CN104959163A - Controllable and adjustable metal nanoparticle-loaded polymer catalyst and preparation method thereof - Google Patents
Controllable and adjustable metal nanoparticle-loaded polymer catalyst and preparation method thereof Download PDFInfo
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- CN104959163A CN104959163A CN201510257781.7A CN201510257781A CN104959163A CN 104959163 A CN104959163 A CN 104959163A CN 201510257781 A CN201510257781 A CN 201510257781A CN 104959163 A CN104959163 A CN 104959163A
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Abstract
The invention provides a controllable and adjustable metal nanoparticle-loaded polymer catalyst, and a preparation method thereof. According to the metal nanoparticle of the controllable and adjustable metal nanoparticle-loaded polymer catalyst, a shape memory polymer is taken as a carrier, and the carrier possesses a crosslinked stationary phase and a long chain mobile phase; a long chain compound and a short chain compound, which are capable of generating the crosslinked stationary phase and the long chain mobile phase via polymerization, are taken as functional monomers, and are dissolved in an organic solvent together with an active component precursor, a cross-linking agent, and an initiator; under nitrogen protection, polymerization is initiated via heating, reduction is carried out with sodium borohydride, an obtained product is washed with water and ethanol repeatedly, and is subjected to vacuum drying so as to obtain the metal nanoparticle-loaded polymer catalyst. The preparation method is capable of solving key technique problems that thermal sensitive phase transition of most polymer carriers can not be initiated, and controllable and adjustable catalytic action can not be realized; the raw materials are easily available, and are convenient to obtain; technology is simple; and the preparation method possesses certain universality.
Description
Technical field
The invention belongs to functional high molecule material technical field, be specifically related to a kind ofly to control, the polyalcohol catalyst of adjustable metal nanoparticle load and preparation method thereof.
Background technology
For a long time, realize catalytic action process control system, adjustable catalyst is the important scientific problems that industry is badly in need of solving always.The realization developing into this target in synthetic chemistry and New Intelligent Material field creates condition.By the inspiration of drug controlled release technology, scientists finds, employing poly-N-isopropyl acrylamide (PNIPAm) is carrier, metal nanoparticle is active component, can develop the new ideas catalyst with temperature-responsive ability; When using polyacrylic acid etc. instead for metal nanoparticle carrier, the new catalyst with pH responding ability can be obtained.In like manner, employing crown ether polymer is carrier, metal nanoparticle is active component, can obtain the new ideas catalyst with Ion response ability; When adopt triphenylmenthane based polyalcohol be metal nanoparticle etc. for carrier time, the new catalyst of photoresponse ability can be developed.Thus, scientists drawn can control, the concept of adjustable intelligent polymer catalyst.Compared with change pH, ion etc., the control realizing temperature is easier to operation, therefore becomes most widely used modulation means.Because critical temperature condition is gentle, and response rapidly, and PNIPAm based polyalcohol catalyst is current most widely used intelligent polymer catalyst.Trace it to its cause and be, the design feature of the hydrophilic amide base-hydrophobicity isopropyl of PNIPAm makes it define unique critical solution temperature (~ 32 DEG C) in an aqueous medium.Intelligent polymer catalyst, by the temperature-sensitive phase transformation of PNIPAm under critical temperature condition, makes chemical reaction obtain transition immediately or " freezing ", skips or rest on default position, thus the control realized chemical action process and adjustment.
But, in actual applications, the polymer of most applicable carrying metal nano particle, unlike poly-N-isopropyl acrylamide, does not have temperature-sensitive transformation behavior, cannot meet can control, the requirement of adjustable catalytic action, thus cause obvious obstacle to the application of intelligent catalysis agent.International and domestic patent is all reported without effective alternative.For overcoming this present situation, some researchers have carried out deep exploration work, have employed function and the polymer that the comes in every shape carrier as metal nanoparticle, the functional polymer catalyst developing function and come in every shape, as: the polyalcohol catalysts such as nucleocapsid structure polymer microballoon, function nano particle.But because these carrier polymers do not possess character and the ability of intelligent response, the polyalcohol catalyst therefore obtained at present cannot meet the requirement that can control, can modulate catalytic action, cannot cater to the current demand of catalysis development.This present situation seriously constrains the development of catalysis industry, makes industry be difficult to produce the polyalcohol catalyst of Practical significance, thus forces people to be developed to have more the new method of universality and higher intelligent polymer catalyst.
Summary of the invention
The present invention is directed to industry urgent problem, there is provided a kind of and control, the polyalcohol catalyst of adjustable metal nanoparticle load and preparation method thereof, from solve at all most polymer carrier without temperature-sensitive phase transformation, cannot meet can control, the Key technique problem of adjustable catalytic action, have that raw material is easy to get, facility of drawing materials, technique is simple, and has the features such as certain universality.
