CN103071530B - Application of metal nanoparticles - Google Patents
Application of metal nanoparticles Download PDFInfo
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- CN103071530B CN103071530B CN201310004140.1A CN201310004140A CN103071530B CN 103071530 B CN103071530 B CN 103071530B CN 201310004140 A CN201310004140 A CN 201310004140A CN 103071530 B CN103071530 B CN 103071530B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method for metal nanoparticles. According to the method, polyamide-amine dendritic polymers are taken as a template and a dispersing agent, and the methyl alcohol is taken as a reducing agent, so that the metal nanoparticles with the advantages of uniform size, high stability and favorable catalytic activity are prepared. The method is simple to operate and has good repeatability, and the prepared nanoparticles can be directly applicable to the system of hydrogen production by water decomposed by visible light without postprocessing. The invention further provides the application of the metal nanoparticles, which can be used for the system of hydrogen production by water decomposed by visible light.
Description
Technical field
The invention belongs to material science, energy science and catalytic science field, relate to a kind of application of metal nanoparticle particularly.
Background technology
Solar energy, as a kind of clean regenerative resource, is that plant carries out photosynthetic energy source, is also the total source including wind energy, water energy, tide energy equal energy source on the earth simultaneously.For a long time, be the energy crisis that reply is facing, people strive to find effective approach always and utilize solar energy.Photochemistry conversion is one of important form of solar energy utilization, it is one of effective means that can thoroughly solve energy problem that Hydrogen Energy is recognized, if can utilize the solar energy photocatalytic hydrogen production by water decomposition of cleanliness without any pollution, convert solar energy into Hydrogen Energy, will fundamentally solve the energy and the environmental problem of facing mankind.The homogeneous phase decomposing water with solar energy that current research is maximum produces ternary system (Komatsu, T.eta.lJ.Am.Chem.Soc., 2006,128,16297 that hydrogen system is made up of sensitising agent, electron carrier and proton reducing catalyst; Probst, B.etal.Inorg.Chem., 2008,48,1836).In this system, reaction is normally carried out under sacrificial body exists, and photic electronics shifts the sensitizer oxidation state forming must pass through sacrificial body reducing/regenerating.Produce in hydrogen process in catalysis, the catalytic efficiency of proton reducing catalyst often becomes the key factor of hydrogen generation speed.Therefore, find more efficiently, more stable proton reducing catalyst has great significance for improving energy conversion efficiency.
Research discovery, the noble metals such as gold, platinum, palladium have good catalysis and produce hydrogen character.Conventionally adopt the macromolecules such as polyvinyl alcohol, polyvinylpyrrolidone to prepare the metal nanoparticle of different size as dispersant.But due to high molecular polymolecularity, the metal nanoparticle size heterogeneity that causes it to prepare.And the size of metallic particles can obviously affect the catalysis hydrogen generation efficiency (Varpness, Z.etal.Nano Lett., 2005,5,2306) of catalyst.Therefore, find a kind of method of preparing controlled, the particle homogeneous metal nano catalyst of size, for the utilization rate that improves noble metal, reduce that to produce hydrogen cost significant.
In recent years, the seminar such as Crooks, Tomalia and Esumi use respectively polyamide-amide dendritic as template and dispersant, prepare the different metal particle homogeneous phase aqueous solution (Zhao that big or small homogeneous, structure are comparatively stable, M.Q.eta.lJ.Am.Chem.Soc., 1998,120,4877; Lajos, B.etal.Inorg.Chem., 1998,120,7355; Kunio, E.etal.Langmuir., 1998,14,3157), in its preparation process, need to add excessive sodium borohydride as reducing agent, but the speed that adds of sodium borohydride can have a strong impact on size and the stability of metal nanoparticle, and reaction condition requires strict, poor repeatability; In addition, the excessive sodium borohydride adding is difficult for removing from system, has limited it and has further applied.
The metal nanoparticle that polyamide-amide dendritic disperses is showing very high catalytic activity (Scott, R.W.J. aspect some organic chemical reactionses; Wilson, O.M.; Crooks, R.M.J.Phys.Chem.B., 2005,109,692-704; Niu, Y.H.; Yeung, L.K.; Crooks, R.M.J.Am.Chem.Soc.2001,123,6840-6846; Scott, R.W.J.; Wilson, O.M.; Oh, S.K.; Kenik, E.A.; Crooks, R.M.J.Am.Chem.Soc.2004,126,15583-15591.), but use it in light hydrogen production by water decomposition system also not relevant research and report.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of preparation method of metal nanoparticle; The method is using polyamide-amide class dendritic as template and dispersant, using methyl alcohol as reducing agent, makes the metal nanoparticle that big or small homogeneous, stability are high, have superior catalytic activity; The method is simple to operate, has good repeatability, and the nano particle making does not need just can directly apply to using visible light to decompose water and make hydrogen system through post processing.
