CN104722333A - Multilayer thin film with palladium protamine and preparation method thereof - Google Patents
Multilayer thin film with palladium protamine and preparation method thereof Download PDFInfo
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- CN104722333A CN104722333A CN201510059832.5A CN201510059832A CN104722333A CN 104722333 A CN104722333 A CN 104722333A CN 201510059832 A CN201510059832 A CN 201510059832A CN 104722333 A CN104722333 A CN 104722333A
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- palladium
- thin film
- nucleoprotamine
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Abstract
The invention discloses a multilayer thin film with palladium protamine and a preparation method thereof. The multilayer compound thin film disclosed by the invention is obtained on the surface of a mica sheet material by a layer-by-layer assembling method, the preparation process is simple, and the cost is low, so that the multilayer compound thin film is suitable for mass production; the components and the morphology of a product can be controlled in the aspect of preparation of the functional thin film, no special limitation is formed for a film-forming matrix, special equipment is not needed, the prepared thin film is good in chemical stability, the composition and the thickness of the thin film can be controlled and the like. The prepared compound multilayer thin film is a palladium-containing functional thin film and can be used for catalytic coupling reaction, the catalytic efficiency is high, and the yield can reach 90%-99%, so that the thin film has wide application prospect.
Description
Technical field
The present invention relates to technical field of material chemistry, refer to a kind of palladium nucleoprotamine complex multi layer films and preparation method thereof especially.
Background technology
In recent years, film material with function, because of the optics of its uniqueness, electricity, magnetics and chemical characteristic, is widely used in the technical fields such as microelectronic component, wearing layer and catalytic chemistry.It is also varied that the diversity of thin-film material kind determines its preparation method, is broadly divided into physical method and the large class of chemical method two.Physical method mainly comprises vacuum evaporation (VE), vacuum sputtering (VS), pulsed laser deposition (PLD), molecular beam epitaxy (MBE) etc.; Chemical method then comprises various chemical vapour deposition (CVD) (CVD), chemical bath deposition (CBD), electrodeposition process (ED), sol-gel process (So1-Ge1), successive ionic layer adsorption and reaction method (SILAR), numerator self-assembly technique method (Molecular Self-assembly) and template synthesis method (TemplateSynthesis) etc.In these preparations and protection painting technology, molecule layer-by-layer shows unique advantage in film material with function preparation field, and many film material with function are prepared by this technology and obtain.
Molecule layer-by-layer is even as preparation, the effective ways of multilayer complex films have caused people to pay close attention to greatly.Inorganic nanoparticles (NPs), organic component can be combined in film by profit in this way in an orderly manner, solid substrate is constructed polyfunctional supramolecular structure, and structure and the thickness of multilayer film can be regulated and controled on a molecular scale, thus realize optical, electrical, the function such as magnetic, nonlinear optics of film.
At present, people with self assembly successfully by different types of inorganic nanoparticles and nano-cluster, as TiO
2, sulfide, noble metal etc. be assembled in film.And noble metal nano particles is owing to having large specific surface, there is good catalytic property.The preparation of the nanoscale precious metal catalyst of high dispersive, support type is subject to the attention of catalysis scholar especially, this is because carrier and polymolecularity thereof greatly can improve again the utilization rate of noble metal while improving nano-metal particle stability.The high-sequential of LBL self-assembly film self, controllability and ultra-thin property, for inorganic nano-particle assembling thereon provides special microenvironment and measured response site.Bruening has prepared the polyelectrolyte membrane comprising Pd nano particle by layer-by-layer, this film can be used for the catalytic hydrogenation reaction of ethanol.
Palladium salt homogeneous catalysis C-C coupling reaction has the feature that activity is high, accessory substance is few.But because carrying capacity on palladium salt homogeneous catalyst is large, not easily separation and recovery, palladium runs off serious, and not only use cost is high, and contaminated environment.And be there is by the complex multi layer films that layer assembly method is formed the activity of high catalyst, repeatedly can recycle, decrease the consumption of catalyst, thus greatly reduce costs, have important application at catalytic field.
Summary of the invention
In view of this, the object of the invention is to propose that a kind of preparation process is simple and cost is low, and have good catalytic palladium nucleoprotamine complex multi layer films.
