CN115301293A - beta-CD modified polyelectrolyte stable metal nanoparticle, and preparation method and application thereof - Google Patents
beta-CD modified polyelectrolyte stable metal nanoparticle, and preparation method and application thereof Download PDFInfo
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- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 28
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 25
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- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 14
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 230000009467 reduction Effects 0.000 claims description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 2
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- 238000006555 catalytic reaction Methods 0.000 abstract description 9
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- MLBMCAGVSIMKNT-UHFFFAOYSA-N β-cds Chemical compound O1C(C(C2OS(O)(=O)=O)OS(O)(=O)=O)C(COS(O)(=O)=O)OC2OC(C(C2OS(O)(=O)=O)OS(O)(=O)=O)C(COS(O)(=O)=O)OC2OC(C(C2OS(O)(=O)=O)OS(O)(=O)=O)C(COS(O)(=O)=O)OC2OC(C(C2OS(O)(=O)=O)OS(O)(=O)=O)C(COS(O)(=O)=O)OC2OC(C(OS(O)(=O)=O)C2OS(O)(=O)=O)C(COS(=O)(=O)O)OC2OC(C(C2OS(O)(=O)=O)OS(O)(=O)=O)C(COS(O)(=O)=O)OC2OC2C(OS(O)(=O)=O)C(OS(O)(=O)=O)C1OC2COS(O)(=O)=O MLBMCAGVSIMKNT-UHFFFAOYSA-N 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/23—
-
- 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
Abstract
The invention relates to a beta-CD modified polyelectrolyte stable metal nanoparticle, a preparation method and application thereof.A mixed solution of a beta-CD modified polyelectrolyte and a metal precursor solution is used as a No. 1 solution, a sodium borohydride solution is used as a reducing agent and is used as a No. 2 solution, the No. 1 solution and the No. 2 solution are used as two flow solutions and are simultaneously injected into a double-channel jet mixer to be collided and mixed, and the beta-CD modified polyelectrolyte stable metal nanoparticle is simultaneously reduced to obtain the beta-CD modified polyelectrolyte stable metal nanoparticle. The invention adopts a method of a limited domain reinforced mixing process to prepare a series of cyclodextrin grafted polyelectrolyte supported nano metal catalysts with controllable catalytic rate. The invention can regulate and control the size of metal nano particles and the synergistic catalysis effect between the cyclodextrin group and the nano metal by regulating the flow rate of liquid flow and the concentration of a reducing agent, a polymer and the like, thereby regulating and controlling the catalysis rate. The method is simple and quick, and the obtained metal nano particles have high-efficiency controllable catalytic performance.
Description
Technical Field
The invention relates to the technical field of metal nanoparticle preparation, in particular to a cyclodextrin polyelectrolyte supported metal nano catalyst with adjustable particle size and catalytic performance, which is prepared by a method of a limited-domain reinforced mixing process, and belongs to the field of new materials.
Background
Metal nanoparticles, which have been extensively studied in the field of catalysis due to their high specific surface area and high proportion of surface active sites, exhibit good catalytic activity, but the high surface energy makes them easily agglomerated, resulting in oversize and uneven size distribution, thereby impairing catalytic performance. Various stabilizers have been widely studied, such as polymers, organic surfactants, carbon materials, silica, and the like. The functional groups rich in polyelectrolyte can well disperse and stabilize the nanoparticles through coordination, static electricity or space interaction, prevent the oxidation of the metal nanoparticles, cannot block catalytic active sites, and is an excellent material of the supported metal nanoparticles. The metal-ligand concerted catalysis is an effective strategy for improving the catalytic performance of metal catalysts, and beta-cyclodextrin (beta-CDs) as a supermolecular catalyst shows good concerted catalysis. The hydrophobic inner cavity of the beta-CD and organic molecules can form a inclusion complex, so that a large number of molecules can be more quickly close to active sites on the surfaces of the metal nanoparticles, and the catalytic efficiency is improved. The surface hydroxyl of the cyclodextrin molecule can easily react with a specific functional group on a polymer chain, and the cyclodextrin is grafted to the polymer chain, so that the limitation that a single cyclodextrin monomer is used as a metal nanoparticle stabilizer due to low water solubility of the cyclodextrin monomer can be improved, the dispersion and immobilization of the nanoparticles are facilitated, and therefore, the beta-CD grafted polymer can be a material with wide prospect for preparing the metal nanoparticles with high catalytic activity.
At present, a wet chemical reduction method is widely used for preparing metal nanoparticles with stable polymers, and the method is relatively simple and economical to operate, but the traditional wet chemical reduction method has the defects of long reaction time, large toxicity, uneven size distribution of the nanoparticles and the like, and most of the traditional wet chemical reduction method needs medium-high temperature and a large amount of organic reagents. In recent years, the limited-domain intensified mixing method, as a method for rapidly preparing nanoparticles, has been widely used due to its simple equipment, rapid process, small particle size and narrow size distribution.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a beta-CD modified polyelectrolyte stable metal nanoparticle, a preparation method thereof and an application thereof in catalyzing nitro compound reduction.