Second technical problem that the present invention will solve is to provide a kind of application of metal nanoparticle; It can be for using visible light to decompose water and make hydrogen system.
For solving above-mentioned first technical problem, the invention provides a kind of preparation method of metal nanoparticle, comprise the following steps:
1) polyamide-amide class dendritic is added to the water, stirs and make abundant dispersion;
2) what obtain to step 1) adds metal ion containing in the aqueous solution of polyamide-amide class dendritic, continues to stir to make both abundant combinations;
3) continue to stir, to step 2) absorption that obtains has in the polyamide-amide class dendritic aqueous solution of metal ion and adds methyl alcohol, adds hot reflux 4 hours under oxygen free condition, is down to room temperature, remove the methyl alcohol in reactant liquor, obtain the metal nanoparticle that polyamide-amide base polymer disperses.
In described step 1); the inside of described polyamide-amide class dendritic is multiamide structure, and peripheral functional group is carboxyl, hydroxyl, amino, sulfydryl, sulfonic group, sulfophenyl, phosphono, phosphine acylamino, phosphate, borono, silanol, formoxyl, acyl group or amide groups.
Described polyamide-amide class dendritic polymer molecule comprised for 2 generation～10 generations.
Described polyamide-amide class dendritic polymer molecule size is 1nm～20nm.
Described step 1) is to carry out under 0 DEG C～100 DEG C conditions of temperature; Preferably, under 10 DEG C～40 DEG C conditions, carry out.
In described step 1), the concentration of aqueous solution containing polyamide-amide class dendritic obtaining is 1 × 10
-10m～1 × 10
-1m.
Described step 2) in, described metal ion comprises the ion of silver, gold, platinum, palladium, copper, mercury; Preferably, described metal ion is the ion of gold, platinum, palladium.
Described metal ion also comprises by the metal ion of ligand complex effect combination, as PtCl
4 2+, AuCl
4 +deng.
Described metal ion also comprises some containing metal complex acid, as H
2ptCl
6deng.
Described step 2) in, adding metal ion is that one or more metal ions are added to the aqueous solution containing polyamide-amide class dendritic.
In described step 3), it is 1:1 that the methyl alcohol adding has the volume ratio of the polyamide-amide class dendritic aqueous solution of metal ion with absorption.
The metal nanoparticle that described step 3) makes is the metal nanoparticle of single-element.
The metal nanoparticle that described step 3) makes is the nano particle of two or more metal Uniform Doped.
The metal nanoparticle that described step 3) makes is the nano particle that two or more metal forms with nucleocapsid structure.
Described polyamide-amide (PAMAM) class dendritic can be that unimolecule disperses single metal nano particle, can be also that a metal nanoparticle is stablized in the common participation of multiple polyamide-amides (PAMAM) class dendritic polymer molecule.
Described stirring can coordinate ultrasonic dispersion one to work.
This preparation method utilizes methyl alcohol as reducing agent, and reducing condition gentleness there will not be rapidly reduction and separate out the situation of precipitation of metal ion, reaction condition is easy to control, reproducible, and after reduction, in system, methyl alcohol is easy to remove, can not introduce new component, can be directly used in corresponding catalyst system and catalyzing.
For solving above-mentioned second technical problem, the invention provides a kind of metal nanoparticle for Photocatalyzed Hydrogen Production, comprise the following steps:
1) by sensitising agent, sacrificial body, electron carrier and above-mentioned make the mixed solution of the water-soluble and acetonitrile of metal nanoparticle in, mix, regulate pH to 3～13;
2), to reaction vessel deoxygenation, squeeze into methane as interior gas;
3) with visible ray illumination 0.5 hour～1000 hours.
In described step 1), described sensitising agent, sacrificial body, electron carrier are respectively terpyridyl platinum complex (Pt-tpy
+), triethanolamine (TEOA), bromo-ethyl purpurine (EV-Br
2+), there is following structure:
In the mixed solution of described water and acetonitrile, the volume ratio (V of water and acetonitrile
water: V
acetonitrile) be 3:2.
Described adjusting pH regulates with watery hydrochloric acid or dilute sodium hydroxide aqueous solution.
The wave-length coverage of described visible ray is 390nm-780nm.
After radiation of visible light, adopt hydrogen in the gas of gas chromatography determination solution top and the peak area of methane, just can calculate the volume of hydrogen according to formula.