Control, the preparation method of the polyalcohol catalyst of adjustable metal nanoparticle load, it is characterized in that, comprise the following steps:
(1) function monomer, active constituent presoma, crosslinking agent and initator are dissolved in organic solvent; Described function monomer selects the long-chain compound and short chain compound that can be polymerized and produce crosslinked stationary phase and long-chain mobile phase, and the mol ratio of described long-chain compound and short chain compound is 1:7 ~ 14, and described active constituent presoma is metal ion state compound;
(2) under nitrogen protection, add thermal-initiated polymerization, form the polyalcohol catalyst presoma of metal nanoparticle load;
(3) metal ion in the polyalcohol catalyst presoma of metal nanoparticle load after sodium borohydride reduction, and cleans final vacuum drying repeatedly through water, ethanol, namely obtains the polyalcohol catalyst of described metal nanoparticle load.
Preferably, the consumption of described organic solvent is can lytic activity component presoma, initator, function monomer and crosslinking agent be as the criterion; The consumption of crosslinking agent is 1 ~ 10wt% of function monomer; The consumption of active component presoma is as the criterion with the maximum coordination ratio being no more than function monomer; The consumption of initator is 1 ~ 10wt% of function monomer.
Preferably, described long-chain compound is the one in octadecenic acid, 2-nonenoic acid, N-dodecylacrylamide, and short chain compound is acrylic acid or acrylamide.
Preferably, crosslinking agent is N, N-methylene-bisacrylamide.
Preferably, active component presoma is the one in nickel nitrate, silver nitrate, chloroplatinic acid.
Preferably, initator is azodiisobutyronitrile (AIBN).
Preferably, described organic solvent is methyl-sulfoxide.
Preferably, polymeric reaction temperature scope is 60-70 DEG C.
By described preparation method obtain control, the polyalcohol catalyst of adjustable metal nanoparticle load, it is characterized in that, metal nanoparticle take shape-memory polymer as carrier, and described carrier has crosslinked stationary phase and long-chain mobile phase.
The present invention's principal character compared with other are invented is: the inducing memory behavior of mimic biology soma, take shape-memory polymer as carrier, metal nanoparticle is active component, by motion or " freezing " of shape-memory polymer mobile phase molecule segment, form the commutation territory that substrate channels controls automatically, direct realization can control, the preparation of adjustable Ni-based polyalcohol catalyst, from solve at all most polymer carrier without temperature-sensitive phase transformation, cannot meet can control, the Key technique problem of adjustable catalytic action.Preparation method of the present invention is simple, easy to operate, and has certain universality, and equipment needed thereby is less demanding, is easy to realize large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the know-why of prepared catalyst in the embodiment of the present invention 1.
Fig. 2 is the FTIR collection of illustrative plates of prepared catalyst and reference substance in the embodiment of the present invention 1.
Fig. 3 is the TEM photo of prepared catalyst and reference substance in the embodiment of the present invention 1.
Fig. 4 is the dynamic scattering DLS transformation curve of prepared catalyst and reference substance in the embodiment of the present invention 1.
Fig. 5 is the SME of prepared catalyst polymer in the embodiment of the present invention 1.
Fig. 6 is the modulation catalytic action of prepared catalyst and reference substance temperature-responsive in the embodiment of the present invention 1.
Fig. 7 is the modulation catalytic action of prepared catalyst and reference substance temperature-responsive in the embodiment of the present invention 2.
Fig. 8 is the modulation catalytic action of prepared catalyst and reference substance temperature-responsive in the embodiment of the present invention 3.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1:
With octadecenic acid and acrylic acid be function monomer, nickel nitrate is active constituent presoma, N, N methylene-bisacrylamide is crosslinking agent and be in organic solvent with azodiisobutyronitrile (AIBN) for initator is dissolved in methyl-sulfoxide.
Be active constituent presoma by 1mmol octadecenic acid, 9mmol acrylic acid, 1mmol nickel nitrate, 0.1mmol N, N methylene-bisacrylamide, 0.1g azodiisobutyronitrile (AIBN) be dissolved in 10mL methyl-sulfoxide.
Under nitrogen protection, in 70 DEG C of initiated polymerizations, form the polyalcohol catalyst presoma of metal nanoparticle load.
In presoma, nickel ion is through excessive sodium borohydride reduction, dry through cleaning final vacuum, obtained described catalyst.The consumption of concrete described sodium borohydride be 10 times to nickel ion.
Described catalyst is labeled as " NiPC-S ", wherein, Ni is nickel nano particle, PC is polyalcohol catalyst, S is commutation character.
