CN103143394A - Nano-noble metal@magnetic polymer composite microsphere and preparation method thereof - Google Patents
Nano-noble metal@magnetic polymer composite microsphere and preparation method thereof Download PDFInfo
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- CN103143394A CN103143394A CN2013100476102A CN201310047610A CN103143394A CN 103143394 A CN103143394 A CN 103143394A CN 2013100476102 A CN2013100476102 A CN 2013100476102A CN 201310047610 A CN201310047610 A CN 201310047610A CN 103143394 A CN103143394 A CN 103143394A
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Abstract
The invention relates to a composite material and a preparation method thereof. With a magnetic polymer microsphere as a carrier, the composite material contains the following three parts: ferroferric oxide, a polystyrene core layer and a maleic acid isoalcohol diester shell layer. Specifically, ferroferric oxide is wrapped in the microsphere core layer, and a nano-noble metal is loaded on the microsphere shell layer. The microsphere prepared by the invention can subjected to separation recovery by a magnetic field so as to solve the waste problem of noble metals. With the polymer as the carrier, the catalytic efficiency of the nano-noble metal is substantially improved based on the enrichment effect of the polymer on an organic substrate, and also the biocompatibility of the composite material is improved. Thus, the composite microsphere provided in the invention is expected to have important application in selective catalysis and biomedicine fields in the future.
Description
Technical field
The invention belongs to polymer organic inorganic composite materials field and noble metal nano catalyst technical field, being specifically related to a kind of nano-noble metal@magnetic polymer composite microspheres and preparation method thereof, is exactly polymer microballoon of bag tri-iron tetroxide in shell nano-noble-metal-loaded, stratum nucleare and preparation method thereof.
Background technology
Nano-noble metal becomes an emerging study hotspot in recent years, and common noble metal has gold, platinum, rhodium, silver, ruthenium, palladium etc.The d electron orbit of these noble metals does not all fill up, and the surface is the adsorption reaction thing easily, has higher catalytic activity.Nano-noble metal also has the comprehensive good characteristics such as high temperature resistant, anti-oxidant, corrosion-resistant simultaneously, is widely used in chemical industry, petroleum refinement, medicine and other fields.
In the prior art, being used for the carrier of carried noble metal has metal oxide, zeolite, material with carbon element etc., but its load efficiency is low, environment for use is limited.Noble metal is combined with the magnetic polymer carrier, not only kept the original characteristic of nano material, also can greatly improve its dispersiveness, solve the nano-noble metal material and easily reunite and reclaim difficult problem; Simultaneously, the introducing of polymer has improved the biocompatibility of noble metal, has widened its application at biological technical field.
In this field, and Conghui Yuan etc. (Angew.Chem.Int.Ed.2011,50,3515-3519) take polystyrene spheres as matrix, first use gold chloride (HAuCl
4) it is etched into to a certain degree, then add reducing agent at the inner nano Au particle that generates of microballoon, this Polymer/nano gold system has very high selecting catalytic performance, but technique is comparatively complicated, and can't realize the magnetic separation of noble metal is reclaimed.Cheng Zhen equality a kind of (method for preparing noble metal/polymer nanometer hybrid particles, Chinese patent, publication number CN101544805A) take nano-silicon dioxide particle as core, the nano-silicon dioxide particle of preparation poly 4 vinyl pyridine layer parcel, obtain a kind of noble metal/polymer nanometer hybrid particles at its area load noble metal again, but can't solve equally the recovery problem of noble metal.(but a kind of noble metal of Magnetic Isolation and preparation method thereof such as Li Hongfang, Chinese patent, publication number CN102527437A) utilize the method for self assembly layer by layer that golden nanometer particle is loaded on magnetic microsphere, make catalyst effectively to separate and to reuse from reacted solution by externally-applied magnetic field.But the top layer of its magnetic microsphere is silica, and not only biocompatibility is poor, and can't use in alkaline environment, and practical application is greatly limited.
At present, take magnetic polymer with nucleocapsid structure as carrier, stratum nucleare comprises magnetic ferroferric oxide, and the complex microsphere of shell nano-noble-metal-loaded yet there are no report.
