CN102527437A - Magnetically-separable noble metal catalyst and preparation method thereof - Google Patents
Magnetically-separable noble metal catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnetically-separable noble metal catalyst and a preparation method thereof. The catalyst consists of a magnetic carrier and noble metal nanoparticles, wherein the magnetic carrier is a microsphere with a core-shell structure; the core is made of ferroferric oxide and the shell is made of silicon dioxide; and the noble metal nanoparticles are aurum nanoparticles. The aurum nanoparticles are loaded on the magnetic microsphere by a layer-by-layer self-assembling method, so that the catalyst can be effectively separated out from a solution obtained after reaction through an external magnetic field and can be reused, and the problem that the metal nanoparticles in the conventional noble metal catalytic reaction system are difficult to separate is solved.
Description
Technical field
The invention belongs to the noble metal nano catalyst technical field, but be specifically related to a kind of Au catalyst and preparation method thereof and the application in organic and inorganic reduction reaction of Magnetic Isolation.
Background technology
Noble metal nano particles is owing to its smaller particle size, higher surface activity are widely used as catalyst.Noble metal nano particles under proper condition can catalysis fracture H-H, C-H, C-C and C-O key.Because this particle does not have hole, can avoid owing to reactant causes some side reaction to the slow diffusion of endoporus, thereby its activity all is higher than similar traditional catalyst with selectivity.Yet two drawbacks limit that noble metal nano particles itself exists its application at catalytic field.At first, because noble metal nano particles has little size and high dispersiveness is arranged in reaction system, therefore be difficult to it is thoroughly separated from system; In addition, noble metal nano particles has high surface can make it tend to assemble the big particle of formation, finally loses the characteristic of its nano particle.A kind of method that addresses these problems is exactly that they are fixed on the solid-state carrier.The carrier as noble metal nano particles such as material with carbon element, metal oxide and zeolite reported in a large amount of articles, yet their application has also run into the difficult problem of catalyst separation.Because these carriers are the granule of powder, adopt traditional mechanical separation method such as filtration and centrifugal, length consuming time, energy consumption is high, and the efficient of separating is also not ideal enough.Magnetic Isolation is a kind of novel green separation process.It can reclaim catalyst fast and effectively, reduces the pollution to environment, reduces the energy consumption of separation process.Thereby load on noble metal nano particles on the carrier of magnetic, being assembled into the magnetic supported noble metal catalyst, magnetic capable of using separates realizes catalyst recovery, makes it both keep good catalytic activity, can reuse again.
Composite material of core-shell structure has unique character and in the potential using value of numerous areas.On magnetic core, wrap one deck indifferent oxide shell such as silica, can avoid magnetic core in the solution of strong acid and strong base, to be corroded, again can be in the new functional group of the outer surface grafting of indifferent oxide shell, thus greatly enrich its surface chemistry.Noble metal nano particles immobilized can make on the magnetic carrier of such nucleocapsid structure metallic recycling in the high catalytic activity of maintenance; Simultaneously noble metal nano particles is modified on the core-shell structure magnetic ball with functional characteristic, obtained difunctional or multi-functional composite.Synergy in the composite between each composition will promote the character of each component in this material to improve respectively.
Self assembly layer by layer is a kind of simple method of constructing membrane material.It is polycation that the present invention's employing gathers ethylene diamine, and the golden nanometer particle of citrate parcel is as anion, through electrostatic interaction, at the magnetic microsphere surface-assembled multilayer film of nucleocapsid structure.Golden nanometer particle is fixed in the multilayer film that gathers ethylene diamine, and its loose structure guarantees that catalytic substrate can arrive the active site of golden nanometer particle fast, thus guarantee fund's nano particle catalytic performance efficiently.
Summary of the invention
But the present invention has prepared a kind of noble metal catalyst of Magnetic Isolation, and this catalyst is made up of magnetic carrier and noble metal nano particles.Wherein magnetic carrier is the nucleocapsid structure microballoon that tri-iron tetroxide and silica constitute, and noble metal nano particles is a golden nanometer particle.
