CN111790379A - Silver-carbonized resin compound and preparation method thereof - Google Patents
Silver-carbonized resin compound and preparation method thereof Download PDFInfo
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- CN111790379A CN111790379A CN202010693579.XA CN202010693579A CN111790379A CN 111790379 A CN111790379 A CN 111790379A CN 202010693579 A CN202010693579 A CN 202010693579A CN 111790379 A CN111790379 A CN 111790379A
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- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 44
- 239000000805 composite resin Substances 0.000 claims abstract description 40
- 239000004332 silver Substances 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- -1 silver ions Chemical class 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000004005 microsphere Substances 0.000 description 9
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000012258 culturing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000008223 sterile water Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Images
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/60—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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 belongs to the technical field of catalytic materials. The invention provides a preparation method of a silver-carbonized resin compound, which adopts cation exchange resin and silver salt to react, and silver ions are replaced on the surface of the resin; the high temperature resistance and the adsorption capacity of the resin are improved through carbonization; and finally, carrying out reduction reaction on the resin subjected to carbonization treatment and a reducing agent, and reducing silver ions into silver simple substance particles to obtain the silver-carbonized resin compound. The preparation method provided by the invention has the advantages of simple process and low cost, and is suitable for large-scale industrial preparation. The invention also provides the silver-carbonized resin compound prepared by the preparation method. The resin compound provided by the invention contains silver nanoparticles and carbonized resin, wherein the silver nanoparticles are distributed on the surface of the carbonized resin and have catalytic and antibacterial effects; the surface of the carbonized resin consists of macropores, mesopores and mesopores, the specific surface area of the composite resin is large, and the adsorption capacity is enhanced.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a silver-carbonized resin compound and a preparation method thereof.
Background
The nano Ag particles have the performances of catalysis, antibiosis and the like, and have a wide application range, but because the nano Ag particles have the problems of easy agglomeration, easy loss and the like, people often load the nano Ag particles on the surface of a certain carrier to be used as an industrial catalytic material, an electrode material, an antibacterial material and the like. But the main component of the cation exchange resin is organic polymer, so the cation exchange resin is not high in temperature resistance; some carriers are inorganic substances, have no pores on the surface, small specific surface area and lack adsorption performance. Therefore, the application field of the composite is limited, and the application of the Ag composite material in many fields is influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a silver-carbonized resin compound and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a silver-carbonized resin compound, which comprises the following steps:
(1) performing a displacement reaction on the cation exchange resin and a silver source to obtain silver ion exchange resin;
(2) carbonizing the silver ion exchange resin to obtain carbonized resin;
(3) and carrying out reduction reaction on the carbonized resin and a reducing agent to obtain the silver-carbonized resin compound.
Preferably, the cation exchange resin in the step (1) is one or more of a sodium type strong acid cation exchange resin, a hydrogen type strong acid cation exchange resin, a sodium type weak acid cation exchange resin and a hydrogen type weak acid cation exchange resin;
the silver source is a silver nitrate solution, and the concentration of silver ions in the silver source is 0.05-0.5 mol/L.
Preferably, the mass ratio of the solute in the cation exchange resin and the silver source in the step (1) is 1: 1-6, wherein the time of the replacement reaction is 20-100 min.
Preferably, the carbonization in the step (2) is performed in vacuum or in a protective atmosphere, the vacuum degree of the vacuum is 0.01-0.03 Pa, and the protective atmosphere is nitrogen, helium or argon.
Preferably, the carbonization temperature in the step (2) is 250-850 ℃, and the carbonization time is 2-8 h.
Preferably, the reducing agent in the step (3) is a hydrazine hydrate solution or a sodium borohydride solution, the mass concentration of the reducing agent is 0.05-0.5%, and the mass ratio of the carbonized resin to the reducing agent is 1: 0.03 to 0.3.
Preferably, the time of the reduction reaction in the step (3) is 1-6 h.
The invention also provides the silver-carbonized resin compound prepared by the preparation method.
Preferably, the silver-carbonized resin composite comprises silver nanoparticles and carbonized cationic resin, and the silver nanoparticles are distributed on the surface of the carbonized cationic resin.
The invention provides a preparation method of a silver-carbonized resin compound, which adopts cation exchange resin and silver salt to react, and silver ions are replaced on the surface of the resin; the high temperature resistance and the adsorption capacity of the resin are improved through carbonization; and finally, carrying out reduction reaction on the resin subjected to carbonization treatment and a reducing agent, and reducing silver ions into silver simple substance particles to obtain the silver-carbonized resin compound. The preparation method provided by the invention has the advantages of simple process and low cost, and is suitable for large-scale industrial preparation.
