CN104722333B - A kind of palladium nucleoprotamine plural layers and preparation method thereof - Google Patents
A kind of palladium nucleoprotamine plural layers and preparation method thereof Download PDFInfo
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- CN104722333B CN104722333B CN201510059832.5A CN201510059832A CN104722333B CN 104722333 B CN104722333 B CN 104722333B CN 201510059832 A CN201510059832 A CN 201510059832A CN 104722333 B CN104722333 B CN 104722333B
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Abstract
The invention discloses a kind of palladium nucleoprotamine plural layers and preparation method thereof, obtain multi-layer compound film on the surface of mica sheet material by layer assembly method, and preparation process is simple, at low cost, are suitble to mass production；The ingredient and pattern that product can be controlled in terms of function film preparation, are not particularly limited film forming matrix, do not need special equipment, and the film of preparation has a good chemical stability, and the composition and thickness of film are controllable etc..The complex multi layer films of preparation are a kind of functional films containing palladium, can be used for catalyzed coupling reaction, high catalytic efficiency, yield is up to 90~99%, thus the film is with a wide range of applications.
Description
Technical field
The present invention relates to technical field of material chemistry, a kind of palladium nucleoprotamine complex multi layer films and its preparation side are particularly related to
Method.
Background technique
In recent years, film material with function is widely used in micro- because of its unique optics, electricity, magnetics and chemical characteristic
The technical fields such as electronic device, wearing layer and catalytic chemistry.The diversity of thin-film material type determines that preparation method is also more
Kind multiplicity, is broadly divided into physical method and chemical method two major classes.Physical method mainly includes being evaporated in vacuo (VE), vacuum to splash
Penetrate (VS), pulse laser deposition (PLD), molecular beam epitaxy (MBE) etc.；Chemical method then includes various chemical vapor depositions
(CVD), chemical bath deposition (CBD), electrodeposition process (ED), sol-gel method (So1-Ge1), successive ionic layer adsorption and reaction
Method (SILAR), numerator self-assembly technique method (Molecular Self-assembly) and template synthesis method (Template
Synthesis) etc..In these preparations and protection painting technology, molecule layer-by-layer is prepared in film material with function and is led
Domain shows unique advantage, and many film material with function are prepared by this technology and obtained.
As preparation, uniform, multilayer complex films effective ways have caused people greatly to be closed to molecule layer-by-layer
Note.Inorganic nanoparticles (NPs), organic component can be combined in film in an orderly manner with this method, in solid substrate
On construct multi-functional supramolecular structure, and the structure and thickness of multilayer film can be regulated and controled on a molecular scale, thus real
The functions such as light, electricity, magnetic, the nonlinear optics of existing film.
Currently, people are with self assembly successfully by different types of inorganic nanoparticles and nano-cluster, such as TiO2, vulcanization
Object, noble metal etc. are assembled into film.And noble metal nano particles are due to having good catalytic with big specific surface
Matter.High dispersive, support type nanoscale precious metal catalyst preparation be even more by catalysis scholar attention, this is because carrier
And its polymolecularity can greatly improve again the utilization rate of noble metal while improving nano-metal particle stability.Layer by layer from group
High-sequential, controllability and the ultra-thin property of film itself are filled, is provided for the assembling of inorganic nano-particle on it special micro-
Environment and measured response site.Bruening is prepared for the polyelectrolyte comprising Pd nano particle by layer-by-layer
Film, this film can be used for the catalytic hydrogenation reaction of ethyl alcohol.
The active feature high, by-product is few of palladium salt homogeneous catalysis C-C coupling reaction.But due on palladium salt homogeneous catalyst
Carrying capacity is big, is not readily separated recycling, and palladium is lost serious, not only use cost height, but also pollution environment.And pass through layer assembly method shape
At complex multi layer films have high catalyst activity, can be recycled for multiple times, reduce the dosage of catalyst, thus greatly
Cost is reduced greatly, has important application in catalytic field.
Summary of the invention
In view of this, it is an object of the invention to propose that a kind of preparation process is simple and at low cost, and there is good catalysis
The palladium nucleoprotamine complex multi layer films of performance.