For the purpose of contrasting with NiPC-S, the present embodiment has also prepared reference polymer catalyst n iPC-N and PC-HCS under similarity condition.Wherein, NiPC-N is traditional non-response nickel-base catalyst, and its carrier is made up of polyacrylic acid, not containing poly-octadecenic acid; PC-S is NiPC-S carrier, not containing nickel nano particle.
Fig. 2 and Fig. 3 is respectively FTIR collection of illustrative plates and the TEM photo of the catalyst obtained by reference polymer catalyst and the present embodiment, its composition and structural form are characterized, show that the NiPC-S catalyst prepared is the form designed by the present invention, wherein containing the nickel nano particle of about 10nm size.
In NiPC-S polyalcohol catalyst, molecule segment mobility is the driving force automatically controlling commutation territory, and its transformation behavior is measured by dynamic light scattering DLS.By changing the temperature of catalyst system, obtain the change of intelligent catalysis agent relative to traditional non-response catalyst Dynamic Radius, it the results are shown in Figure 4.The NiPC-S catalyst of preparation presents intelligent response, controls the ability of commutation, and its phase in version appears at about 36 DEG C.Based on the mensuration of transformation behavior, the SME of preparation NiPC-S is shown in Fig. 5.At room temperature 25 DEG C, initial configuration is the polymer of bar shaped, higher than load deflection during phase transition temperature 50 DEG C, is cooled to room temperature, and temporary shapes obtains fixing; After being again heated to above the deformation of phase transition temperature condition, preliminary form obtains to be recovered.The NiPC-S catalyst of preparation demonstrates obvious memory effect, presents intelligent response, controls the ability of commutation.
Based on the mensuration to transformation behavior and molecule segment mobility, select respectively to carry out catalytic determination lower than with higher than 25 DEG C and 50 DEG C of transformation temperature.Catalytic performance test adopts following reduction system: being substrate with methylene blue, take sodium borohydride as reducing agent.Be that to join 2mL concentration be in 20 μ g/mL sodium borohydride aqueous solutions to 4 μ g/mL methylene blue solutions by 2mL concentration, in triplicate.Respectively the catalyst obtained by the reference polymer catalyst of 1.0mg and the present embodiment is added on above-mentioned system to measure, it the results are shown in Figure 6.Lower catalytic activity is presented 25 DEG C time relative to traditional non-response polyalcohol catalyst NiPC-N, NiPC-S; Otherwise 50 DEG C time, NiPC-S presents the higher catalytic activity of more traditional non-response polyalcohol catalyst NiPC-N.The NiPC-S catalyst of preparation obviously present can control, the characteristic of adjustable catalytic action, its classification catalytic mechanism is as shown in Figure 1.
Embodiment 2:
Polymerization catalyst thing mobile phase long-chain is controlled monomer and changes 2-nonenoic acid into by octadecenic acid, other operates with embodiment 1 completely, and obtained transformation temperature is the catalyst n iPC-S of 38 DEG C.Under the catalysis test condition that same embodiment 1 is identical, be catalytic substrate with rhodamine B, select lower than and carry out comparative determination higher than 30 DEG C and 45 DEG C of transformation temperature, it the results are shown in Figure 7.Lower catalytic activity is presented 30 DEG C time relative to traditional non-response polyalcohol catalyst NiPC-N, NiPC-S; Otherwise 45 DEG C time, NiPC-S presents the higher catalytic activity of more traditional non-response polyalcohol catalyst NiPC-N.The NiPC-S catalyst of preparation again present can control, the characteristic of adjustable catalytic action, show that the preparation method of catalyst of the present invention has certain applicability in other catalyst system and catalyzing.
Embodiment 3:
Will with acrylamide, N-dodecylacrylamide for function monomer, other operates with embodiment 1 completely, and obtained transformation temperature is the raw catelyst NiPC-S of about 40 DEG C.Under the catalysis test condition that same embodiment 1 is identical, select lower than and carry out comparative determination higher than 30 DEG C and 55 DEG C of transformation temperature, it the results are shown in Figure 8.Lower catalytic activity is presented when 30 DEG C lower than transformation temperature relative to traditional non-response polyalcohol catalyst NiPC-N, NiPC-S; Otherwise when 55 DEG C higher than transition point, NiPC-S presents the higher catalytic activity of more traditional non-response polyalcohol catalyst NiPC-N.The NiPC-S catalyst of preparation again present can control, the feature of adjustable catalytic action, show that the preparation method of NiPC-S catalyst of the present invention has certain applicability in other catalyst preparing.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; when not deviating from flesh and blood of the present invention, any apparent improvement that those skilled in the art can make, replacement or modification all belong to protection scope of the present invention.