Described Fe 3 O 4 magnetic microballoon is under the high-temperature water heat condition, to prepare, and its granular size (is seen accompanying drawing 1) between the 300-360 nanometer; The thickness of silica shell in 20 nanometers between 25 nanometers; Golden nanometer particle utilizes citric acid reduction preparation under fluidized state.This gold nano grain of preparation in advance can be controlled its pattern and particle diameter effectively.Golden nanometer particle granular size among the present invention is about 12 nanometers, and pattern is spherical
But the noble metal catalyst of the Magnetic Isolation of the present invention's preparation is the method through self assembly layer by layer; Wherein gather ethylene diamine as polycation; The golden nanometer particle of citrate parcel is as anion; Through electrostatic interaction, load to golden nanometer particle on the magnetic microsphere surface (seeing accompanying drawing 2) of nucleocapsid structure.
But the noble metal catalyst of the Magnetic Isolation of the present invention's preparation all has excellent catalytic activity in organic reducing reaction (the p-nitrophenol reduction generates para-aminophenol) and inorganic reduction reaction (the potassium ferricyanate reduction generates ferrous potassium cyanate).
But the noble metal catalyst of the Magnetic Isolation of the present invention's preparation is convenient to Separation and Recovery.After reaction finishes, under the effect of outside magnetic field, separate rapidly in 30 seconds.This catalyst has good recycling, and after repeatedly recycling, its catalytic activity remains on more than 90%.
Description of drawings
The stereoscan photograph of the magnetic microsphere of Fig. 1 load gold
The transmission electron microscope photo of the magnetic microsphere of Fig. 2 load gold
Uv-vis spectra changed before and after Fig. 3 nitrophenol and sodium borohydride reaction added Au catalyst
Uv-vis spectra changed before and after Fig. 4 potassium ferricyanate and sodium thiosulfate reaction added Au catalyst
Fig. 5, five circular response rate variation of Au catalyst curve
The specific embodiment
Embodiment 1: the preparation of the magnetic core of nucleocapsid structure
At first, preparation tri-iron tetroxide microballoon.2.7g FeCl
36H
2O and 7.2g sodium acetate join in the 100mL ethylene glycol solution, and magnetic is stirred to the yellow settled solution that forms homogeneous, change over to then in the teflon-lined high pressure water heating kettle, and 200 ℃ are reacted 8h down.The four iron oxide magnetic particle waters and the ethanol cyclic washing that obtain, 50 ℃ of vacuum drying are subsequent use then.Before tri-iron tetroxide area load silica shell, the 0.1g tri-iron tetroxide is at first used 15mL 2M HCl solution sonicated 5min.Magnetic Isolation, washing joins 400mL ethanol then, in the mixed solution of 100mL ultra-pure water and 15mL concentrated ammonia liquor, behind the mechanical agitation 15min, dropwise adds the positive tetraethyl orthosilicate of 3.5mL, continues mechanical agitation reaction 6h.Silica impurity in the solution, the core-shell structure magnetic microballoon that obtains are removed in the external magnetic field separation.With ethanol and ultra-pure water cyclic washing, subsequent use after the last vacuum drying.
Embodiment 2: the preparation of golden nanometer particle
250mL HAuCl
43H
2The O aqueous solution (1mM) and 25mL sodium citrate aqueous solution (38.3mM) all are heated to boiling under magnetic agitation.Join the sodium citrate solution of boiling rapidly in the precursor solution of gold then, mixed solution removes thermal source after continuing to stir 10min, and solution continues to stir 15min, obtains containing the purplish red solution of golden nanometer particle.After the cooling, stored refrigerated, subsequent use.