Based on a kind of above-mentioned purpose palladium nucleoprotamine plural layers provided by the invention, the film be by nucleoprotamine and
Palladium salt is combined, and preparation method includes the following steps:
1) one layer of gold thin film of spraying is adopted in clean mica sheet substrate material surface with vacuum vapour deposition；
2) dry after spraying one layer of aqueous solution containing nucleoprotamine on above-mentioned gold thin film surface with high pressure vacuum rifle；
3) dry with high pressure vacuum rifle after above-mentioned nucleoprotamine film surface sprays one layer of aqueous solution containing palladium salt；
4) the mica sheet base material of palladium is put into reducing agent above-mentioned load, solution temperature is 30~60 DEG C, is impregnated
120~720min；By control reaction time and temperature, divalent palladium (II) is reduced to zeroth order palladium (0), the valence state and content of palladium
It is measured by x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP)；
5) above-mentioned 2), 3) He 4) step is repeated, forms plural layers in above-mentioned mica sheet surface, as composite multi-layer is thin
Film.
Preferably, the concentration of the nucleoprotamine aqueous solution is 5.0~15mg/mL.
Preferably, the palladium salt is palladium chloride or palladium acetate, and the concentration of aqueous solution of palladium is 1.0~5.0mmol/L.
Preferably, the reducing agent is sodium borohydride, and sodium citrate etc., the concentration of reducing agent is 10~20mmol/L.
From the above it can be seen that a kind of palladium nucleoprotamine plural layers provided by the invention, advantage are as follows: the present invention
Multi-layer compound film is obtained on the surface of mica sheet base material by layer-layer spray coating method, preparation process is simple, and cost is relatively low,
The ingredient and pattern that product can be controlled in terms of film material with function preparation do not need special equipment, the film tool of preparation
There is a good chemical stability, the composition and thickness of film are controllable etc., it is suitble to mass production.Gold thin film helps fixed milt egg
White, nucleoprotamine plays a part of fixed in the film and disperses palladium particle, while having certain work to the catalytic activity of palladium
Change effect.Keep the partial size of palladium particle in catalyst smaller by slowly restoring, improves the dispersion degree and the uniformity of palladium particle, and
Increase the activated centre of palladium catalyst.The palladium nucleoprotamine functionalization film of preparation, catalytic activity is high, can be used for catalytic coupling
Reaction, high catalytic efficiency are 90~99%, which is with a wide range of applications in catalytic field.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of palladium of embodiment of the present invention complex multi layer films.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in more detail.
Embodiment 1
One layer of gold thin film of spraying is adopted in clean mica sheet substrate material surface with vacuum vapour deposition.Then high pressure vacuum is used
It is dry after rifle sprays one layer of nucleoprotamine aqueous solution containing 15mg/mL on gold thin film surface.Again with high pressure vacuum rifle in milt egg
White film surface sprays one layer of PdCl for being contained in 5.0mmol/L2It is dry after in aqueous solution.Above-mentioned load is had to the mica sheet of palladium
Base material is put into the sodium borohydride aqueous solution of 20mmol/L, in 30 DEG C of immersion 720min.By the divalent palladium (II) on film
It is reduced to zeroth order palladium (0).It repeats the above steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and contain
Amount is measured by the analysis methods such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).Use scanning electron microscopic observation
The pattern of five layer film of palladium, as shown in Figure 1.
Embodiment 2
One layer of gold thin film of spraying is adopted in clean mica sheet substrate material surface with vacuum vapour deposition.Then high pressure vacuum is used
It is dry after rifle sprays one layer of nucleoprotamine aqueous solution containing 5.0mg/mL on gold thin film surface.Again with high pressure vacuum rifle in milt
It is dry after one layer of protein films surface spraying is contained in the acetic acid aqueous palladium of 1.0mmol/L.Above-mentioned load is had to the mica of palladium
Piece base material is put into the sodium borohydride aqueous solution of 10mmol/L, in 60 DEG C of immersion 120min.By the divalent palladium on film
(II) it is reduced to zeroth order palladium (0).It repeats the above steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium
It is measured with content by the analysis methods such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).Use scanning electron microscope
Observe the pattern of five layer film of palladium.
Embodiment 3
One layer of gold thin film of spraying is adopted in clean mica sheet substrate material surface with vacuum vapour deposition.Then high pressure vacuum is used
It is dry after rifle sprays one layer of nucleoprotamine aqueous solution containing 10mg/mL on gold thin film surface.Again with high pressure vacuum rifle in milt egg
It is dry after one layer of white film surface spraying is contained in the acetic acid aqueous palladium of 2.0mmol/L.Above-mentioned load is had to the mica sheet of palladium
Base material is put into the sodium citrate aqueous solution of 15mmol/L, in 45 DEG C of immersion 480min.By the divalent palladium (II) on film
It is reduced to zeroth order palladium (0).It repeats the above steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and contain
Amount is measured by the analysis methods such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).Use scanning electron microscopic observation
The pattern of five layer film of palladium.
