CN102847534A - Light-driven regulation preparation method and electrocatalysis activity of nanometer material - Google Patents
Light-driven regulation preparation method and electrocatalysis activity of nanometer material Download PDFInfo
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Abstract
The invention relates to a light-driven regulation preparation method and electrocatalysis activity of a nanometer material. According to the present invention, a light-driven in situ nucleation method is adopted to regulate the average particle size of metal and alloy nanometer materials and the uniformity of particle size distribution, and modulate an illumination time, an illumination intensity, light source types, metal macrocyclic compound concentration and metal precursor concentration so as to achieve optically controlled synthesis of metal and alloy nanometer materials. The method of the present invention has characteristics of light controlling, simple operation, mild conditions, environment-friendliness, and easy amplification synthesis. The spherical branched platinum nanometer material prepared by the light controlled method of the present invention has a high electrochemical activity specific surface area, shows excellent electrocatalysis activity in an oxygen reduction reaction, and provides excellent electrocatalysis activity for methanol electrocatalysis oxidation reaction.
Description
Technical field
The invention belongs to the catalyst of fuel batter with proton exchange film field, relate to a kind of optical drive regulation and control preparation method and electro catalytic activity thereof of nano material.
Background technology
The various functions characteristic of Metal and Alloy nano material is not only closely bound up with pattern and composition, and in close relations with size and distribution of sizes.Effectively particle diameter and the distribution of sizes of control Metal and Alloy nano particle are most important to the practical application of material, are emphasis of material science research.Carried out relevant research both at home and abroad, and made some progress.
Such as: Li Yadongs etc. have prepared the monodispersed CuAu of particle diameter and Cu
3Au two group member nanocrystalline (Chen, W.; Yu, R.; Li, L., et al.Angew.Chem.2010,122,2979.).Shi Jianlin etc. have reported that particle diameter is monodispersed with Fe
3O
4Au is the nano composite material of shell for nuclear, and has studied its application (Dong, W. aspect Biological imaging and photo-thermal therapy; Li, Y.; Niu, D., et al.Adv.Mater.2011,23,5332.).Sun etc. have obtained the Pt nano cubic body structure about the monodispersed 8nm of particle diameter, find simultaneously activity (Wang, the C. of the electrical catalyze reduction oxygen that it has obvious improvement; Daimon, H.; Lee, Y., et al.J.Am.Chem.Soc.2007,129,6974.).Sun etc. have also studied the monodispersed Ni nano particle of particle diameter, and have investigated its catalytic activity to ammonia borane dehydrogenation hydrolysis (Metin, O.; Mazumder, V.;
S., et al.J.Am.Chem.Soc.2010,132,1468.).Fang etc. have synthesized the monodispersed Pt of particle diameter
3Fe nano cubic body structure, and its electro-chemical activity carried out detailed investigation (Zhang, J.; Yang, H.; Yang, K., et al.Adv.Funct.Mater.2010,20,3727.); In addition, also obtained the Pt-Cu nano cubic body structure of the monodispersed 8nm of particle diameter, found that it has high methanol oxidation active (Xu, D.; Liu, Z.; Yang, H., et al.Angew.Chem.Int.Edit.2009,48,4217.).Lee etc. have synthesized a series of Ag, Au, Pd particle diameter mono-dispersed nano particle (Zhang, Q. with icosahedral structure of virus; Xie, J.; Yang, J., et al.ACS nano 2008,3,139.).(Song, the Y. such as Song; Yang, Y.; Medforth, C.J., et al.J.Am.Chem.Soc.2004,126,635.) utilize soft template control to synthesize two dimension and three-dimensional dendritic Platinum Nanoparticles.
Reaction time and organic solvent that above-mentioned synthetic method mostly need to adopt higher temperature, grow, and lack universality.The method of a kind of blanket control Metal and Alloy nano particle diameter size and monodispersity is the two traditional steps to add crystal seed method.Then at first synthetic crystal seed is incorporated into crystal seed in the synthetic system, separates nucleation and growth course, suppresses to continue, nucleation process slowly, guarantees that each nuclearing centre all has roughly close growth time, realizes the homogeneity regulation and control of particle diameter.Simultaneously, the ratio of modulation crystal seed and metal precursor realizes the control of particle size.