Embodiment 3: the load of golden nanometer particle on magnetic microsphere
Golden nanometer particle passes through self-assembling method layer by layer in the load of magnetic microsphere; Carry out according to following steps: (i) at first to join 10mL concentration be that 10mg/mL gathers in ethylene diamine (PEI) aqueous solution to the magnetic microsphere carrier of 0.25g nucleocapsid structure; Stir 30min, at microsphere surface absorption one deck PEI polycation.Magnetic Isolation then, cyclic washing is removed unnecessary PEI.Contain 0.5M NaCl in the PEI solution as supporting electrolyte, the pH of solution is adjusted into 8.5.The magnetic microsphere that has (ii) adsorbed PEI continues to join in the synthetic in advance Au solution of 10mL; Stir 30min; At PEI polycation surface adsorption last layer golden nanometer particle, repeat above the separation and washing process, the magnetic microsphere that PEI/Au is double-deck that obtained load.Repeat (i) and (ii) two steps, obtain assembling the magnetic microsphere of different PEI/Au bilayer numbers, the load capacity of its golden nanometer particle from 1.27% to 5.70% is adjustable continuously.
Embodiment 4: load the catalytic performance test in the p-nitrophenol reduction reaction of the magnetic microsphere of golden nanometer particle
Contain 0.75 * 10
-3The mmol load magnetic microsphere of golden nanometer particle add and to contain 1.5mL p-nitrophenol (0.01M), 100mL water and 1.5mL NaBH
4In the mixed solution (1M), continuous electronic stirring reaction under 25 ℃, every at a distance from 5min sampling, Magnetic Isolation catalyst, the uv-vis spectra of test solution.Be reflected in the 20min and accomplish, solution colour becomes colourless from glassy yellow.
Catalytically active assessment: p-nitrophenol adds NaBH
4After, uv-vis spectra medium wavelength 400nm place is corresponding to the absorption of p-nitrophenyl phenates.Along with the carrying out of reaction, the intensity of this absworption peak reduces.Owing in the course of reaction, add excessive N aBH
4So this reaction can be similar to regards first order reaction as.After getting negative logarithm to the absorbance value that records the 400nm wavelength, be abscissa with time, mapping.After the curve match, the slope of the straight line that obtains i.e. the reaction rate of reduction reaction for this reason.Blank assay only adds the reaction substrate of the same concentration of equal volume and does not add catalyst.Uv-vis spectra is characterized in the ultraviolet-visual spectrometer of the Lambda-35 type of U.S. PerkinElmer company production.
Do not add catalyst, that reaction is carried out and slow.And after adding a spot of catalyst, be swift in response and carry out, the absworption peak of 400nm sharply reduces.According to-lnA
400/ t the slope of curve calculates reaction rate, and behind the adding catalyst, reaction rate has improved 90 times nearly.
Embodiment 5: load the catalytic performance test in the potassium ferricyanate reduction reaction of the magnetic microsphere of golden nanometer particle
Contain 1.0 * 10
-3The magnetic microsphere of mmol golden nanometer particle adds and contains 2mL K
3[Fe (CN)
6] (0.01M), 30mL H
2O and 2mL Na
2S
2O
3(0.1M) in the solution, 40 ℃ of following continuous electronic stirring reaction 90min, every at a distance from 10min sampling, the uv-vis spectra of Magnetic Isolation catalyst test solution.Catalytically active assessment carries out according to the method for embodiment 4.Owing to add excessive sodium thiosulfate in the course of reaction, regard first order reaction as so this reaction also can be similar to.K
3[Fe (CN)
6] characteristic absorption peak at 420nm, get negative logarithm to the absorbance value that records the 420nm wavelength in the experiment after, be the abscissa mapping with time.After the curve match, the slope that obtains straight line i.e. the reaction rate of reduction reaction for this reason.Do not add catalyst, reaction almost can not be carried out.Add the catalyst afterreaction and carry out smoothly, the absworption peak at 420nm place reduces gradually.According to-lnA
420/ t the slope of curve calculates reaction rate.After adding catalyst, reaction rate has improved 8 times nearly.
