CN112246241A - DNA silver nanocluster-metal organic framework composite catalytic material and preparation method and application thereof - Google Patents
DNA silver nanocluster-metal organic framework composite catalytic material and preparation method and application thereof Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 75
- 239000004332 silver Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 62
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 55
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 29
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000013094 zinc-based metal-organic framework Substances 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000003260 vortexing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LNCBPUWMGYOISS-UHFFFAOYSA-N 2'-hydroxy-5'-nitroacetophenone Chemical compound CC(=O)C1=CC([N+]([O-])=O)=CC=C1O LNCBPUWMGYOISS-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- SXLHPBDGZHWKSX-UHFFFAOYSA-N 1-(5-amino-2-hydroxyphenyl)ethanone Chemical group CC(=O)C1=CC(N)=CC=C1O SXLHPBDGZHWKSX-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
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Classifications
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Abstract
The invention discloses a DNA silver nanocluster-metal organic framework composite catalytic material, a preparation method and application thereof. After the DNA silver nanocluster-metal organic framework composite catalytic material prepared by the method is obtained, the material is added into a nitro-group-containing solution, and an amino-group-containing compound is obtained through catalytic reduction reaction. The composite catalytic material can efficiently catalyze the nitro-containing compound, has good thermal stability and chemical stability, and can realize repeated recycling and maintain higher catalytic activity.
Description
Technical Field
The invention relates to a composite catalytic material, in particular to a DNA silver nanocluster-metal organic framework composite catalytic material as well as a preparation method and application thereof.
Background
The environment-preferred pollutant is that a plurality of toxic pollutants are classified and arranged, pollutants with high potential hazard and high occurrence frequency in the environment are screened out as monitoring and control objects, and the pollutants which are preferentially selected become environment-preferred pollutants. P-nitrophenol (p-nitrophenol, p-NP) is an environment priority pollutant, widely exists in industrial wastewater such as pesticide and dye, is difficult to degrade in nature, and has carcinogenic, mutagenic and teratogenic 'triple effect'. P-nitrophenol is widely applied to industrial production as an important raw material and an intermediate product, and causes serious pollution to the environment and certain harm to human bodies along with the discharge of industrial wastewater. The p-nitrophenol is one of intermediate metabolites of the organophosphorus pesticide, has chemical and biological stability and is not easy to degrade.
Researchers at home and abroad make a great deal of research on the degradation of p-NP, and physical methods, biological methods and chemical methods are three common treatment methods. The physical method mainly comprises the following steps: adsorption, extraction, membrane filtration, and the like; the biological method mainly comprises the following steps: the chemical methods mainly comprise an electrochemical oxidation method, an ultrasonic electrolytic degradation method, an ozone oxidation method, a photocatalytic oxidation method, a Fenton reagent oxidation method, a permanganate oxidation method and the like. The traditional method is very difficult to degrade the nitro group, an economic, efficient and environment-friendly method for degrading the p-nitrophenol needs to be found, and according to reports, the DNA silver nanocluster can catalyze sodium borohydride to reduce the nitro group, but the DNA silver nanocluster has the defects of poor stability, high value and the like. Therefore, a novel composite catalytic material is urgently needed, the activity of the DNA silver nanoclusters can be maintained to a great extent on the basis of environmental protection, the reuse is realized, and the catalytic cost is reduced.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a DNA silver nanocluster-metal organic framework composite catalytic material which can protect the DNA silver nanoclusters, so that the DNA silver nanoclusters can endure a certain degree of denaturation conditions, the activity of the DNA silver nanoclusters is maintained, and the DNA silver nanoclusters are repeatedly utilized for many times. The invention also aims to provide a preparation method of the DNA silver nanocluster-metal organic framework composite catalytic material. The invention also aims to provide application of the material, and the nitro-containing compound is reduced to the amino-containing compound by using the DNA silver nanocluster-metal organic framework composite catalytic material as a catalyst.
The technical scheme is as follows: the DNA silver nanocluster-metal organic framework composite catalytic material takes Zn-based MOFs material as a carrier, and the DNA silver nanoclusters are wrapped inside the composite catalytic material.
The DNA silver nanocluster-metal organic framework composite catalytic material is characterized in that the Zn-based MOFs material is ZIF-8.
The DNA silver nanocluster-metal organic framework composite catalytic material is characterized in that the DNA is C34 with a sequence from 5 '-3' to CCCCTAATTCCC.