The present invention relates to a kind of nano-noble metal@magnetic polymer composite microspheres, with magnetic polymer microsphere as carrier, not only can separate recovery to noble metal by magnetic field, also take full advantage of polymer and " enrichment " effect of organic substrates has been improved greatly the catalytic efficiency of nano-noble metal, improve simultaneously the biocompatibility of composite, be expected to future obtain important application at selective catalysis, biomedicine field.
Summary of the invention
The object of the invention is to provide a kind of nano-noble metal@magnetic polymer composite microspheres and preparation method thereof.
Described nano-noble metal is a kind of in Au Ag Pt Pd.
Described magnetic polymer composite microspheres is a kind of polymer microsphere with nucleocapsid structure, and its stratum nucleare is polystyrene spheres and the interior bag magnetic ferroferric oxide of size 100 ~ 200nm, and shell is the different pure dibasic acid esters of the poly of 30 ~ 50nm.
The different pure dibasic acid esters of described maleic acid is a kind of polymerisable non-ionic surface active agent, is formed through two step esterifications by 18 alcohol, maleic anhydride, polyethylene glycol.
Described tri-iron tetroxide particle diameter is 5 ~ 15nm, adopts the chemical coprecipitation preparation, and utilizes in addition modification of oleic acid, and the mass ratio of oleic acid and tri-iron tetroxide is 1:1.05 ~ 1:1.15.
The preparation method of described nano-noble metal@magnetic polymer composite microspheres is as follows:
(1) ferriferrous oxide particles, styrene monomer, octane are mixed to get magnetic fluid, three's mass percent is followed successively by 5 ~ 60wt%, 35 ~ 80wt%, 5 ~ 15wt%.
(2) the different pure dibasic acid esters of maleic acid is dissolved in deionized water, stirs and add magnetic fluid after 1 ~ 2 hour, continue to stir and add initator to be warming up to 60 ~ 65 ℃ of reactions after 6 ~ 12 hours namely to obtain the magnetic polymer microsphere emulsion in 12 ~ 24 hours.Wherein, the content of the different pure dibasic acid esters of maleic acid is 0.1 ~ 3wt%, and magnetic fluid content is 1 ~ 5wt%, and surplus is deionized water; Initator is water soluble starter, and as potassium peroxydisulfate, ammonium persulfate etc., consumption accounts for 0.1 ~ 1wt% of magnetic fluid.
(3) get described magnetic polymer microsphere emulsion, add the noble metal acidulants aqueous solution, ultrasonic agitation added reducing agent aqueous solution continuation stirring namely to obtain nano-noble metal@magnetic polymer microsphere in 2 ~ 6 hours in 20 ~ 50 minutes.Described noble metal acidulants is a kind of in gold chloride, silver nitrate, chloroplatinic acid, the acid of chlorine palladium, and addition accounts for 0.1 ~ 1wt% of magnetic polymer microsphere emulsion; Described reducing agent is a kind of in sodium borohydride, ascorbic acid, citric acid, and addition accounts for 0.5 ~ 5wt% of magnetic polymer microsphere emulsion.
Nano-noble metal@magnetic polymer composite microspheres of the present invention is take magnetic polymer with nucleocapsid structure as carrier, stratum nucleare comprises magnetic ferroferric oxide, the shell nano-noble-metal-loaded takes full advantage of polymer " enrichment " of organic substrates effect is improved catalytic efficiency and biocompatibility greatly.
The explanation of accompanying drawing table
Fig. 1 is the TEM figure of nano-noble metal@magnetic polymer composite microspheres in embodiment 1.
Fig. 2 is the hysteresis curve figure of nano-noble metal@magnetic polymer composite microspheres in embodiment 1.
The experimental result of table 1 embodiment 2 ~ 4.
The experimental result of table 2 embodiment 5 ~ 7.
The specific embodiment
The present invention will be further described below by embodiment.