The specific technical scheme is as follows:
a method for regulating and controlling the catalytic rate of cyclodextrin polyelectrolyte-supported nano metal comprises the following steps:
the method comprises the steps of taking a mixed solution of beta-CD modified polyelectrolyte and metal precursor solution as a No. 1 solution, taking a sodium borohydride solution as a reducing agent as a No. 2 solution, setting a certain flow rate, and simultaneously injecting the No. 1 solution and the No. 2 solution as two flow solutions into a double-channel jet mixer for rapid collision and mixing and reducing to obtain the beta-CD modified polyelectrolyte stable metal nanoparticles.
The polyelectrolyte is one of polyacrylic acid, hyaluronic acid and sodium polystyrene sulfonate, and the metal precursor solution is AgNO 3 、NiCl 3 、RhCl 3 Or PdCl 2 One kind of (1).
Preferably, in the solution No. 1, the polyelectrolyte is PAA, and the metal precursor solution is AgNO 3 。
Further, the PAA-beta-CD configuration concentration is 0.004-0.02M.
Further, the AgNO 3 The concentration ratio of the solution to the sodium borohydride solution is 1:10-100.
Further, the AgNO 3 The concentration ratio of the solution to the sodium borohydride solution is 1:20.
further, the flow rate is 5-50ml/min.
Further, the flow rate was 30ml/min.
beta-CD modified polyelectrolyte stable metal nanoparticles
The metal nano-particles prepared by the invention are applied to the catalytic reduction of nitro compounds.
The invention has the advantages that: the preparation method has simple operation and rapid process, and the prepared metal nano particles have small size and are easy to regulate and control. The catalyst is used in catalysis, and shows high-efficiency controllable catalytic activity.
The invention uses the method of limited-area reinforced mixing to prepare the metal nano particles with stable beta-CD modified polyelectrolyte, shortens the preparation time of the metal nano particles, and is easy to regulate the size of the metal nano particles and the synergistic catalysis between the cyclodextrin group and the nano metal, thereby realizing the effective regulation of the catalytic performance. The preparation method has the advantages of simple equipment, rapid process, low energy consumption, easy control and amplification and the like, and has great industrial application prospect.
Drawings
FIG. 1 is a schematic diagram of an experimental apparatus for preparing beta-CD modified polyelectrolyte-stabilized metal nanoparticles;
FIG. 2 is a transmission electron microscope image of PAA- β -CD stabilized silver nanoparticles prepared in example 3;
FIG. 3 is a graph of the variation of the particle size of silver nanoparticles at different PAA- β -CD concentrations prepared in examples 1-4;
FIG. 4 is a graph of the catalytic UV-Vis spectra of PAA- β -CD stabilized silver nanoparticles prepared in example 4.
Figure 5 is a graph of the catalytic rates of PAA- β -CD and PAA-stabilized silver nanoparticles prepared using different polymer concentrations.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.
Example 1
PAA-beta-CD and AgNO 3 Dissolving in ultrapure water at concentrations of 0.004M and 0.4mM respectively to obtain No. 1 flow; sodium borohydride was dissolved in ultrapure water at a concentration of 8mM as stream No. 2. Injecting the No. 1 and No. 2 liquid flows into a double-channel jet mixer through a numerical control injection pump (Harvard Apparatus, PHD 2000) at the flow rate of 30ml/min for rapid collision mixing and simultaneously carrying out reduction reaction to obtain the PAA-beta-CD stable silver nanoparticles.
The catalytic effect of the product prepared by the embodiment is shown in fig. 4, and the result shows that the p-nitrophenol is completely converted into the p-aminophenol after 4min, which shows that the prepared silver nanoparticles with stable polymer have good catalytic performance.
Example 2
PAA-beta-CD and AgNO 3 Dissolving in ultrapure water at concentrations of 0.008M and 0.4mM respectively to obtain No. 1 flow liquid; sodium borohydride was dissolved in ultrapure water at a concentration of 8mM as stream No. 2. Injecting the No. 1 and No. 2 liquid flows into a double-channel jet mixer through a numerical control injection pump (Harvard Apparatus, PHD 2000) at the flow rate of 30ml/min for rapid collision mixing and simultaneously carrying out reduction reaction to obtain the PAA-beta-CD stable silver nanoparticles.
Example 3
PAA-beta-CD and AgNO 3 Dissolving in ultrapure water at concentrations of 0.01M and 0.4mM respectively to obtain No. 1 flow; sodium borohydride was dissolved in ultrapure water at a concentration of 8mM as stream 2. Injecting the No. 1 and No. 2 liquid flows into a double-channel jet mixer through a numerical control injection pump (Harvard Apparatus, PHD 2000) at the flow rate of 30ml/min for rapid collision mixing and reduction to obtain the PAA-beta-CD stable silver nanoparticles. FIG. 2 is a transmission electron microscope analysis of the product of this example, and the result shows that the stable silver nanoparticles of PAA-beta-CD have a particle size of about 8nm (core structure) and good dispersibility.