Based on above-mentioned purpose a kind of palladium nucleoprotamine plural layers provided by the invention, described film is composited by nucleoprotamine and palladium salt, and its preparation method comprises the following steps:
1) spraying one deck gold thin film is adopted by vacuum vapour deposition at the mica sheet substrate material surface of cleaning;
2) use high pressure vacuum rifle after above-mentioned gold thin film surface spraying one deck is containing the aqueous solution of nucleoprotamine, dry;
3) one deck is sprayed containing after palladium saline solution with high pressure vacuum rifle at above-mentioned nucleoprotamine film surface, dry;
4) above-mentioned load had the mica sheet base material of palladium to put into reducing agent, solution temperature is 30 ~ 60 DEG C, soaks 120 ~ 720min; By controlling reaction time and temperature, divalent palladium (II) is reduced to zeroth order palladium (0), the valence state of palladium and content are measured by x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP);
5) repeat above-mentioned 2), 3) and 4) step, form plural layers in above-mentioned mica sheet surface, be complex multi layer films.
Preferably, the concentration of the described nucleoprotamine aqueous solution is 5.0 ~ 15mg/mL.
Preferably, described palladium salt is palladium bichloride or palladium, and the concentration of aqueous solution of palladium is 1.0 ~ 5.0mmol/L.
Preferably, described reducing agent is sodium borohydride, natrium citricum etc., and the concentration of reducing agent is 10 ~ 20mmol/L.
As can be seen from above, a kind of palladium nucleoprotamine plural layers provided by the invention, advantage is as follows: the present invention obtains multi-layer compound film by layer-layer spraying process on the surface of mica sheet base material, preparation process is simple, and cost is lower, can control composition and the pattern of product in prepared by film material with function, do not need special equipment, the film of preparation has good chemical stability, the composition of film and thickness controlled etc., be applicable to a large amount of production.Gold thin film helps fixing nucleoprotamine, and nucleoprotamine plays a part fixing and dispersion palladium particle in the film, has certain activation to the catalytic activity of palladium simultaneously.Making the particle diameter of palladium particle in catalyst less by slowly reducing, improve decentralization and the uniformity of palladium particle, and adding the activated centre of palladium catalyst.The palladium nucleoprotamine functionalization film of preparation, catalytic activity is high, can be used for catalyzed coupling reaction, and catalytic efficiency is high, and be 90 ~ 99%, this film is with a wide range of applications at catalytic field.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment of the present invention palladium complex multi layer films.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
Embodiment 1
Spraying one deck gold thin film is adopted at the mica sheet substrate material surface of cleaning by vacuum vapour deposition.Then use high pressure vacuum rifle after gold thin film surface spraying one deck is containing the nucleoprotamine aqueous solution of 15mg/mL, dry.Spray at nucleoprotamine film surface the PdCl that one deck is contained in 5.0mmol/L again with high pressure vacuum rifle
2after in the aqueous solution, dry.Above-mentioned load there is the mica sheet base material of palladium to put into the sodium borohydride aqueous solution of 20mmol/L, soak 720min at 30 DEG C.Divalent palladium (II) on film is reduced to zeroth order palladium (0).Repeat above-mentioned steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and content are measured by the analytical method such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).With the pattern of scanning electron microscopic observation palladium five layer film, as shown in Figure 1.
Embodiment 2
Spraying one deck gold thin film is adopted at the mica sheet substrate material surface of cleaning by vacuum vapour deposition.Then use high pressure vacuum rifle after gold thin film surface spraying one deck is containing the nucleoprotamine aqueous solution of 5.0mg/mL, dry.Spray one deck with high pressure vacuum rifle at nucleoprotamine film surface to be again contained in after in the palladium aqueous solution of 1.0mmol/L, dry.Above-mentioned load there is the mica sheet base material of palladium to put into the sodium borohydride aqueous solution of 10mmol/L, soak 120min at 60 DEG C.Divalent palladium (II) on film is reduced to zeroth order palladium (0).Repeat above-mentioned steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and content are measured by the analytical method such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).With the pattern of scanning electron microscopic observation palladium five layer film.