From traditional to add crystal seed method different, the invention provides a kind of optical drive, original position nucleation process.(such as zinc protoporphyrin, ZnP) (see figure 1) makes it become excitation state (ZnP to the illumination transition metal macrocycle
*), it is a kind of strong reductant (ZnTPPS
4 .+/ ZnTPPS
4 *,-0.87V) can be reduced to metallic atom with metal ion rapidly, its oxidation product (ZnP
.+) can be generated ground state (ZnP) by the electron donor reduction, then can under illumination, carry out next light cyclic process (see figure 2) again.The optical drive nucleation method have the original position nucleation, can be light-operated, simple to operate, normal temperature and pressure synthesizes, be swift in response, the large and nucleation site of nuclearing centre number controlled characteristics within the specific limits in the unit volume, can obtain metal and the alloy nano-material of narrow diameter distribution.
Summary of the invention
The objective of the invention is to be to provide a kind of optical drive regulation and control preparation method and electro-chemical activity thereof of nano material, the method is to utilize optical drive original position, the fast Average Particle Diameters of nucleation regulation and control Metal and Alloy nano material and the method for particle diameter distribution uniformity, the method is simple to operate, can be light-operated, mild condition, environmental friendliness.
The invention provides a kind of optical drive regulation and control preparation method of nano material, the concrete steps of the method are: 1) transition metal macrocycle is dissolved in the aqueous solution that contains surfactant; 2) in above-mentioned steps 1) add successively the aqueous solution of water soluble metallic compound and the aqueous solution of water-soluble reducing agent in the solution of gained, to react under the illumination, centrifugation gets solid product; 3) with above-mentioned steps 2) obtain the metal or alloy nano material after the washing of the solid matter with deionized water of gained, drying; It is characterized in that: one or more in the concentration by changing light source, intensity of illumination, light application time, transition metal macrocycle, the concentration of water soluble metallic compound are used for homogeneity that regulation and control Metal and Alloy nano material Average Particle Diameters and particle diameter distribute.
The optical drive regulation and control preparation method of nano material provided by the invention, described light source is one or more in laser, visible light, the ultraviolet light.
The optical drive regulation and control preparation method of nano material provided by the invention, in the situation that other conditions are certain, along with the increase of intensity of illumination, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and described intensity of illumination scope is 0.1nmol cm
-2s
-1-10
6Nmol cm
-2s
-1
The optical drive regulation and control preparation method of nano material provided by the invention, in the situation that other conditions are certain, along with the increase of light application time, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and described light application time scope is 0.1-600s.
The optical drive regulation and control preparation method of nano material provided by the invention, described transition metal macrocycle is zinc (II) porphyrin, tin (IV) porphyrin, germanium (IV) porphyrin, magnesium (II) porphyrin, antimony (IV) porphyrin, zinc (II) phthalocyanine, tin (IV) phthalocyanine, germanium (IV) phthalocyanine, magnesium (II) phthalocyanine, antimony (IV) phthalocyanine, polypyrrole zinc (II), polypyrrole tin (IV), polypyrrole germanium (IV), polypyrrole magnesium (II), polypyrrole antimony (IV), polypyridine zinc (II), polypyridine tin (IV), polypyridine germanium (IV), polypyridine magnesium (II), polypyridine antimony (IV), phenanthroline zinc (II), phenanthroline tin (IV), phenanthroline germanium (IV), phenanthroline magnesium (II), one or more mixtures in phenanthroline antimony (IV) and the analog thereof.
The optical drive regulation and control preparation method of nano material provided by the invention, in the situation that other conditions are certain, increase along with transition metal macrocycle concentration, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and the concentration of described transition metal macrocycle is 0.1 μ mol/L-500mmol/L.
The optical drive regulation and control preparation method of nano material provided by the invention, described water soluble metallic compound is one or two or more kinds mixture in platinum compounds, ruthenium compound, rhodium compound, palladium compound, silver compound, rhenium compound, osmium compound, iridic compound, gold compound, iron compound, cobalt compound, nickel compound, the copper compound.
The optical drive regulation and control preparation method of nano material provided by the invention, in the situation that other conditions are certain, along with reducing of water soluble metallic compound concentration, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and the concentration of described water soluble metallic compound is 0.1mmol/L-500mmol/L.
