder loaded with antiviral material, preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| J. N. ASAAD，等: "Evaluation of Some New Hyperbranched Polyesters as Binding Agents for Heavy Metals", 《THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING》 * |
| 卢朝阳，等: "硅藻土负载纳米银光催化降解罗丹明B", 《闽南师范大学学报（自然科学版）》 * |
| 黎洋: "超支化聚酯改性纳米SiO2/环氧树脂绝缘性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅱ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978987A (en) * | 2021-02-19 | 2021-06-18 | 北京九泉科技有限公司 | Novel water purification unit made of environment-friendly materials |
| CN114717118A (en) * | 2022-05-19 | 2022-07-08 | 中南大学 | Silver-loaded diatom material and preparation method and application thereof |
| CN115215411A (en) * | 2022-08-05 | 2022-10-21 | 东莞理工学院 | MOF-Ti doped with rare earth metal 4 O 7 Preparation method of composite electrode |
| CN115215411B (en) * | 2022-08-05 | 2023-12-08 | 东莞理工学院 | Rare earth metal doped MOF-Ti 4 O 7 Preparation method of composite electrode |
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