Embodiment 1
(1) preparation of magnetic polymer microsphere
9mL styrene, 1.5mL octane and 1.0g oleic acid improved ferroferric oxide mix, and ultrasonicly disperse to such an extent that magnetic fluid is standby.The different pure dibasic acid esters of 40mg maleic acid is dissolved in the 40mL deionized water, mechanical agitation 2 hours, add the described magnetic fluid of 3mL, logical nitrogen continues to stir and adds the 30mg potassium peroxydisulfate to be warming up to 65 ℃ of reactions after 12 hours to obtain having the magnetic polymer microsphere emulsion of nucleocapsid structure in 24 hours.
(2) preparation of nano-noble metal@magnetic polymer composite microspheres
Get the described magnetic polymer microsphere emulsion of 1mL and be diluted to 10mL with deionized water; Dropwise drip the aqueous solution of chloraurate that 1mL concentration is 10mmol/L under ultrasonic agitation; Adding 1mL concentration after 30 minutes is the sodium borohydride aqueous solution of 20mmol, and stirring at normal temperature namely obtains nano-noble metal@magnetic polymer composite microspheres after 6 hours.Take p-nitrophenol as substrate, carry out the catalytic reduction experiment, catalytic efficiency was 99.4% in 1 hour.
(TEM) carries out structural characterization to thus obtained microsphere by transmission electron microscope, and as Fig. 1, the overall dimensions of microballoon is the 250nm left and right, and wherein stratum nucleare is of a size of the 150nm left and right, and shell thickness is the 50nm left and right.Noble-metal-supported is of a size of the 10nm left and right on microballoon shell surface; Tri-iron tetroxide is included in microballoon inside, is of a size of the 8nm left and right; Its magnetic property is characterized by SQUID superconductive quantum interference magnetometer, and as Fig. 2, result shows that the saturated magnetic intensity of ratio of gained nano-noble metal@magnetic polymer microsphere is 20emug
-1, remanent magnetization and coercivity almost exist without magnetic hysteresis all close to 0, have superparamagnetism.
Embodiment 2 ~ 4
With embodiment 1 technique, change (1) middle feeding intake of oleic acid improved ferroferric oxide and be respectively 0.5g, 1.5g, 2g, result is as shown in table 1.
Embodiment 5 ~ 7
With embodiment 1 technique, change (2) middle noble metal acidulants kind and be respectively silver nitrate, chloroplatinic acid, the acid of chlorine palladium, obtain dissimilar nano-noble metal@magnetic polymer composite microspheres, result is as shown in table 2.
Table 1
Table 2
Claims (5)
1. nano-noble metal magnetic polymer composite microspheres, take magnetic polymer with nucleocapsid structure as carrier, stratum nucleare comprises magnetic ferroferric oxide, the complex microsphere of shell nano-noble-metal-loaded, described magnetic polymer composite microspheres is a kind of polymer microsphere with nucleocapsid structure, its stratum nucleare is polystyrene spheres and the interior bag magnetic ferroferric oxide of size 100 ~ 200nm, and shell is the different pure dibasic acid esters of the poly of 30 ~ 50nm.
2. a kind of nano-noble metal@magnetic polymer composite microspheres according to claim 1 is characterized in that described nano-noble metal is a kind of in Au Ag Pt Pd.
3. the preparation method of the nano-noble metal@of a place magnetic polymer composite microspheres is characterized in that step is as follows:
(1) ferriferrous oxide particles, styrene monomer, octane are mixed to get magnetic fluid, three's mass percent is followed successively by 5 ~ 60wt%, 35 ~ 80wt%, 5 ~ 15wt%.；
(2) the different pure dibasic acid esters of maleic acid is dissolved in deionized water, stirs and add described magnetic fluid after 1 ~ 2 hour, continue to stir and add initator to be warming up to 60 ~ 65 ℃ of reactions after 6 ~ 12 hours namely to obtain the magnetic polymer microsphere emulsion in 12 ~ 24 hours; Wherein, the content of the different pure dibasic acid esters of maleic acid is 0.1 ~ 3wt%, and magnetic fluid content is 1 ~ 5wt%, and surplus is deionized water; Initator is water soluble starter, and potassium peroxydisulfate or ammonium persulfate, consumption account for 0.1 ~ 1wt% of magnetic fluid;
(3) get described magnetic polymer microsphere emulsion, add the noble metal acidulants aqueous solution, ultrasonic agitation added reducing agent aqueous solution continuation stirring namely to obtain nano-noble metal@magnetic polymer microsphere in 2 ~ 6 hours in 20 ~ 50 minutes; Described noble metal acidulants is 0.1 ~ 1wt% that addition accounts for the magnetic polymer microsphere emulsion; Described reducing agent is a kind of in sodium borohydride, ascorbic acid, citric acid, and addition accounts for 0.5 ~ 5wt% of magnetic polymer microsphere emulsion.