Embodiment 3
Spraying one deck gold thin film is adopted at the mica sheet substrate material surface of cleaning by vacuum vapour deposition.Then use high pressure vacuum rifle after gold thin film surface spraying one deck is containing the nucleoprotamine aqueous solution of 10mg/mL, dry.Spray one deck with high pressure vacuum rifle at nucleoprotamine film surface to be again contained in after in the palladium aqueous solution of 2.0mmol/L, dry.Above-mentioned load there is the mica sheet base material of palladium to put into the sodium citrate aqueous solution of 15mmol/L, soak 480min at 45 DEG C.Divalent palladium (II) on film is reduced to zeroth order palladium (0).Repeat above-mentioned steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and content are measured by the analytical method such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).With the pattern of scanning electron microscopic observation palladium five layer film.
Embodiment 4
Spraying one deck gold thin film is adopted at the mica sheet substrate material surface of cleaning by vacuum vapour deposition.Then use high pressure vacuum rifle after gold thin film surface spraying one deck is containing the nucleoprotamine aqueous solution of 5.0mg/mL, dry.Spray at nucleoprotamine film surface the PdCl that one deck is contained in 3.0mmol/L again with high pressure vacuum rifle
2after in the aqueous solution, dry.Above-mentioned load there is the mica sheet base material of palladium to put into the sodium citrate aqueous solution of 10mmol/L, soak 36min at 60 DEG C.Divalent palladium (II) on film is reduced to zeroth order palladium (0).Repeat above-mentioned steps five times, five layer films can be formed on the surface of mica sheet.The valence state of palladium and content are measured by the analytical method such as x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP).With the pattern of scanning electron microscopic observation palladium five layer film.
For palladium nucleoprotamine film prepared by embodiment 1 and embodiment 3, carry out catalytic reaction:
The palladium nucleoprotamine plural layers using above-described embodiment 1 to prepare carry out catalytic reaction for catalyst, and reaction condition is: will to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol) and K
2cO
3(3.0mmol) in air atmosphere in EtOH/H
2react in the mixed solvent of O (3mL/4mL), reaction temperature is 50 DEG C, and the reaction time is 4h.Adopt column chromatography separated product, productive rate is 99%.Reaction skeleton symbol is as follows:
The palladium nucleoprotamine plural layers using above-described embodiment 3 to prepare carry out catalytic reaction as catalyst, and reaction condition is: by para-bromoanisole (1.0mmol), to methylphenylboronic acid (1.2mmol) and K
2cO
3(3.0mmol) in air atmosphere in EtOH/H
2react in the mixed solvent of O (3mL/4mL), reaction temperature is 50 DEG C, and the reaction time is 4h.Adopt column chromatography separated product, productive rate is 90%.Reaction skeleton symbol is as follows:
Those of ordinary skill in the field are to be understood that: the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. palladium nucleoprotamine plural layers, is characterized in that, described film is composited by nucleoprotamine and palladium salt, comprises following preparation process:
1) spraying one deck gold thin film is adopted by vacuum vapour deposition at the mica sheet substrate material surface of cleaning;
2) use high pressure vacuum rifle after above-mentioned gold thin film surface spraying one deck is containing the aqueous solution of nucleoprotamine, dry;
3) one deck is sprayed containing after palladium saline solution with high pressure vacuum rifle at above-mentioned nucleoprotamine film surface, dry;
4) above-mentioned load had the mica sheet base material of palladium to put into reducing agent, solution temperature is 30 ~ 60 DEG C, soaks 120 ~ 720min; By controlling reaction time and temperature, divalent palladium (II) is reduced to zeroth order palladium (0), the valence state of palladium and content are measured by x-ray photoelectron spectroscopy (XPS) and plasma emission spectrum (ICP);
5) repeat above-mentioned 2), 3) and 4) step, mica sheet surface formed plural layers, be complex multi layer films.
2. palladium nucleoprotamine plural layers according to claim 1, is characterized in that, the concentration of the described nucleoprotamine aqueous solution is 5.0 ~ 15mg/mL.
3. palladium nucleoprotamine plural layers according to claim 1, is characterized in that, described palladium salt is palladium bichloride or palladium, and the concentration of aqueous solution of palladium is 1.0 ~ 5.0mmol/L.
4. palladium nucleoprotamine plural layers according to claim 1, is characterized in that, described reducing agent is sodium borohydride, natrium citricum etc., and 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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