The optical drive regulation and control preparation method of nano material provided by the invention, described platinum compounds is one or two or more kinds in chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite and the analog thereof;
Described ruthenium compound is one or two or more kinds in ruthenium trichloride, ruthenium hydrochloride, ruthenium hydrochloride salt and the analog thereof;
Described rhodium compound is one or two or more kinds in rhodium chloride, the acid of chlorine rhodium, chlorine rhodate and analog thereof;
Described palladium compound is one or two or more kinds in palladium chloride, tetrachloro-palladium acid, tetrachloro-palladium acid salt and the analog thereof;
Described silver compound is one or more in silver nitrate and the analog thereof;
Described rhenium compound includes but not limited to one or two or more kinds in rhenium pentachloride, perrhenic acid, perrhenate and the analog thereof;
Described osmium compound is one or two or more kinds in osmium tetrachloride, chlorine osmic acid, chloro-osmate and the analog thereof;
Described iridic compound is one or two or more kinds in iridic chloride, chloro-iridic acid, chloroiridate and the analog thereof;
Described gold compound is one or two or more kinds in gold trichloride, gold chloride, chloroaurate and the analog thereof;
Described iron compound is one or two or more kinds in ferric trichloride, dichloride ferrous iron, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate and the analog thereof;
Described cobalt compound is one or two or more kinds in cobaltous dichloride, cobaltic chloride, cobalt nitrate, cobaltous sulfate and the analog thereof;
Described nickel compound is one or two or more kinds in nickel chloride, nickelous sulfate, nickel nitrate and the analog thereof;
Described copper compound is one or two or more kinds in copper chloride, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate and the analog thereof.
The optical drive regulation and control preparation method of nano material provided by the invention, the concentration of described surfactant is 0.01mmol/L-1000mmol/L, and surfactant is one or more mixtures in Pluronic F-127 lauroyl ether, stearic acid, neopelex, softex kw and the analog thereof.
The optical drive regulation and control preparation method of nano material provided by the invention, the concentration of described water-soluble reducing agent is 0.5mmol/L-5000mmol/L, and water-soluble reducing agent is one or two or more kinds mixture in formaldehyde, formic acid, lithium borohydride, sodium borohydride, potassium borohydride, methyl alcohol, ethanol, polyalcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid and their derivative and the analog.
The present invention also provides a kind of sphere branched platinum nano catalyst, and this catalyst is to be prepared by method described above, and this catalyst has higher electrochemically active specific surface area, shows excellent activity in the reaction of electrical catalyze reduction oxygen.
The branched platinum nano catalyst of sphere provided by the invention, this catalyst shows excellent catalytic activity to anodic oxidation of methanol.
Compare with the method for dimensional homogeneity with the control nano particle diameter size of existing report, the present invention has the following advantages:
A) the present invention can be light-operated, original position nucleation, quick, simple to operate, mild condition, environmental friendliness, be easy to amplify synthetic.
B) adopt described method Kaolinite Preparation of Catalyst, one or two or more kinds in the concentration of the concentration by changing light source kind, light application time, intensity of illumination, transition metal macrocycle solution, the kind of transition metal macrocycle and water soluble metallic compound solution can be regulated and control the Average Particle Diameters of metal and alloy nano-material and the homogeneity that particle diameter distributes.
C) repeatedly inorganic and organic by-products in the preparation process can be effectively removed in washing, has solved difficult removal of accessory substance in the catalyst preparation and affects the problem of catalyst performance.
D) platinum catalyst that adopts described method to prepare, its pattern are spherical branched, and spherical branched Platinum Nanoparticles particle diameter is 10-500nm, and particle diameter is distributed as 5%-15%.
E) prepared spherical branched platinum nano catalyst has the high electrochemical activity specific area, shows excellent activity in oxygen reduction reaction, and anodic oxidation of methanol is shown excellent catalytic activity and durability.