Example 4
PAA-beta-CD and AgNO 3 Dissolving in ultrapure water at concentrations of 0.012M and 0.4mM respectively to obtain No. 1 flow liquid; sodium borohydride was dissolved in ultrapure water at a concentration of 8mM as stream No. 2. Will be No. 1And the No. 2 fluid is injected into a double-channel jet mixer through a numerical control injection pump (Harvard Apparatus, PHD 2000) at the flow rate of 30ml/min for rapid collision mixing and reduction reaction to obtain the PAA-beta-CD stable silver nanoparticles.
Example 5
Catalytic performance testing of the product of example 1:
3ml of 0.04M sodium borohydride solution and 3ml of 0.2mM p-nitrophenol solution are mixed uniformly and nitrogen is introduced for 5 min. Adding 10 mu L of PAA-beta-CD stable silver nanoparticle suspension prepared without using the polymer concentration into 3ml of the mixed solution in a quartz cuvette with the path length of 1cm, uniformly stirring, measuring the absorbance of the solution by an ultraviolet spectrophotometer, and testing the absorbance of the solution at intervals. Likewise, 10. Mu.L of PAA-stabilized silver nanoparticle suspension prepared under the same experimental conditions was added to 3ml of the mixed solution as a control experiment.
The invention adopts a method of a limited domain reinforced mixing process to prepare a series of cyclodextrin grafted polyelectrolyte supported nano metal catalysts with controllable catalytic rate. The method comprises the steps of taking a mixed solution of a beta-CD modified polyelectrolyte and a metal precursor solution as a No. 1 solution, taking a solution of a reducing agent sodium borohydride as a No. 2 solution, setting a certain flow rate, taking the No. 1 solution and the No. 2 solution as two liquid flows, simultaneously injecting the two liquid flows into a double-channel jet mixer, rapidly colliding and mixing, simultaneously reducing to obtain the beta-CD modified polyelectrolyte-loaded nano metal catalyst, and regulating the size of metal nano particles and the cooperative catalysis between a cyclodextrin group and nano metal by regulating the flow rate of the liquid flows and the concentration of the reducing agent, a polymer and the like so as to regulate and control the catalysis rate. The method is simple and quick, and the obtained metal nano particles have high-efficiency controllable catalytic performance.
Claims (10)
1. The beta-CD modified polyelectrolyte stable metal nanoparticles are characterized in that a mixed solution of beta-CD modified polyelectrolyte and metal precursor solution is used as a No. 1 solution, a sodium borohydride solution is used as a reducing agent and is used as a No. 2 solution, the No. 1 solution and the No. 2 solution are used as two flow solutions and are simultaneously injected into a double-channel jet mixer to be collided and mixed, and reduction is simultaneously carried out to obtain the beta-CD modified polyelectrolyte stable metal nanoparticles.
2. The preparation method of the beta-CD modified polyelectrolyte stable metal nanoparticles according to claim 1 is a method for regulating and controlling the catalytic rate of cyclodextrin polyelectrolyte-supported nano metal, and is characterized by comprising the following steps:
the method comprises the following steps of taking a mixed solution of a beta-CD modified polyelectrolyte and a metal precursor solution as a No. 1 solution, taking a solution of a reducing agent sodium borohydride as a No. 2 solution, taking the No. 1 solution and the No. 2 solution as two streams of solutions, simultaneously injecting the two streams of solutions into a double-channel jet mixer for rapid collision and mixing, simultaneously reducing to obtain a beta-CD modified polyelectrolyte-loaded nano metal catalyst, regulating and controlling the size of metal nanoparticles by regulating the flow rate of the liquid streams and the concentration of the reducing agent, a polymer and the like, and regulating and controlling the catalytic rate by the synergistic catalytic action between a cyclodextrin group and the nano metal;
the polyelectrolyte is one of polyacrylic acid, hyaluronic acid and sodium polystyrene sulfonate, and the metal precursor solution is AgNO 3 、NiCl 3 、RhCl 3 Or PdCl 2 One kind of (1).
3. The method of claim 2, wherein the method comprises the steps of: the polyelectrolyte in the No. 1 solution is polyacrylic acid (PAA); the metal precursor liquid is AgNO 3 。
4. The method of claim 2, wherein the method comprises the steps of: the molecular weight of polyacrylic acid in the solution No. 1 is 8000-200000, and the grafting rate of beta-cyclodextrin is 1-10%.
5. The method of claim 3, wherein the method comprises the steps of: the configuration concentration of the PAA-beta-CD is 0.004-0.02M.
6. The method of claim 3, wherein the method comprises the steps of: agNO 3 The concentration ratio of the solution to the sodium borohydride solution is 1:10-100.
7. The method of claim 6, wherein the method comprises the steps of: agNO 3 The concentration ratio of the solution to the sodium borohydride solution is 1:20.
8. the method of claim 2, wherein the method comprises the steps of: the flow rates of the solutions No. 1 and No. 2 as two streams were 5 to 50ml/min.
9. The method of claim 8, wherein the method comprises the steps of: the flow rate was 30ml/min.
10. An application of metal nanoparticles stabilized by beta-CD modified polyelectrolyte in catalytic reduction of nitro compounds.
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