The invention also provides the silver-carbonized resin compound prepared by the preparation method. The resin compound provided by the invention contains silver nanoparticles and carbonized cationic resin, wherein the silver nanoparticles are distributed on the surface of the carbonized cationic resin and have catalytic and antibacterial effects; the surface of the carbonized cation resin consists of macropores, mesopores and mesopores, the specific surface area of the composite resin is large, and the adsorption capacity is enhanced.
Drawings
FIG. 1 is a scanning electron micrograph of the overall structure of a silver-carbonized resin composite prepared in example 1;
fig. 2 is a scanning electron microscope image of surface silver nanoparticles of the silver-carbonized resin composite prepared in example 1.
Detailed Description
The invention provides a preparation method of a silver-carbonized resin compound, which comprises the following steps:
(1) performing a displacement reaction on the cation exchange resin and a silver source to obtain silver ion exchange resin;
(2) carbonizing the silver ion exchange resin to obtain carbonized resin;
(3) and carrying out reduction reaction on the carbonized resin and a reducing agent to obtain the silver-carbonized resin compound.
In the present invention, the cation exchange resin in the step (1) is preferably one or more of a sodium type strong acid cation exchange resin, a hydrogen type strong acid cation exchange resin, a sodium type weak acid cation exchange resin and a hydrogen type weak acid cation exchange resin, and is more preferably a sodium type strong acid cation exchange resin and/or a hydrogen type strong acid cation exchange resin.
In the invention, the silver source is preferably a silver nitrate solution, and the concentration of silver ions in the silver source is preferably 0.05-0.5 mol/L, more preferably 0.1-0.4 mol/L, and even more preferably 0.2-0.3 mol/L.
In the present invention, the mass ratio of the solute in the cation exchange resin and the silver source in the step (1) is preferably 1: 1 to 6, and more preferably 1: 1.2 to 5.2, more preferably 1: 2-4; the time of the displacement reaction is preferably 20 to 100min, more preferably 30 to 90min, and still more preferably 50 to 70 min.
In the invention, the displacement reaction is carried out under the oscillation condition, and the oscillation has no specific requirement, and the silver source and the cation exchange resin can be fully mixed.
In the present invention, it is preferable that the mixture after completion of shaking is filtered to obtain a silver ion exchange resin.
In the invention, the silver ion exchange resin is preferably dried, and the drying temperature is preferably 40-80 ℃, more preferably 50-70 ℃, and more preferably 55-65 ℃; the drying time is preferably 6-10 h, more preferably 7-9 h, and even more preferably 7.5-8.5 h; in the present invention, the purpose of drying is to remove moisture from the silver ion exchange resin.
In the invention, silver ions in the silver source are adsorbed to the surface of the cation exchange resin through the cation exchange function of the cation exchange resin, and the silver ions are introduced into the resin.
In the present invention, the carbonization in the step (2) is preferably performed in a vacuum or a protective atmosphere, and the vacuum degree is preferably 0.01 to 0.03Pa, more preferably 0.012 to 0.028Pa, and more preferably 0.018 to 0.022 Pa; the protective atmosphere is preferably nitrogen, helium or argon, more preferably nitrogen.
In the invention, the carbonization temperature in the step (2) is preferably 250-850 ℃, more preferably 350-750 ℃, and more preferably 450-650 ℃; the carbonization time is preferably 2-8 h, more preferably 3-7 h, and even more preferably 4-6 h.
In the invention, the high temperature resistance and the adsorption capacity of the composite resin are improved through carbonization treatment, and a carbon simple substance is generated; and because the cation exchange resin contains partial sulfonic acid groups, the cation exchange resin can be combined with carbon simple substances in the carbonization process to become carbon disulfide which is distributed on the surface of the composite resin in a small amount.
In the present invention, the reducing agent in the step (3) is preferably a hydrazine hydrate solution or a sodium borohydride solution, and is more preferably a hydrazine hydrate solution; the mass concentration of the reducing agent is preferably 0.05-0.5%, more preferably 0.1-0.4%, and even more preferably 0.2-0.3%; the mass ratio of the carbonized resin and the reducing agent is preferably 1: 0.03 to 0.3, preferably 1: 0.075-0.255.
In the invention, the time of the reduction reaction in the step (3) is preferably 1-6 h, more preferably 2-5 h, and even more preferably 3-4 h; the reduction reaction is preferably carried out at room temperature.
