Summary of the invention
The purpose of this invention is to provide a kind of method that in polyelectrolyte multilayer film, prepares gold-silver alloy nanoparticles.
Described preparation method may further comprise the steps:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 5.0-9.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of the polymine of branching of 5mg/ml or linear polymine, and is clean with pure water rinsing;
3) then, with step 2) to be soaked in pH be 3.0-7.0 for the sheet glass handled, and concentration is the polyacrylic acid of 5mg/ml or polymethyl acid solution 10 minutes, and water is rinsed well again;
4) repeating step 2) and step 3), polyelectrolyte multilayer film obtained;
5) polyelectrolyte multilayer film that step 4) is obtained is 2.0-3.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; In the aqueous solution of 10mM silver nitrate, soaked 1-10 minute then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, obtains gold-silver alloy nanoparticles.
Beneficial effect: characteristics of the present invention are directly to connect a layer self assembly polyelectrolyte multilayer film by the electrostatic interaction layer on base material, adsorb gold chloride anion and silver ion successively after, prepare gold-silver alloy nanoparticles by adding thermal reduction.Whole process of preparation is easy and simple to handle, directly obtains nano particle in multilayer film, and particle diameter is 3.8 ± 0.8nm.This method can be used for preparing the preparation of the alloy that contains different gold and silver ratios.The gold-silver alloy nanoparticles that is obtained has the surface plasma body resonant vibration absorption signal of feature, has high using value in fields such as catalysis, optics.
The specific embodiment
Embodiment 1:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 7.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of branching of 5mg/ml, and is clean with pure water rinsing;
3) then, with step 2) to be soaked in pH be 3.5 to sheet glass, concentration is the polyacrylic acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 10 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; At last, this multilayer film that obtains is placed baking oven, heated 1 hour down, promptly obtain gold-silver alloy nanoparticles at 200 ℃.Can clearly see the existence of product nano particle from Fig. 1.
Embodiment 2:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 9.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of branching of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 3.0, and concentration is the polyacrylic acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.5 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 10 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Embodiment 3:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 5.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of branching of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 7.0, and concentration is the polyacrylic acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 5 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 5 polyelectrolyte multilayer film is 3.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 10 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Embodiment 4:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 7.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of branching of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 3.5, and concentration is the polyacrylic acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 5 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Embodiment 5:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 7.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of branching of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 3.5, and concentration is the polyacrylic acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 1 minute in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Embodiment 6:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 7.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of linearity of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 3.5, and concentration is the polyacrylic acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 10 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Embodiment 7:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 7.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of branching of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 3.5, and concentration is the polymethyl acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 10 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Embodiment 8:
1) be that 7: 3 mass percent is after 98% sulfuric acid and mass percent are to soak 30 fens kinds in the mixed solution of 30% hydrogen peroxide, with pure water this sheet glass to be rinsed well with sheet glass in volume ratio;
2) sheet glass that step 1) was handled is 7.0 at pH, and concentration is to soak 10 minutes in the aqueous solution of polymine of linearity of 5mg/ml, and is clean with pure water rinsing;
3) then sheet glass being soaked in pH is 3.5, and concentration is the polymethyl acid solution 10 minutes of 5mg/ml, and is clean with pure water rinsing again;
4) repeating step 2) and step 3) be 7 polyelectrolyte multilayer film to the double-deck number that obtains polyelectrolyte;
5) the double-deck number that step 4) is obtained is that 7 polyelectrolyte multilayer film is 2.0 at pH, and concentration is to soak 15 minutes in the aqueous solution of gold chloride of 5mM, and is clean with pure water rinsing; Be to soak 10 minutes in the aqueous solution of 10mM silver nitrate in concentration then, clean with pure water rinsing; This multilayer film that will obtain at last places baking oven, heats 1 hour down at 200 ℃, promptly obtains gold-silver alloy nanoparticles.
Curve 1-3 among Fig. 2 is respectively embodiment 5,4, the ultraviolet-visible absorption spectroscopy of 1 gold-silver alloy nanoparticles that makes, show that the nano particle that makes has unimodal plasma and absorbs feature, its absworption peak is between monometallic Nano silver grain and golden nanometer particle, and along with the increase of the mol ratio of silver ion in the system and gold ion, absworption peak moves to short wavelength's direction.