Embodiment 6: load the recycle of magnetic microsphere in two reaction systems of golden nanometer particle
After a catalysis of embodiment 4,5 completion experiment, adopt the catalyst in the external magnetic field separation solution, with ultra-pure water cyclic washing, oven dry.Repeat above experimental procedure, get into multiple cycles and use.Among the present invention, catalyst recycling 5 times.After using for 5 times, the catalytic performance of catalyst remains on more than 90%.Therefore, but the Magnetic Isolation gold nano catalyst structure among the present invention is stable, has excellent recycling.
Claims (8)
1. but the noble metal catalyst of a Magnetic Isolation comprises magnetic carrier with superparamagnetism and the noble metal nano particles with catalytic activity, and it is characterized in that: magnetic carrier is the microballoon of nucleocapsid structure, and noble metal nano particles is a golden nanometer particle.
2. noble metal catalyst as claimed in claim 1 is characterized in that: the microballoon of described nucleocapsid structure, and examining to particle diameter is the ferriferrous oxide particles of 300-360nm, shell is that thickness is the silica of 20-25nm.
3. noble metal catalyst as claimed in claim 1 is characterized in that: the golden nanometer particle pattern is for spherical, and particle diameter is about 12nm.
4. but the preparation method of the noble metal catalyst of a kind of Magnetic Isolation as claimed in claim 1 is characterized in that: adopt self-assembling method layer by layer.
5. but like the purposes of the noble metal catalyst of claim 1,2 or 3 described Magnetic Isolation, it is characterized in that: this catalyst be used for catalysis organic with the inorganic reduction reaction.
6. purposes as claimed in claim 5 is characterized in that: described organic reducing reaction is the reaction of p-nitrophenol and sodium borohydride, and the inorganic reduction reaction is the reaction of potassium ferricyanate and sodium thiosulfate.
7. but the noble metal catalyst of a kind of Magnetic Isolation as claimed in claim 1 is characterized in that: adopt external magnetic field to carry out the separation and the recycle of catalyst fast.
8. but the noble metal catalyst of a kind of Magnetic Isolation as claimed in claim 1 is characterized in that: after recycling for five times, catalytic activity remains on more than 90%.
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Cited By (14)
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|---|---|---|---|---|
| CN102990078A (en) * | 2013-01-16 | 2013-03-27 | 无锡市寰创环境科技发展有限公司 | Method for preparing nanoscale zero-valent iron loaded on surfaces of glass beads by virtue of layer-by-layer assembly |
| CN103157493A (en) * | 2013-03-21 | 2013-06-19 | 北京化工大学 | Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol |
| CN103191784A (en) * | 2013-03-28 | 2013-07-10 | 北京化工大学 | Magnetic nickel aluminum hydrotalcite composite material loaded with gold nanoparticles and application thereof for catalyzing reduction reaction of p-nitrophenol |
| CN103212441A (en) * | 2013-04-12 | 2013-07-24 | 中国科学院福建物质结构研究所 | Bimetal pyridine film catalyst and preparation and application thereof |
| CN104307578A (en) * | 2014-11-12 | 2015-01-28 | 东南大学 | Reactivation method of ceramic catalyst in sodium borohydride reduction reaction of p-nitrophenol |
| CN104888868A (en) * | 2015-05-29 | 2015-09-09 | 广西大学 | Preparation method of precious metal loaded Fe3O4 nanospheres |
| CN105126869A (en) * | 2015-08-26 | 2015-12-09 | 辽宁石油化工大学 | Method for preparing p-aminophenol by adopting Ni/Ag/Fe3O4 complex catalyst |
| CN107649184A (en) * | 2017-09-27 | 2018-02-02 | 武汉工程大学 | A kind of perfusion silica gel/nanogold complex microsphere and its preparation method and application |