Turn over number n (H in this description
2)/n (X) represents the ratio of hydrogen molal quantity and metal X atomic molar number.This ratio can be weighed the utilization ratio of catalyst, and numerical value is larger, illustrates that the utilization ratio of catalyst is higher, and economic benefit is also larger.
The present invention has following outstanding advantages:
The present invention adopts methyl alcohol as reducing agent first, the metal nanoparticle of the polyamide-amide class dendritic that is amide structure for the preparation of inside parcel.Methyl alcohol is that reduction process is slow as the advantage of reducing agent, mild condition, and favorable repeatability, can effectively prevent from generating precipitation in reduction process, the metal nanoparticle of preparing by this method size homogeneous, and there is good stability.After reduction, in system, excessive methyl alcohol is easy to remove simultaneously, can be directly used in corresponding catalyst system and catalyzing.
The present invention is first using the metal nanoparticle of polyamide-amide class dendritic parcel as proton reducing catalyst, for visible light catalytic hydrogen production by water decomposition process, produce in hydrogen process, catalyst property is stable, and have good catalytic effect, the metal nanoparticle of polyamide-amide class dendritic parcel of the present invention is a kind of good proton reducing catalyst.
Brief description of the drawings
Fig. 1 is the schematic diagram that the present invention prepares metal nanoparticle;
Fig. 2 is the schematic diagram of metal nanoparticle of the present invention for Photocatalyzed Hydrogen Production system;
Fig. 3 is the G4-NH of preparation in the embodiment of the present invention 3
2(Pt
20) nano particle transmission electron microscope (TEM) picture and particle diameter distribution map;
Fig. 4 is the G2-OH (Pt preparing in embodiment of the present invention 19-22
5), G2-OH (Pt
10), G2-OH (Pt
15), G2-OH (Pt
20) nano particle transmission electron microscope (TEM) picture and corresponding particle diameter distribution map;
Fig. 5 is the G10-OH (Pt preparing in inventive embodiments 24-27
100), G10-OH (Pt
200), G10-OH (Pt
300), G10-OH (Pt
400) nano particle transmission electron microscope (TEM) picture and corresponding particle diameter distribution map.
Detailed description of the invention
For understanding better the present invention, will further illustrate the solution of the present invention by specific embodiment below, but protection scope of the present invention should comprise the full content of claim, is not limited to this.
Embodiment 1
Taking the 4th generation periphery as amino PAMAM dendritic G4-NH
2for template is prepared G4-NH
2(Pt
5) nano particle, comprise the following steps:
Wherein, periphery is that amino 0 generation of PAMAM dendritic is as follows to the molecular structure in 10 generations:
1) 40 DEG C in 50ml eggplant-shape bottle, add successively 10ml water and amino-terminated daiamid (PAMAM) dendritic 4 generations (G4) 1ml/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
2) there is the G4-NH of chloroplatinic acid to absorption
2in the aqueous solution, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 2
Preparation G4-NH
2(Pt
10) nano particle:
Preparation process is identical with embodiment 1, and difference is in step 1), changes the amount that adds amino-terminated polyamide-amide (PAMAM) dendritic 4 generations (G4) into 0.5ml/0.5mM, and the inventory of all the other materials is identical.