Claims (9)
1. can control, the preparation method of the polyalcohol catalyst of adjustable metal nanoparticle load, it is characterized in that, comprise the following steps:
(1) function monomer, active constituent presoma, crosslinking agent and initator are dissolved in organic solvent; Described function monomer selects the long-chain compound and short chain compound that can be polymerized and produce crosslinked stationary phase and long-chain mobile phase, and the mol ratio of described long-chain compound and short chain compound is 1:7 ~ 14, and described active constituent presoma is metal ion state compound;
(2) under nitrogen protection, add thermal-initiated polymerization, form the polyalcohol catalyst presoma of metal nanoparticle load;
(3) metal ion in the polyalcohol catalyst presoma of metal nanoparticle load after sodium borohydride reduction, and cleans final vacuum drying repeatedly through water, ethanol, namely obtains the polyalcohol catalyst of described metal nanoparticle load.
2. preparation method according to claim 1, is characterized in that, the consumption of described organic solvent is can lytic activity component presoma, initator, function monomer and crosslinking agent be as the criterion; The consumption of crosslinking agent is 1 ~ 10wt% of function monomer; The consumption of active component presoma is as the criterion with the maximum coordination ratio being no more than function monomer; The consumption of initator is 1 ~ 10wt% of function monomer.
3. preparation method according to claim 1, is characterized in that, described long-chain compound is the one in octadecenic acid, 2-nonenoic acid, N-dodecylacrylamide, and short chain compound is acrylic acid or acrylamide.
4. preparation method according to claim 1, is characterized in that, crosslinking agent is N, N-methylene-bisacrylamide.
5. preparation method according to claim 1, is characterized in that, active component presoma is the one in nickel nitrate, silver nitrate, chloroplatinic acid.
6. preparation method according to claim 1, is characterized in that, initator is azodiisobutyronitrile (AIBN).
7. preparation method according to claim 1, is characterized in that, described organic solvent is methyl-sulfoxide.
8. preparation method according to claim 1, is characterized in that, polymeric reaction temperature scope is 60-70 DEG C.
9. what preparation method according to claim 1 obtained controls, the polyalcohol catalyst of adjustable metal nanoparticle load, it is characterized in that, metal nanoparticle take shape-memory polymer as carrier, and described carrier has crosslinked stationary phase and long-chain mobile phase.
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| CN106076414A (en) * | 2016-06-06 | 2016-11-09 | 江苏大学 | The metallic nanoparticle subbase catalyst that a kind of substrate is catalyzed in order |
| CN106311326A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Preparation method of Ni-based catalyst with adjustable selectivity/non-selectivity |
| CN106311327A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Preparation method of silver-loaded selectivity-changeable polymer catalyst |
| CN107317041A (en) * | 2017-07-12 | 2017-11-03 | 中国石油大学(北京) | A kind of catalyst layer and metal-air battery for metal air battery cathodes |
| CN110327973A (en) * | 2019-07-26 | 2019-10-15 | 湖北工程学院 | A kind of crosslinking norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst and the preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076414A (en) * | 2016-06-06 | 2016-11-09 | 江苏大学 | The metallic nanoparticle subbase catalyst that a kind of substrate is catalyzed in order |
| CN106076414B (en) * | 2016-06-06 | 2018-12-14 | 江苏大学 | A kind of metallic nanoparticle subbase catalyst that substrate is catalyzed in order |
| CN106311326A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Preparation method of Ni-based catalyst with adjustable selectivity/non-selectivity |
| CN106311327A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Preparation method of silver-loaded selectivity-changeable polymer catalyst |
| CN106311326B (en) * | 2016-07-25 | 2019-03-05 | 江苏大学 | A kind of preparation method of " selectivity/non-selective " adjustable Ni base catalyst |
| CN106311327B (en) * | 2016-07-25 | 2019-05-31 | 江苏大学 | A kind of preparation method of the convertible selective polyalcohol catalyst of silver load |
| CN107317041A (en) * | 2017-07-12 | 2017-11-03 | 中国石油大学(北京) | A kind of catalyst layer and metal-air battery for metal air battery cathodes |
| CN110327973A (en) * | 2019-07-26 | 2019-10-15 | 湖北工程学院 | A kind of crosslinking norbornene copolymer/carbon black three-dimensional network supported copper nanocatalyst and the preparation method and application thereof |
| CN110327973B (en) * | 2019-07-26 | 2021-12-21 | 湖北工程学院 | Crosslinked norbornene copolymer/carbon black three-dimensional network loaded copper nano catalyst and preparation method and application thereof |
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Application publication date: 20151007 |