| CN107824198A (en) * | 2017-11-09 | 2018-03-23 | 武汉工程大学 | A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold |
| CN109626549A (en) * | 2019-01-17 | 2019-04-16 | 上海理工大学 | A kind of method of quick catalysis degradation 4- nitrophenol |
| CN109847762A (en) * | 2019-01-18 | 2019-06-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst, preparation method and application for the reaction of hydrogenation synthesis para-aminophenol |
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| CN114910435A (en) * | 2022-05-09 | 2022-08-16 | 洛阳莱博图电子科技有限公司 | Water quality total nitrogen detection reagent and preparation method thereof |
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Cited By (21)
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| CN102990078A (en) * | 2013-01-16 | 2013-03-27 | 无锡市寰创环境科技发展有限公司 | Method for preparing nanoscale zero-valent iron loaded on surfaces of glass beads by virtue of layer-by-layer assembly |
| CN103157493A (en) * | 2013-03-21 | 2013-06-19 | 北京化工大学 | Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol |
| CN103157493B (en) * | 2013-03-21 | 2015-01-28 | 北京化工大学 | Noble metal supported composite functional nano sphere catalyst having recoverability function and application thereof in catalyzing reduction of p-nitrophenol |
| CN103191784A (en) * | 2013-03-28 | 2013-07-10 | 北京化工大学 | Magnetic nickel aluminum hydrotalcite composite material loaded with gold nanoparticles and application thereof for catalyzing reduction reaction of p-nitrophenol |
| CN103191784B (en) * | 2013-03-28 | 2015-05-13 | 北京化工大学 | Magnetic nickel aluminum hydrotalcite composite material loaded with gold nanoparticles and application thereof for catalyzing reduction reaction of p-nitrophenol |
| CN103212441A (en) * | 2013-04-12 | 2013-07-24 | 中国科学院福建物质结构研究所 | Bimetal pyridine film catalyst and preparation and application thereof |
| CN104307578A (en) * | 2014-11-12 | 2015-01-28 | 东南大学 | Reactivation method of ceramic catalyst in sodium borohydride reduction reaction of p-nitrophenol |
| CN104307578B (en) * | 2014-11-12 | 2016-06-29 | 东南大学 | Ceramic catalyst rejuvenation method in sodium borohydride reduction paranitrophenol reacts |
| CN104888868A (en) * | 2015-05-29 | 2015-09-09 | 广西大学 | Preparation method of precious metal loaded Fe3O4 nanospheres |
| CN105126869A (en) * | 2015-08-26 | 2015-12-09 | 辽宁石油化工大学 | Method for preparing p-aminophenol by adopting Ni/Ag/Fe3O4 complex catalyst |
| CN107649184A (en) * | 2017-09-27 | 2018-02-02 | 武汉工程大学 | A kind of perfusion silica gel/nanogold complex microsphere and its preparation method and application |
| CN107824198A (en) * | 2017-11-09 | 2018-03-23 | 武汉工程大学 | A kind of preparation method and applications of the magnetic nano-catalyst of supported nano-gold |
| CN109626549A (en) * | 2019-01-17 | 2019-04-16 | 上海理工大学 | A kind of method of quick catalysis degradation 4- nitrophenol |
| CN109626549B (en) * | 2019-01-17 | 2021-11-30 | 上海理工大学 | Method for rapidly catalyzing and degrading 4-nitrophenol |
| CN109847762A (en) * | 2019-01-18 | 2019-06-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst, preparation method and application for the reaction of hydrogenation synthesis para-aminophenol |
| CN112619666A (en) * | 2020-11-30 | 2021-04-09 | 深圳市人民医院 | Preparation method and application of central radial-diplopore nano composite material |
| CN112619666B (en) * | 2020-11-30 | 2023-10-03 | 深圳市人民医院 | Preparation method and application of center radial-double-hole nano composite material |
| 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 |
| CN114910435A (en) * | 2022-05-09 | 2022-08-16 | 洛阳莱博图电子科技有限公司 | Water quality total nitrogen detection reagent and preparation method thereof |
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Application publication date: 20120704 |