The preparation method of the DNA silver nanocluster-metal organic framework composite catalytic material comprises the following steps:
(1) preparing DNA silver nanocluster DNA-AgNCs: dissolving DNA in PB buffer solution, and adding AgNO3Centrifuging the solution, adding NaBH4 solution at normal temperature in a dark place, violently vortexing, and centrifuging;
(2) after the reaction is finished, placing the mixture at the temperature of 2-8 ℃ for storage, and placing the mixture to obtain a DNA silver nanocluster solution;
(3) preparing a DNA silver nanocluster-metal organic framework composite catalytic material: adding the prepared DNA silver nanocluster solution into a mixed solution of a zinc acetate dihydrate solution and an imidazole solution, uniformly stirring, and reacting to obtain a reaction solution containing the composite catalytic material;
(4) and (4) centrifugally washing the reaction solution obtained in the step (3) to obtain the DNA silver nanocluster-metal organic framework composite catalytic material.
The preparation method comprises the steps that in the step (1), the PB buffer solution is 10-30mM, the pH value is 7.2-7.6, and the centrifugal rotation speed is 10000-; and (3) adding the DNA silver nanocluster solution into a zinc acetate dihydrate solution and an imidazole solution for mixing, and reacting at 25-30 ℃ for 15-25 h to obtain a reaction solution containing the composite catalytic material.
The DNA silver nanocluster-metal organic framework composite catalytic material is applied to preparation of a catalytic reduction nitro-containing compound.
The application comprises the following steps:
(1) dissolving nitro-containing compounds with different solubilities in an organic solvent or water;
(2) adding a DNA silver nanocluster-metal organic framework composite catalytic material and NaBH4 into a solution containing a nitro compound, then carrying out metal bath oscillation reaction, and standing;
(3) and (3) centrifuging the reaction liquid in the step (2), taking the upper layer liquid, centrifuging the rest liquid to collect the composite catalytic material, and washing for recycling.
The application is that the nitro-containing compound in the step (1) is acetyl protected p-nitrophenol, tert-butyl dimethyl silicon group protected p-nitrophenol and other aromatic conjugated nitro; the organic solvent comprises methanol, ethanol and DMSO.
The application is that the metal bath condition in the step (2) is 25-30 ℃ at room temperature and the rotating speed is 800-.
The application is that the adding amount of the DNA silver nanocluster-metal organic framework composite catalytic material in the step (2) is 1-2% of the mass of the nitro-containing compound; standing for 10-12 h.
According to the invention, a Metal-Organic framework (MOFs) is used for wrapping DNA silver nanoclusters to form a DNA silver nanocluster-Metal Organic framework composite catalytic material, the composite catalytic material is used for carrying out catalytic reduction on p-nitrophenol, and finally the composite catalytic material is collected for recycling. The MOF material is a two-dimensional or three-dimensional crystal structure formed by self-assembly between metal ions and organic ligands by taking the metal ions as connecting points and the organic ligands as supports. In the catalytic reduction reaction of the DNA silver nanoclusters, the DNA silver nanoclusters are wrapped and fixed by the metal organic framework material, so that the DNA silver nanoclusters can be protected from the influence of the external environment, the DNA silver nanoclusters can endure the change of temperature, pH and organic solvent, the activity of the DNA silver nanoclusters is maintained, the recycling rate of the DNA silver nanoclusters is improved, the DNA silver nanoclusters can be particularly recycled for catalytic reduction of p-nitrophenol, and the catalytic reduction reaction cost of the p-nitrophenol is reduced.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) the DNA silver nanocluster-metal organic framework composite catalytic material prepared by the invention is a stable material with high porosity, high specific surface area and adjustable structure, and after the DNA silver nanocluster is wrapped to form the composite catalytic material, the original high-efficiency catalytic activity of the DNA silver nanocluster can be maintained to a great extent, meanwhile, the instability of the DNA silver nanocluster is overcome, the stability of the DNA silver nanocluster is improved, the subsequent recovery is easy, the recycling rate is improved, and the reaction cost is reduced. (2) According to the invention, the DNA silver nanoclusters are wrapped in the metal organic framework material, so that the influence of the environment on the activity of the DNA silver nanoclusters is reduced, the activity of the DNA silver nanoclusters is maintained, the mechanical property of the DNA silver nanoclusters is enhanced, and the operation stability is improved. The composite catalytic material can efficiently catalyze the catalytic reduction reaction of p-nitrophenol, has good thermal stability and chemical stability, is more resistant to organic solvents such as ethanol, methanol, DMSO and the like, increases the practicability of a reduced substrate, and can be recycled to further reduce the production cost. (3) The preparation method is simple and convenient to use, and the prepared DNA silver nanocluster-metal organic framework composite catalytic material maintains the catalytic activity of the DNA silver nanocluster and improves the stability of the DNA silver nanocluster, so that the utilization range of the DNA silver nanocluster is greatly improved, and the DNA silver nanocluster-metal organic framework composite catalytic material can be widely applied to the industries of medicines, foods and the like.