Description of drawings
Fig. 1 is zinc protoporphyrin molecular structural formula of the present invention;
Fig. 2 is zinc protoporphyrin optical drive reduction Pt of the present invention
2+The nucleation principle;
Fig. 3 is transmission electron microscope (TEM) picture of the embodiment of the invention 1 preparation product;
Fig. 4 is that the particle diameter of the embodiment of the invention 1 preparation product distributes;
Fig. 5 is X-ray powder diffraction (XRD) spectrogram of the embodiment of the invention 1 preparation product;
Fig. 6 is cyclic voltammetric (CV) curve of the embodiment of the invention 1 preparation product;
Fig. 7 is hydrogen reduction (ORR) curve of the embodiment of the invention 1 preparation product;
Fig. 8 is the anodic oxidation of methanol cyclic voltammetry curve of the embodiment of the invention 1 preparation product;
Fig. 9 is that the embodiment of the invention 1 preparation product is at 0.69V(vs RHE) anodic oxidation of methanol chronoa mperometric plot under the constant potential;
Figure 10 is transmission electron microscope (TEM) photo of the embodiment of the invention 2 preparation products;
Figure 11 is that the particle diameter of the embodiment of the invention 2 preparation products distributes;
Figure 12 is transmission electron microscope (TEM) photo of the embodiment of the invention 3 preparation products;
Figure 13 is that the particle diameter of the embodiment of the invention 3 preparation products distributes;
Figure 14 is transmission electron microscope (TEM) photo of the embodiment of the invention 4 preparation products.
Figure 15 is transmission electron microscope (TEM) photo of the embodiment of the invention 5 preparation products.
The specific embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1:
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL zinc protoporphyrin (10 μ M), 1mM) aqueous solution joins in the reaction bulb, solution is in stirring, the aqueous ascorbic acid that adds successively 1mL 20mM chloroplatinous acid aqueous solutions of potassium and 1mL 150mM, (75V, luminous intensity is 570nmol cm at halogen tungsten lamp in reaction
-2s
-1) irradiation under carried out 60 seconds, close light source, afterreaction was finished at least 30 minutes.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains spherical branched platinum nano catalyst after the drying.
Such as Fig. 3, the TEM photo shows that spherical branched structure and morphology is single, and size evenly.
Such as Fig. 4, particle diameter distributes and shows that average grain diameter is 15.61 ± 1.96nm, and particle diameter is distributed as 12.56%.
Such as Fig. 5, XRD spectra shows that products therefrom is comprised of the metal platinum of face-centred cubic structure.
Such as Fig. 6, catalyst and cyclic voltammetry curve (50mV/s, 25 ℃, the 50 μ gPt/cms of commercial platinum black in the saturated high chloro acid solution of nitrogen of embodiment 1 preparation
2), be respectively 23.2m by the electrochemically active specific surface area that calculates spherical branched platinum nano catalyst and commercial platinum black
2g
-1And 18.1m
2g
-1, to compare with commercial platinum black, the electrochemical surface area of spherical branched platinum nano catalyst is higher, illustrates that its catalytic activity is better.
Such as Fig. 7, catalyst and hydrogen reduction curve (50mV/s, 1600rpm, 25 ℃, the 50 μ gPt/cms of commercial platinum black in the saturated high chloro acid solution of oxygen of embodiment 1 preparation
2), spherical branched platinum nano catalyst presents the initial reduction potential of ORR (15mV shuffles) than commercial platinum black corrigendum.Under the 0.85V polarization potential, active (the 114.6mA mg of the specific mass of spherical branched platinum nano catalyst
-1) and active (the 0.49mA cm of specific area
-2) all be higher than active (the 83.8mA mg of specific mass of commercial platinum black
-1) and the active (0.46mAcm of specific area
-2).
Such as Fig. 8, the catalyst of embodiment 1 preparation and commercial platinum black are at 0.5M H
2SO
4With 1.5M CH
3Electroxidation cyclic voltammetry curve in the OH aqueous solution (20mV/s, 25 ℃, 50 μ g
Pt/ cm
2), the catalyst that shows embodiment 1 preparation has the current density that is higher than commercial platinum black and lower take-off potential.
Such as Fig. 9, the methanol electro-oxidizing chronoa mperometric plot shows, under 0.69V voltage, carry out polarization scan (25 ℃, 50 μ gPt/cm
2), through behind the electric potential scanning of 3600s, the current density of the catalyst that embodiment 1 is prepared still is higher than commercial platinum black.
Embodiment 2:(light application time is different)
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL zinc protoporphyrin (10 μ M), 1mM) aqueous solution joins in the reaction bulb, solution is in stirring, the ascorbic acid solution that adds successively 1mL 20mM chloroplatinous acid potassium solution and 1mL 150mM, (75V, luminous intensity is 570nmol cm at halogen tungsten lamp in reaction
-2s
-1) irradiation under carried out 20 seconds, close light source, afterreaction was finished at least 30 minutes.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains spherical branched platinum nano catalyst after the drying.