Embodiment 4
One layer of gold thin film of spraying is adopted in clean mica sheet substrate material surface with vacuum vapour deposition.Then high pressure vacuum is used
It is dry after rifle sprays one layer of nucleoprotamine aqueous solution containing 5.0mg/mL on gold thin film surface.Again with high pressure vacuum rifle in milt
Protein films surface sprays one layer of PdCl for being contained in 3.0mmol/L2It is dry after in aqueous solution.Above-mentioned load is had to the mica of palladium
Piece base material is put into the sodium citrate aqueous solution of 10mmol/L, in 60 DEG C of immersion 36min.By the divalent palladium (II) on film
It is reduced to zeroth order palladium (0).It repeats the above steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and contain
Amount is measured by the analysis methods such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).Use scanning electron microscopic observation
The pattern of five layer film of palladium.
By taking palladium nucleoprotamine film prepared by embodiment 1 and embodiment 3 as an example, catalysis reaction is carried out:
The palladium nucleoprotamine plural layers prepared using above-described embodiment 1 are that catalyst carries out catalysis reaction, reaction condition
Are as follows: will to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol) and K2CO3(3.0mmol) in air atmosphere in
EtOH/H2The in the mixed solvent of O (3mL/4mL) is reacted, and reaction temperature is 50 DEG C, reaction time 4h.Using column chromatography point
From product, yield 99%.It is as follows to react skeleton symbol:
The palladium nucleoprotamine plural layers for using above-described embodiment 3 to prepare carry out catalysis reaction as catalyst, react item
Part are as follows: by para-bromoanisole (1.0mmol), to methylphenylboronic acid (1.2mmol) and K2CO3(3.0mmol) in air atmosphere in
EtOH/H2The in the mixed solvent of O (3mL/4mL) is reacted, and reaction temperature is 50 DEG C, reaction time 4h.Using column chromatography point
From product, yield 90%.It is as follows to react skeleton symbol:
It should be understood by those ordinary skilled in the art that: the above is only a specific embodiment of the present invention, and
It is not used in the limitation present invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done,
It should be included within protection scope of the present invention.
Claims (1)
1. a kind of palladium nucleoprotamine plural layers, which is characterized in that the film is combined by nucleoprotamine and palladium salt, packet
Include following preparation step:
1) one layer of gold thin film of spraying is adopted in clean mica sheet substrate material surface with vacuum vapour deposition；
2) dry after spraying one layer of aqueous solution containing nucleoprotamine on above-mentioned gold thin film surface with high pressure vacuum rifle；
3) dry with high pressure vacuum rifle after above-mentioned nucleoprotamine film surface sprays one layer of aqueous solution containing palladium salt；
4) the mica sheet base material of palladium is put into reducing agent above-mentioned load, solution temperature is 30~60 DEG C, immersion 120~
720min；By control reaction time and temperature, the palladium of divalent is reduced to the palladium of zeroth order；
5) above-mentioned 2), 3) He 4) step is repeated, forms plural layers, as palladium nucleoprotamine plural layers in mica sheet surface；
The concentration of the nucleoprotamine aqueous solution is 5.0~15mg/mL；
The palladium salt is palladium chloride or palladium acetate, and the concentration of aqueous solution of palladium is 1.0~5.0mmol/L；
The reducing agent is sodium borohydride, and sodium citrate, the concentration of reducing agent is 10~20mmol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186333A (en) * | 2007-12-19 | 2008-05-28 | 天津大学 | Bionic preparation method for nanometer titanium dioxide micro-sphere |
| WO2010083589A1 (en) * | 2009-01-23 | 2010-07-29 | Kane Biotech Inc. | Biofilm-removing antimicrobial compositions and uses thereof |
| CN103934022A (en) * | 2013-12-04 | 2014-07-23 | 宁波大学 | Palladium composite multilayered film |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186333A (en) * | 2007-12-19 | 2008-05-28 | 天津大学 | Bionic preparation method for nanometer titanium dioxide micro-sphere |
| WO2010083589A1 (en) * | 2009-01-23 | 2010-07-29 | Kane Biotech Inc. | Biofilm-removing antimicrobial compositions and uses thereof |
| CN103934022A (en) * | 2013-12-04 | 2014-07-23 | 宁波大学 | Palladium composite multilayered film |
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