Drawings
FIG. 1 is a schematic representation of the conversion of DNA-AgNCs @ ZIF-8 to catalytically reduce p-nitrophenol;
FIG. 2 is a schematic diagram of the activity of DNA-AgNCs @ ZIF-8 in different environments.
Detailed Description
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The experimental procedures, in which specific conditions are not indicated in the examples, are generally carried out under conventional conditions or conditions recommended by the manufacturer. Among them, C34 (purchased from Sigma Co., Ltd., sequence CCCCTAATTCCC from 5 '-3'), silver nitrate (purchased from Aladdin reagent Co., Ltd.); sodium borohydride (available from alatin reagent, ltd); 2-methyl-imidazole (2-methylimidazole, available from Alatin reagent, Inc.), Zinc acetate dihydrate (available from Alatin reagent, Inc.), p-nitrophenol (available from Alatin reagent, Inc.).
Example 1
Preparation of DNA-AgNCs:
1OD C34 was centrifuged, dissolved in 196.8. mu.l PB (20mM, pH 7.4), vortexed, and added 28.8. mu.l of 1mM AgNO3Centrifuging at 14000rpm for 30s, shielding from light at room temperature for 10min, adding 14.4 μ l of 1mM NaBH4After vigorous vortex, the DNA-AgNCs solution is centrifuged for 30s at 14000rpm and put in a dark place at 4 ℃ for overnight reaction, and finally the DNA-AgNCs solution is obtained.
Example 2
Preparation of DNA-AgNCs @ ZIF-8:
80 μ l of 10 μ M DNA-AgNCs liquid (example 1) was added to 72.7 μ l of 2-methylimidazole (1.735M), and 72.7 μ l of zinc acetate dihydrate (86.8mM) was added, mixed and reacted overnight, centrifuged at 5000rpm, after 15min the precipitate was recovered, washed with ultrapure water and centrifuged three times to remove DNA silver nanoclusters not coated with MOFs, and then stored at 4 ℃ for future use.
Example 3
And (3) carrying out catalytic reduction on p-nitrophenol by using DNA-AgNCs:
mu.l of 2mM 4-NP was taken and 180. mu.l of 200mM NaBH was added4Then, 90. mu.l of 10. mu.M DNA-AgNCs was added and mixed for reaction.
The absorbance of p-nitrophenol by an ultraviolet spectrophotometer at 400nm shows a gradual absorption peak at 300nm as p-nitrophenol is reduced to aminophenol, while the absorption peak at 400nm decreases gradually.
Example 4
DNA-AgNCs @ ZIF-8 catalytic reduction of p-nitrophenol:
mu.l of 2mM 4-NP was taken and 180. mu.l of 200mM NaBH was added4Then, 90. mu.l of 10. mu.M DNA-AgNCs was added and mixed for reaction.
The absorbance of p-nitrophenol by an ultraviolet spectrophotometer at 400nm shows a gradual absorption peak at 300nm as p-nitrophenol is reduced to aminophenol, while the absorption peak at 400nm decreases gradually.
In this example, after the catalytic reduction reaction is completed, the product is centrifuged, the upper layer liquid is taken, the rest of the precipitate is centrifugally collected, the precipitate is washed with ultrapure water and then is repeatedly subjected to the p-nitrophenol catalytic reduction reaction, the conversion rate can be calculated to reach 82.0%, the same catalytic reduction method is used for evaluating the recycling rate of the DNA-AgNCs @ ZIF-8 composite catalytic material, and the conversion rate can still reach more than 70% after 6 times of recycling, as shown in FIG. 1.
Example 5
DNA-AgNCs @ ZIF-8 catalytic reduction of acetyl p-nitrophenol:
example 5 the same reduction procedure as in example 4 was used except that ethanol was used to dissolve acetyl p-nitrophenol.
The position of the spot was observed through the spot plate, at a ratio of 3 for developing agent P: E: 1, two different positions of acetyl p-nitrophenol and acetyl p-aminophenol can be observed.