Such as Figure 10, the TEM photo shows that spherical branched structure and morphology is single, and size evenly.
Such as Figure 11, particle diameter distributes and shows that average grain diameter is 27.82nm ± 3.64nm, and particle diameter is distributed as 13.08%.
Embodiment 3:(light application time is different)
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL zinc protoporphyrin (10 μ M), 1mM) aqueous solution joins in the reaction bulb, solution is in stirring, the ascorbic acid solution that adds successively 1mL 20mM chloroplatinous acid potassium solution and 1mL 150mM, (75V, luminous intensity is 570nmol cm at halogen tungsten lamp in reaction
-2s
-1) irradiation under carried out 40 seconds, close light source, afterreaction was finished at least 30 minutes.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains spherical branched platinum nano catalyst after the drying.
Such as Figure 12, the TEM photo shows that spherical branched structure and morphology is single, and size evenly.
Such as Figure 13, particle diameter distributes and shows that average grain diameter is 19.85 ± 2.5nm, and particle diameter is distributed as 12.62%.
Embodiment 4:(transition metal macrocycle concentration is different)
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL zinc protoporphyrin (70 μ M), 1mM) solution joins in the reaction bulb, solution is in stirring, the ascorbic acid solution that adds successively 1mL 20mM chloroplatinous acid potassium solution and 1mL 150mM, (75V, luminous intensity is 570nmol cm at halogen tungsten lamp in reaction
-2s
-1) irradiation under carried out 20 seconds, close light source, afterreaction was finished at least 30 minutes.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains platinum nano catalyst after the drying.
Such as Figure 14, the TEM photo shows that platinum nano catalyst is the platinum grain of 5-7nm, and size evenly has clustering phenomena.When one timing of water soluble metallic compound concentration, transition metal macrocycle concentration is higher, the nucleus that produces during illumination is more, therefore working as zinc protoporphyrin concentration is 70 μ M, water soluble metallic compound concentration is less, and illumination produces a large amount of nucleus, stops to only have a small amount of unreacted water soluble metallic compound to can be used for the growth of nucleus after the illumination, and can't form spherical branched platinum, so the catalyst that this system obtains is platinum grain.
Embodiment 5:(water soluble metallic compound concentration is different)
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL tin porphyrin (25 μ M), 1mM) aqueous solution joins in the reaction bulb, solution is in stirring, the ascorbic acid solution that adds successively 2mL 2mM chloroplatinous acid potassium solution and 2mL 150mM, (luminous intensity is 800nmol cm at incandescent lamp in reaction
-2s
-1) irradiation under carried out 120 seconds, close light source, afterreaction was finished at least 30 minutes.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains platinum nano catalyst after the drying.
Such as Figure 15, the TEM photo shows that platinum nano catalyst is the platinum grain of 2-3nm, and size evenly.When water soluble metallic compound concentration less, intensity of illumination is stronger, when transition metal macrocycle concentration is larger, illumination produces a large amount of nucleus, after illumination arrived certain hour, all metallic compounds were all for generation of nucleus, stop illumination after, do not remain water soluble metallic compound and form spherical branched platinum in the nucleus growth, so the catalyst that this system obtains is platinum grain of uniform size.
The embodiment 6:(reaction time is different)
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL zinc protoporphyrin (10 μ M), 1mM) aqueous solution joins in the reaction bulb, solution is in stirring, the ascorbic acid solution that adds successively 1mL 20mM chloroplatinous acid potassium solution and 1mL 150mM, (75V, luminous intensity is 570nmol cm at halogen tungsten lamp in reaction
-2s
-1) irradiation under carried out 10 minutes, close light source, afterreaction was finished at least 30 minutes.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains platinum nano catalyst after the drying.
The method gained sample topography is similar to embodiment 5 gained samples, and the platinum grain for 2-3nm has agglomeration.In the certain situation of water soluble metallic compound concentration, illumination produces a large amount of nucleus, when the light application time long enough, the water soluble metallic compound total overall reaction generates nucleus, after stopping illumination, crystal seed can't continue to grow as spherical branched platinum, so the catalyst that this system obtains is platinum grain of uniform size.