Embodiment 3
Preparation G4-NH
2(Pt
20) nano particle:
Preparation process is identical with embodiment 1, and difference is in step 1), changes the amount that adds amino-terminated polyamide-amide (PAMAM) dendritic 4 generations (G4) into 250 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 4
Preparation G4-NH
2(Pt
40) nano particle:
Preparation process is identical with embodiment 1, and difference is in step 1), changes the amount that adds amino-terminated polyamide-amide (PAMAM) dendritic 4 generations (G4) into 125 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 5
Utilize different nano particle prepared by embodiment 1-4 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G4-NH
2(Pt
5), G4-NH
2(Pt
10), G4-NH
2(Pt
20), G4-NH
2(Pt
40) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Table 1G4-NH
2(Pt
5), G4-NH
2(Pt
10), G4-NH
2(Pt
20), G4-NH
2(Pt
40) impact of nano particle on hydrogen output
Embodiment 6
The G4-NH that utilizes embodiment 1 to prepare
2(Pt
5) as catalyst, measure different pH values to G4-NH
2(Pt
5) impact of nano particle catalysis hydrogen generation efficiency:
Configure respectively I, II, III, IV, V, the mixed solvent (V of six parts of 10ml of VI
water: V
acetonitrile=3/2), add wherein respectively 200mM triethanolamine (TEOA), 1 × 10
-4the bromo-ethyl purpurine of M (EV-Br
2+), 5 × 10
-5m terpyridyl platinum complex (Pt-tpy
+) and 5 × 10
-5m (Pt content) G4-NH
2(Pt
5).By I, II, III, IV, V, it is 5,6,7,8,9,10 that six parts of solution of VI regulate pH value with watery hydrochloric acid or dilute sodium hydroxide respectively.After illumination 6 hours, hydrogen output is as following table:
The different pH of table 2 are to G4-NH
2(Pt
5) impact of nano particle hydrogen output
Embodiment 7
Different pH values are to G4-NH
2(Pt
10) impact of nano particle catalysis hydrogen generation efficiency:
Course of reaction is identical with embodiment 6, and difference is, by G4-NH
2(Pt
5) nano particle changes G4-NH into
2(Pt
10) nano particle, all the other conditions are identical.Hydrogen output is as following table:
The different pH of table 3 are to G4-NH
2(Pt
10) impact of nano particle hydrogen output
Embodiment 8
Different pH values are to G4-NH
2(Pt
20) impact of nano particle catalysis hydrogen generation efficiency:
Course of reaction is identical with embodiment 6, and difference is, by G4-NH
2(Pt
5) nano particle changes G4-NH into
2(Pt
20) nano particle, all the other conditions are identical.Hydrogen output is as following table:
The different pH of table 4 are to G4-NH
2(Pt
20) impact of nano particle hydrogen output
Embodiment 9
Different pH values are to G4-NH
2(Pt
40) impact of nano particle catalysis hydrogen generation efficiency:
Course of reaction is identical with embodiment 6, and difference is, by G4-NH
2(Pt
5) nano particle changes G4-NH into
2(Pt
40) nano particle, all the other conditions are identical.Hydrogen output is as following table:
The different pH of table 5 are to G4-NH
2(Pt
40) impact of nano particle hydrogen output
Embodiment 10
Taking the 4th generation periphery prepare G4-OH (Pt as the PAMAM dendritic G4-OH of hydroxyl as template
5) nano particle, comprise the following steps:
Wherein, periphery is that 0 generation of PAMAM dendritic of hydroxyl is as follows to the molecular structure in 10 generations:
1) 10 DEG C in 50ml eggplant-shape bottle, add successively 10ml water and hydroxy-end capped polyamide-amide (PAMAM) dendritic 4 generations (G4) 1ml/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
2) in absorption has the G4-OH aqueous solution of chloroplatinic acid, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, be concentrated into below 10ml, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 11
Preparation G4-OH (Pt
10) nano particle:
Preparation process is identical with embodiment 10, and difference is in step 1), changes the amount that adds hydroxy-end capped daiamid (PAMAM) dendritic G4-OH into 0.5ml/0.5mM, and the inventory of all the other materials is identical.
Embodiment 12
Preparation G4-OH (Pt
20) nano particle:
Preparation process is identical with embodiment 10, and difference is in step 1), changes the amount that adds hydroxy-end capped daiamid (PAMAM) dendritic G4-OH into 250 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 13
Preparation G4-OH (Pt
40) nano particle:
Preparation process is identical with embodiment 10, and difference is in step 1), changes the amount that adds hydroxy-end capped polyamide-amide (PAMAM) dendritic G4-OH into 125 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 14
Utilize different nano particle prepared by embodiment 10-13 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G4-OH (Pt
5), G4-OH (Pt
10), G4-OH (Pt
20), G4-OH (Pt
40) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Table 6G4-OH (Pt
5), G4-OH (Pt
10), G4-OH (Pt
20), G4-OH (Pt
40) impact of nano particle on hydrogen output
Embodiment 15
G4-OH (the Pt that utilizes embodiment 10 to prepare
5) as catalyst, measure different pH values to G4-OH (Pt
5) impact of nano particle catalysis hydrogen generation efficiency:
Configure respectively I, II, III, IV, V, the mixed solvent (V of six parts of 10ml of VI
water: V
acetonitrile=3/2), add wherein respectively 200mM triethanolamine (TEOA), 1 × 10