Example 6
The activities of different DNA silver nanocluster-metal organic framework composite catalytic materials in example 2 of the invention in different environments are tested, and the comparison is the activity of DNA silver nanoclusters which are not wrapped by MOFs materials. The results are shown in FIG. 2 (in the figure, DNA-AgNCs and DNA-AgNCs @ ZIF-8 in order from left to right).
The DNA silver nanocluster-metal organic framework composite catalytic material and the DNA silver nanoclusters in the example 2 are respectively placed in solutions with different temperatures, organic solvents and different pH values for treatment for 2 hours. The three composite catalytic materials and the DNA silver nanoclusters obtained after treatment are used for catalytic reduction reaction of p-nitrophenol, then the p-nitrophenol and the p-aminophenol are analyzed by an ultraviolet spectrophotometer, the conversion rate of the catalytic reduction reaction (the conversion rate is the ratio of the residual p-nitrophenol after the reaction to the p-nitrophenol before the reaction) is calculated, and the catalytic activity ratio (relative activity%) is the ratio of the conversion rate of the catalytic reduction reaction of the treated composite catalytic materials and the DNA silver nanoclusters to the conversion rate of the original DNA silver nanoclusters. Analysis of the experimental results of FIG. 2 shows that DNA-AgNCs @ ZIF-8 has a better protective effect than DNA silver nanoclusters.
Claims (10)
1. The DNA silver nanocluster-metal organic framework composite catalytic material is characterized in that a Zn-based MOFs material is used as a carrier, and the DNA silver nanoclusters are wrapped inside the composite catalytic material.
2. The DNA silver nanocluster-metal organic framework composite catalytic material as recited in claim 1, wherein the Zn-based MOFs material is ZIF-8.
3. The DNA silver nanocluster-metal organic framework composite catalytic material of claim 1, wherein the DNA is C34 sequence from 5 '-3' to CCCCTAATTCCC.
4. The preparation method of the DNA silver nanocluster-metal organic framework composite catalytic material of claim 1 is characterized by comprising the following steps:
(1) preparing DNA silver nanocluster DNA-AgNCs: dissolving DNA in PB buffer solution, and adding AgNO3Centrifuging the solution, adding NaBH4 solution at normal temperature in a dark place, violently vortexing, and centrifuging;
(2) after the reaction is finished, placing the mixture at the temperature of 2-8 ℃ for storage, and placing the mixture to obtain a DNA silver nanocluster solution;
(3) preparing a DNA silver nanocluster-metal organic framework composite catalytic material: adding the prepared DNA silver nanocluster solution into a mixed solution of a zinc acetate dihydrate solution and an imidazole solution, uniformly stirring, and reacting to obtain a reaction solution containing the composite catalytic material;
(4) and (4) centrifugally washing the reaction solution obtained in the step (3) to obtain the DNA silver nanocluster-metal organic framework composite catalytic material.
5. The method according to claim 4, wherein the PB buffer solution in step (1) has a pH of 10-30mM 7.2-7.6 and a centrifugation speed of 10000-; and (3) adding the DNA silver nanocluster solution into a zinc acetate dihydrate solution and an imidazole solution for mixing, and reacting at 25-30 ℃ for 15-25 h to obtain a reaction solution containing the composite catalytic material.
6. The use of the DNA silver nanocluster-metal organic framework composite catalytic material of claim 1 in the preparation of a catalytic reduction of a nitro-containing compound.
7. Use according to claim 6, characterized in that it comprises the following steps:
(1) dissolving nitro-containing compounds with different solubilities in an organic solvent or water;
(2) adding a DNA silver nanocluster-metal organic framework composite catalytic material and NaBH4 into a solution containing a nitro compound, then carrying out metal bath oscillation reaction, and standing;
(3) and (3) centrifuging the reaction liquid in the step (2), taking the upper layer liquid, centrifuging the rest liquid to collect the composite catalytic material, and washing for recycling.
8. The use according to claim 7, wherein the nitro-containing compound of step (1) is acetyl protected p-nitrophenol, tert-butyldimethylsilyl protected p-nitrophenol, other aromatic conjugated nitro group; the organic solvent comprises methanol, ethanol and DMSO.
9. The use as claimed in claim 7, wherein the metal bath conditions in step (2) are 25-30 ℃ at a rotation speed of 800-.
10. The use of claim 7, wherein the DNA silver nanocluster-metal organic framework composite catalytic material of step (2) is added in an amount of 1-2% of the mass of the nitro-containing compound; standing for 10-12 h.
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