Embodiment 7:(light source, light intensity difference)
Pipette the Pluronic F-127 lauroyl ether (Brij-35 of 1mL zinc protoporphyrin (10 μ M), 1mM) aqueous solution joins in the reaction bulb, solution is in stirring, the ascorbic acid solution that adds successively 1mL 20mM chloroplatinous acid potassium solution and 1mL 150mM, (luminous intensity is 13.3 μ mol cm at laser in reaction
-2s
-1) irradiation under carry out 20s, close light source, the 30min afterreaction is finished at least.Reacted mixture is transferred in the centrifuge tube, and centrifugation obtains solid product, with the deionized water washing, obtains platinum nano catalyst after the drying.
The method gained sample topography is similar to embodiment 5 gained samples, and the platinum grain for 2-3nm has agglomeration.In the certain situation of water soluble metallic compound concentration and light application time, illumination produces a large amount of nucleus, when intensity of illumination is enough large, the water soluble metallic compound total overall reaction generates nucleus, after stopping illumination, crystal seed can't continue to grow as spherical branched platinum, so the catalyst that this system obtains is platinum grain of uniform size.
The invention is not restricted to above-mentioned illustrative example.Light source as described herein, intensity of illumination, light application time, transition metal macrocycle concentration, water-soluble metal salinity distribute all influential for Metal and Alloy nano material Average Particle Diameters and particle diameter, influence each other between each factor, interrelated.When other conditions one timings, change within the specific limits average grain diameter and particle diameter distribution that a certain factor can be regulated and control nano material, exceed this scope and then no longer have regulating and controlling effect, and need the mating reaction of other factors.For example, when light application time, transition metal macrocycle concentration, when the water-soluble metal salinity is certain, along with the increase of intensity of illumination, the average grain diameter of Metal and Alloy nano material diminishes, and the homogeneity that particle diameter distributes increases.But after intensity of illumination increases to certain value, namely under this intensity of illumination, behind the illumination certain hour, all water-soluble metal salts all are reduced the generation nucleus, therefore with this understanding, continue to increase intensity of illumination and can not play regulating and controlling effect to average grain diameter and the particle diameter distribution of material, other condition only changes, as reduce transition metal macrocycle concentration, increase metal salt concentrations or reduce light application time, the particle diameter and the particle diameter distribution that this condition are combined with intensity of illumination realize controlled material.
Claims (13)
1. the optical drive of a nano material is regulated and control the preparation method, and the concrete steps of the method are: 1) transition metal macrocycle is dissolved in the aqueous solution that contains surfactant; 2) in above-mentioned steps 1) add successively the aqueous solution of water soluble metallic compound and the aqueous solution of water-soluble reducing agent in the solution of gained, to react under the illumination, centrifugation gets solid product; 3) with above-mentioned steps 2) obtain the metal or alloy nano material after the washing of the solid matter with deionized water of gained, drying; It is characterized in that: one or more in the concentration by changing light source, intensity of illumination, light application time, transition metal macrocycle, the concentration of water soluble metallic compound are used for homogeneity that regulation and control Metal and Alloy nano material Average Particle Diameters and particle diameter distribute.
2. according to the optical drive regulation and control preparation method of the described nano material of claim 1, it is characterized in that: described light source is one or more in laser, visible light, the ultraviolet light.
3. regulate and control the preparation method according to the optical drive of the described nano material of claim 1, it is characterized in that: in the situation that other conditions are certain, increase along with intensity of illumination, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and described intensity of illumination scope is 0.1nmol cm
-2s
-1-10
6Nmol cm
-2s
-1
4. regulate and control the preparation method according to the optical drive of the described nano material of claim 1, it is characterized in that: in the situation that other conditions are certain, increase along with light application time, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and described light application time scope is 0.1-600s.
5. according to the optical drive regulation and control preparation method of the described nano material of claim 1, it is characterized in that: described transition metal macrocycle is zinc (II) porphyrin, tin (IV) porphyrin, germanium (IV) porphyrin, magnesium (II) porphyrin, antimony (IV) porphyrin, zinc (II) phthalocyanine, tin (IV) phthalocyanine, germanium (IV) phthalocyanine, magnesium (II) phthalocyanine, antimony (IV) phthalocyanine, polypyrrole zinc (II), polypyrrole tin (IV), polypyrrole germanium (IV), polypyrrole magnesium (II), polypyrrole antimony (IV), polypyridine zinc (II), polypyridine tin (IV), polypyridine germanium (IV), polypyridine magnesium (II), polypyridine antimony (IV), phenanthroline zinc (II), phenanthroline tin (IV), phenanthroline germanium (IV), phenanthroline magnesium (II), one or more mixtures in phenanthroline antimony (IV) and the analog thereof.