4. a kind of nano-noble metal@magnetic polymer composite microspheres according to claim 3, it is characterized in that the different pure dibasic acid esters of described maleic acid is polymerisable non-ionic surface active agent, formed through two step esterifications by 18 alcohol, maleic anhydride, polyethylene glycol.
5. a kind of nano-noble metal@magnetic polymer composite microspheres according to claim 3, it is characterized in that described tri-iron tetroxide particle diameter is 5 ~ 15nm, employing chemical coprecipitation preparation, and utilize in addition modification of oleic acid, the mass ratio of oleic acid and tri-iron tetroxide is 1:1.05 ~ 1:1.15.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103646745A (en) * | 2013-12-16 | 2014-03-19 | 厦门大学 | Magnetic composite microsphere loaded with precious metal quantum dots and preparation method of magnetic composite microsphere |
| CN103831117A (en) * | 2014-04-04 | 2014-06-04 | 哈尔滨工业大学 | Preparation method for synthesizing platinum nanoparticles supported magnetic hollow capsule type catalyst by taking polystyrene as soft template |
| CN104625044A (en) * | 2015-01-20 | 2015-05-20 | 河南工程学院 | Ferroferric oxide/silver composite material and manufacturing method and application of ferroferric oxide/silver composite material |
| CN110665498A (en) * | 2019-10-16 | 2020-01-10 | 浙江大学台州研究院 | Preparation and application of noble metal-loaded magnetic nano stirrer catalyst |
| CN112121862A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetic immobilized platinum catalyst and preparation method and application thereof |
| CN113740311A (en) * | 2021-08-13 | 2021-12-03 | 电子科技大学 | Metal-dielectric material composite probe SERS substrate and preparation method thereof |
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| CN101698703A (en) * | 2009-10-22 | 2010-04-28 | 厦门大学 | Maleic acid isoalcohol diester and prepration method thereof |
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| CN102364616A (en) * | 2011-09-22 | 2012-02-29 | 华南师范大学 | Nanometer composite material Fe3O4@PS@Ag with core-shell structure and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103646745A (en) * | 2013-12-16 | 2014-03-19 | 厦门大学 | Magnetic composite microsphere loaded with precious metal quantum dots and preparation method of magnetic composite microsphere |
| CN103646745B (en) * | 2013-12-16 | 2016-04-06 | 厦门大学 | Magnetic composite microsphere of a kind of carried noble metal quantum dot and preparation method thereof |
| CN103831117A (en) * | 2014-04-04 | 2014-06-04 | 哈尔滨工业大学 | Preparation method for synthesizing platinum nanoparticles supported magnetic hollow capsule type catalyst by taking polystyrene as soft template |
| CN104625044A (en) * | 2015-01-20 | 2015-05-20 | 河南工程学院 | Ferroferric oxide/silver composite material and manufacturing method and application of ferroferric oxide/silver composite material |
| CN110665498A (en) * | 2019-10-16 | 2020-01-10 | 浙江大学台州研究院 | Preparation and application of noble metal-loaded magnetic nano stirrer catalyst |
| CN110665498B (en) * | 2019-10-16 | 2022-08-26 | 浙江大学台州研究院 | Preparation and application of noble metal-loaded magnetic nano stirrer catalyst |
| CN112121862A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetic immobilized platinum catalyst and preparation method and application thereof |
| CN113740311A (en) * | 2021-08-13 | 2021-12-03 | 电子科技大学 | Metal-dielectric material composite probe SERS substrate and preparation method thereof |
| CN113740311B (en) * | 2021-08-13 | 2022-12-20 | 电子科技大学 | Metal-dielectric material composite probe SERS substrate and preparation method thereof |
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Application publication date: 20130612 |