In the invention, silver ions on the surface of the carbonized resin are reduced into silver nanoparticles through reduction reaction, so that the catalytic and antibacterial effects of the silver-carbonized resin compound are improved.
The invention also provides the silver-carbonized resin compound prepared by the preparation method.
In the invention, the silver-carbonized resin compound is preferably a spherical structure, and the diameter of the spherical structure is preferably 100-400 μm, more preferably 200-300 μm, and even more preferably 240-260 μm; the specific surface area of the spherical structure is preferably 2-5 m2(ii)/g, more preferably 3 to 4m2A more preferable range is 3.4 to 3.6 m/g2/g。
In the present invention, the silver-carbonized resin composite preferably comprises silver nanoparticles and a carbonized resin, more preferably silver nanoparticles, elemental carbon, carbon disulfide particles and a carbonized resin; the silver nanoparticles are preferably distributed on the surface of the carbonized resin, and the diameter of the silver nanoparticles is preferably 50-300 nm, more preferably 100-200 nm, and even more preferably 130-170 nm.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Washing 1g of hydrogen type strong acid cation exchange resin with distilled water in a beaker to remove surface impurities, adding the washed resin into 100mL of 0.1mol/L silver nitrate solution, oscillating the solution on an oscillator for 60 minutes to exchange silver ions with the hydrogen type strong acid cation exchange resin, and then filtering the solution; drying the filtered cation exchange resin at 50 ℃ for 8h to remove water; putting the mixture into a tubular furnace under the vacuum condition of 0.01Pa, controlling the temperature to be 380 ℃ and carbonizing the cation exchange resin for 4 hours; then soaking and reducing the silver-carbonized resin composite in 100mL of 0.1 percent hydrazine hydrate solution for 4 hours, and washing and drying the silver-carbonized resin composite to obtain 0.7 g of silver-carbonized resin composite.
The silver-carbonized resin compound prepared in the embodiment is observed on the surface appearance of the microsphere through a scanning electron microscope, the X-ray diffractometer analyzes the components of the microsphere, the specific surface area determinator analyzes the specific surface area and the pore size distribution of the microsphere, and the result shows that: the prepared silver-carbonized resin composite has the specific surface area of 3.6m2/g。
As can be seen from FIG. 1, the silver-carbonized resin composite prepared by the present embodiment has a spherical structure with porous surface, and the diameter is 100-400 μm;
as can be seen from FIG. 2, the silver-carbonized resin composite prepared in the present example has silver nanoparticles on the surface, and the particle size of the silver nanoparticles is 50-300 nm.
The silver-carbonized resin composite prepared in this example was subjected to a photocatalytic experiment: with a 100w ultraviolet lamp as a light source, 50mg of the silver-carbonized resin composite is placed in 50mL of methyl orange solution with the concentration of 5mg/L, and the decolorization rate of the methyl orange solution after 2 hours can reach 94.6%, so that the silver-carbonized resin composite prepared in the embodiment has a good photocatalytic effect on the methyl orange solution.
The silver-carbonized resin composite prepared in this example was subjected to a high temperature test: and (3) recovering the silver-carbonized resin compound after the photocatalysis experiment, washing, and drying at 100-180 ℃, wherein the shape and the catalytic performance of the silver-carbonized resin compound are not changed.
The silver-carbonized resin composite prepared in this example was subjected to an antibacterial test: lightly taking a small amount of bacterial colonies in strain tubes such as escherichia coli, pseudomonas aeruginosa, staphylococcus aureus and the like, independently dissolving the bacterial colonies in sterile water, fully and uniformly mixing, putting the bacterial colonies into a culture dish, culturing for 24 hours at the temperature of 37 ℃, and observing the bacterial colonies under a microscope with the density of 15.93/mm respectively218.04 pieces/mm213.97 pieces/mm2(ii) a And (2) uniformly mixing 60mg of silver-carbonized resin compound with 25ml of diluted bacterial liquid of the three bacteria respectively, putting the mixture into a culture dish, culturing for 24 hours at the temperature of 37 ℃, observing and counting bacterial colonies under a microscope, and displaying the result: the colony densities are all small, and the colony densities are respectively as follows: 0.08 pieces/mm20.12 pieces/mm20.05 pieces/mm2The antibacterial effect is obvious.