6. regulate and control the preparation method according to the optical drive of claim 1 or 5 described nano materials, it is characterized in that: in the situation that other conditions are certain, increase along with transition metal macrocycle concentration, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and the concentration of described transition metal macrocycle is 0.1 μ mol/L-500mmol/L.
7. according to the optical drive regulation and control preparation method of the described nano material of claim 1, it is characterized in that: described water soluble metallic compound is one or two or more kinds mixture in platinum compounds, ruthenium compound, rhodium compound, palladium compound, silver compound, rhenium compound, osmium compound, iridic compound, gold compound, iron compound, cobalt compound, nickel compound, the copper compound.
8. regulate and control the preparation method according to the optical drive of claim 1 or 7 described nano materials, it is characterized in that: in the situation that other conditions are certain, along with reducing of water soluble metallic compound concentration, the average grain diameter of Metal and Alloy nano material diminishes, the homogeneity that particle diameter distributes increases, and the concentration of described water soluble metallic compound is 0.1mmol/L-500mmol/L.
9. according to the optical drive regulation and control preparation method of the described nano material of claim 7, it is characterized in that:
Described platinum compounds is one or two or more kinds in chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite and the analog thereof;
Described ruthenium compound is one or two or more kinds in ruthenium trichloride, ruthenium hydrochloride, ruthenium hydrochloride salt and the analog thereof;
Described rhodium compound is one or two or more kinds in rhodium chloride, the acid of chlorine rhodium, chlorine rhodate and analog thereof;
Described palladium compound is one or two or more kinds in palladium chloride, tetrachloro-palladium acid, tetrachloro-palladium acid salt and the analog thereof;
Described silver compound is one or more in silver nitrate and the analog thereof;
Described rhenium compound includes but not limited to one or two or more kinds in rhenium pentachloride, perrhenic acid, perrhenate and the analog thereof;
Described osmium compound is one or two or more kinds in osmium tetrachloride, chlorine osmic acid, chloro-osmate and the analog thereof;
Described iridic compound is one or two or more kinds in iridic chloride, chloro-iridic acid, chloroiridate and the analog thereof;
Described gold compound is one or two or more kinds in gold trichloride, gold chloride, chloroaurate and the analog thereof;
Described iron compound is one or two or more kinds in ferric trichloride, dichloride ferrous iron, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate and the analog thereof;
Described cobalt compound is one or two or more kinds in cobaltous dichloride, cobaltic chloride, cobalt nitrate, cobaltous sulfate and the analog thereof;
Described nickel compound is one or two or more kinds in nickel chloride, nickelous sulfate, nickel nitrate and the analog thereof;
Described copper compound is one or two or more kinds in copper chloride, stannous chloride, copper sulphate, cuprous sulfate, copper nitrate, cuprous nitrate and the analog thereof.
10. regulate and control the preparation method according to the optical drive of the described nano material of claim 1, it is characterized in that: the concentration of described surfactant is 0.01mmol/L-1000mmol/L, and surfactant is one or more mixtures in Pluronic F-127 lauroyl ether, stearic acid, neopelex, softex kw and the analog thereof.
11. the optical drive regulation and control preparation method according to the described nano material of claim 1, it is characterized in that: the concentration of described water-soluble reducing agent is 0.5mmol/L-5000mmol/L, and water-soluble reducing agent is one or two or more kinds mixture in formaldehyde, formic acid, lithium borohydride, sodium borohydride, potassium borohydride, methyl alcohol, ethanol, polyalcohol, hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid and their derivative and the analog.
12. the branched platinum nano catalyst of sphere, this catalyst is to be prepared by method claimed in claim 1, and this catalyst has higher electrochemically active specific surface area, shows excellent activity in the reaction of electrical catalyze reduction oxygen.
13. according to the branched platinum nano catalyst of the described sphere of claim 12, it is characterized in that: this catalyst shows excellent catalytic activity to anodic oxidation of methanol.
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