Example 2
Washing 1g of sodium type strong acid cation exchange resin with distilled water in a beaker to remove surface impurities, adding the washed resin into 60mL of 0.5mol/L silver nitrate solution, oscillating the solution on an oscillator for 30 minutes to exchange silver ions with the sodium type strong acid cation exchange resin, and then filtering the solution; drying the filtered cation exchange resin at 60 ℃ for 7h to remove water; putting the mixture into a tubular furnace under the protection of nitrogen, controlling the temperature to be 850 ℃ and carbonizing the cation exchange resin for 2 hours; then soaking and reducing the silver-carbonized resin composite in 60mL of 0.5 percent hydrazine hydrate solution for 1 hour, and washing and drying the silver-carbonized resin composite to obtain 0.5 g of silver-carbonized resin composite.
The silver-carbonized resin compound prepared in the embodiment is observed on the surface appearance of the microsphere through a scanning electron microscope, the X-ray diffractometer analyzes the components of the microsphere, the specific surface area determinator analyzes the specific surface area and the pore size distribution of the microsphere, and the result shows that: the prepared silver-carbonized resin compound is of a spherical structure with porous surface, the diameter of the compound is about 100-250 mu m, and the specific surface area of the compound is 4.6m2/g。
The silver-carbonized resin composite prepared in this example was subjected to a photocatalytic experiment: by taking a 100w ultraviolet lamp as a light source, 30mg of the silver-carbonized resin composite is put into 40mL of methyl orange solution with the concentration of 5mg/L, and the decolorization rate of the methyl orange solution can reach 93.4% after 3 hours, so that the silver-carbonized resin composite prepared by the embodiment has a good photocatalytic effect on the methyl orange solution.
The silver-carbonized resin composite prepared in this example was subjected to a high temperature test: and (3) recovering the silver-carbonized resin compound after the photocatalysis experiment, washing, and drying at 100-180 ℃, wherein the shape and the catalytic performance of the silver-carbonized resin compound are not changed.
The silver-carbonized resin composite prepared in this example was subjected to an antibacterial test: lightly taking a small amount of bacterial colonies in strain tubes such as escherichia coli, pseudomonas aeruginosa, staphylococcus aureus and the like, independently dissolving the bacterial colonies in sterile water, fully and uniformly mixing, putting the bacterial colonies into a culture dish, culturing for 24 hours at the temperature of 37 ℃, and observing the bacterial colonies under a microscope with the density of 16.14 colonies/mm217.97 pieces/mm213.02 pieces/mm2(ii) a 40mg of silver-carbonized resin compound is respectively mixed with 15ml of diluted bacterial liquid of the three bacteria uniformly and then placed into a culture dish, the mixture is cultured for 24 hours at the temperature of 37 ℃, and bacterial colonies are observed and counted under a microscope, and the result shows that: the colony densities are all small, and the colony densities are respectively as follows: 0.16 pieces/mm20.18 pieces/mm20.11 pieces/mm2The antibacterial effect is obvious.
Example 3
Washing 1g of hydrogen type strong acid cation exchange resin with distilled water in a beaker to remove surface impurities, adding the washed resin into 200mL of 0.05mol/L silver nitrate solution, oscillating the solution on an oscillator for 90 minutes to exchange silver ions with the sodium type strong acid cation exchange resin, and then filtering the solution; drying the filtered cation exchange resin at 80 ℃ for 6h to remove water; putting the mixture into a tubular furnace under the vacuum condition of 0.03Pa, controlling the temperature to be 280 ℃ and carbonizing the cation exchange resin for 8 hours; then soaking and reducing the silver-carbonized resin composite in 150mL of 0.05 percent hydrazine hydrate solution for 6 hours, and washing and drying the silver-carbonized resin composite to obtain 0.7 g of silver-carbonized resin composite.
The silver-carbonized resin compound prepared in the embodiment is observed on the surface appearance of the microsphere through a scanning electron microscope, the X-ray diffractometer analyzes the components of the microsphere, the specific surface area determinator analyzes the specific surface area and the pore size distribution of the microsphere, and the result shows that: preparing the obtained silver-carbonized resin composite to be surfaceA porous spherical structure with a diameter of about 150-400 μm and a specific surface area of 2.3m2/g。
The silver-carbonized resin composite prepared in this example was subjected to a photocatalytic experiment: with a 100w ultraviolet lamp as a light source, 23mg of the silver-carbonized resin composite is put into 50mL of methyl orange solution with the concentration of 6mg/L, and the decolorization rate of the methyl orange solution after 2.5 hours can reach 92.3%, so that the silver-carbonized resin composite prepared in the embodiment has a good photocatalytic effect on the methyl orange solution.
The silver-carbonized resin composite prepared in this example was subjected to a high temperature test: and (3) recovering the silver-carbonized resin compound after the photocatalysis experiment, washing, and drying at 100-180 ℃, wherein the shape and the catalytic performance of the silver-carbonized resin compound are not changed.
The silver-carbonized resin composite prepared in this example was subjected to an antibacterial test: lightly taking a small amount of bacterial colonies in strain tubes such as escherichia coli, pseudomonas aeruginosa, staphylococcus aureus and the like, independently dissolving the bacterial colonies in sterile water, fully and uniformly mixing, putting the bacterial colonies into a culture dish, culturing for 24 hours at the temperature of 37 ℃, and observing the bacterial colonies under a microscope with the density of 16.02 colonies/mm218.09 pieces/mm212.94 pieces/mm2(ii) a 50mg of silver-carbonized resin compound is respectively and uniformly mixed with 20ml of diluted bacterial liquid of the three bacteria, then the mixture is placed into a culture dish, the culture is carried out for 24 hours at the temperature of 37 ℃, and bacterial colonies are observed and counted under a microscope, and the result shows that: the colony densities are all small, and the colony densities are respectively as follows: 0.12 pieces/mm20.15 pieces/mm20.09 pieces/mm2The antibacterial effect is obvious.
From the above embodiments, the silver-carbonized resin composite provided by the invention has the advantages of simple preparation process and low cost; the obtained silver-carbonized resin compound has excellent photocatalytic performance, and the antibacterial capability is improved because of the silver nanoparticles on the surface, so that the silver-carbonized resin compound can be applied to the aspects of industrial catalysis, antibacterial materials and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method of preparing a silver-carbonized resin composite, comprising the steps of:
(1) performing a displacement reaction on the cation exchange resin and a silver source to obtain silver ion exchange resin;
(2) carbonizing the silver ion exchange resin to obtain carbonized resin;
(3) and carrying out reduction reaction on the carbonized resin and a reducing agent to obtain the silver-carbonized resin compound.
2. The method according to claim 1, wherein the cation exchange resin in step (1) is one or more of a sodium type strongly acidic cation exchange resin, a hydrogen type strongly acidic cation exchange resin, a sodium type weakly acidic cation exchange resin, and a hydrogen type weakly acidic cation exchange resin;
the silver source is a silver nitrate solution, and the concentration of silver ions in the silver source is 0.05-0.5 mol/L.
3. The method according to claim 2, wherein the mass ratio of the solute in the cation exchange resin and the silver source in step (1) is 1: 1-6, wherein the time of the replacement reaction is 20-100 min.
4. The method according to any one of claims 1 to 3, wherein the carbonization in the step (2) is performed in a vacuum of 0.01 to 0.03Pa or in a protective atmosphere of nitrogen, helium or argon.
5. The method according to claim 4, wherein the carbonization temperature in the step (2) is 250 to 850 ℃, and the carbonization time is 2 to 8 hours.
6. The preparation method according to claim 1, 2, 3 or 5, wherein the reducing agent in the step (3) is hydrazine hydrate solution or sodium borohydride solution, the mass concentration of the reducing agent is 0.05-0.5%, and the mass ratio of the carbonized resin to the reducing agent is 1: 0.03 to 0.3.
7. The preparation method according to claim 6, wherein the time of the reduction reaction in the step (3) is 1 to 6 hours.
8. A silver-carbonized resin composite obtained by the production method according to any one of claims 1 to 7.
9. The silver-carbonized resin composite of claim 8, comprising silver nanoparticles and a carbonized cationic resin, the silver nanoparticles being distributed on the surface of the carbonized cationic resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113952957A (en) * | 2021-10-20 | 2022-01-21 | 常州大学 | Nickel series hydrogenation catalyst and preparation method and application thereof |
| CN115301297A (en) * | 2022-08-02 | 2022-11-08 | 陕西海斯夫生物工程有限公司 | Cation exchange resin loaded with nano silver particles, preparation method and application thereof |
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| JP3094101B1 (en) * | 1999-05-27 | 2000-10-03 | 工業技術院長 | Method for producing tertiary carboxylic acid and its ester using silver ion exchange resin catalyst |
| CN102240576A (en) * | 2011-05-24 | 2011-11-16 | 北京航空航天大学 | Method for preparing transitional metal/active carbon catalyst |
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| JP3094101B1 (en) * | 1999-05-27 | 2000-10-03 | 工業技術院長 | Method for producing tertiary carboxylic acid and its ester using silver ion exchange resin catalyst |
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| CN115301297A (en) * | 2022-08-02 | 2022-11-08 | 陕西海斯夫生物工程有限公司 | Cation exchange resin loaded with nano silver particles, preparation method and application thereof |
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