-4the bromo-ethyl purpurine of M (EV-Br
2+), 5 × 10
-5m terpyridyl platinum complex (Pt-tpy
+) and 5 × 10
-5m (Pt content) G4-OH (Pt
5).By I, II, III, IV, V, it is 5,6,7,8,9,10 that six parts of solution of VI regulate pH value with watery hydrochloric acid or dilute sodium hydroxide respectively.After illumination 6 hours, hydrogen output is as following table:
The different pH of table 7 are to G4-OH (Pt
5) impact of nano particle hydrogen output
Embodiment 16
Different pH values are to G4-OH (Pt
10) impact of nano particle catalysis hydrogen generation efficiency:
Course of reaction is identical with embodiment 15, and difference is, by G4-OH (Pt
5) nano particle changes G4-OH (Pt into
10) nano particle, all the other conditions are identical.Hydrogen output is as following table:
The different pH of table 8 are to G4-OH (Pt
10) impact of nano particle hydrogen output
Embodiment 17
Different pH values are to G4-OH (Pt
20) impact of nano particle catalysis hydrogen generation efficiency:
Course of reaction is identical with embodiment 15, and difference is, by G4-OH (Pt
5) nano particle changes G4-OH (Pt into
20) nano particle, all the other conditions are identical.Hydrogen output is as following table:
The different pH of table 9 are to G4-OH (Pt
20) impact of nano particle hydrogen output
Embodiment 18
Different pH values are to G4-OH (Pt
40) impact of nano particle catalysis hydrogen generation efficiency:
Course of reaction is identical with embodiment 15, and difference is, by G4-OH (Pt
5) nano particle changes G4-OH (Pt into
40) nano particle, all the other conditions are identical.Hydrogen output is as following table:
The different pH of table 10 are to G4-OH (Pt
40) impact of nano particle hydrogen output
Embodiment 19
PAMAM dendritic G2-OH taking second generation periphery as hydroxyl prepares G2-OH (Pt as template
5) nano particle, comprise the following steps:
Wherein, the PAMAM dendritic that in the present embodiment, periphery used is hydroxyl is identical with structure in embodiment 10.
1) 90 DEG C in 50ml eggplant-shape bottle, add successively 10ml water and hydroxy-end capped daiamid (PAMAM) dendritic G2-OH1000 μ L/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
2) in absorption has the G2-OH aqueous solution of chloroplatinic acid, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 20
Preparation G2-OH (Pt
10) nano particle:
Preparation process is identical with embodiment 19, and difference is in step 1), changes the amount that adds hydroxy-end capped polyamide-amide (PAMAM) dendritic G2-OH into 500 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 21
Preparation G2-OH (Pt
15) nano particle:
Preparation process is identical with embodiment 19, and difference is in step 1), changes the amount that adds hydroxy-end capped polyamide-amide (PAMAM) dendritic G2-OH into 333 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 22
Preparation G2-OH (Pt
20) nano particle:
Preparation process is identical with embodiment 19, and difference is in step 1), changes the amount that adds hydroxy-end capped polyamide-amide (PAMAM) dendritic G2-OH into 250 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 23
Utilize different nano particle prepared by embodiment 19-22 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G2-OH (Pt
5), G2-OH (Pt
10), G2-OH (Pt
15), G2-OH (Pt
20) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Different G2-OH (the Pt of table 11
5), G2-OH (Pt
10), G2-OH (Pt
15), G2-OH (Pt
20) nano particle affects hydrogen output
Embodiment 24
Taking the tenth generation periphery prepare G10-OH (Pt as the PAMAM dendritic G10-OH of hydroxyl as template
100) nano particle, comprise the following steps:
Wherein, the PAMAM dendritic that in the present embodiment, periphery used is hydroxyl is identical with structure in embodiment 10.
1) in 50ml eggplant-shape bottle, add successively 10ml water and hydroxy-end capped polyamide-amide (PAMAM) dendritic G10-OH50 μ L/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
2) in absorption has the G10-OH aqueous solution of chloroplatinic acid, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 25
Preparation G10-OH (Pt
200) nano particle:
Preparation process is identical with embodiment 24, and difference is in step 1), changes the amount that adds hydroxy-end capped daiamid (PAMAM) dendritic G10-OH into 25 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 26
Preparation G10-OH (Pt
300) nano particle:
Preparation process is identical with embodiment 24, and difference is in step 1), changes the amount that adds hydroxy-end capped polyamide-amide (PAMAM) dendritic G10-OH into 16.7 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 27
Preparation G10-OH (Pt
400) nano particle:
Preparation process is identical with embodiment 24, and difference is in step 1), changes the amount that adds hydroxy-end capped daiamid (PAMAM) dendritic G10-OH into 12.5 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 28
Utilize different nano particle prepared by embodiment 24-27 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G10-OH (Pt
100), G10-OH (Pt
200), G10-OH (Pt
300), G10-OH (Pt
400) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Table 12G10-OH (Pt
100), G10-OH (Pt
200), G10-OH (Pt
300), G10-OH (Pt
400) nano particle affects hydrogen output
Embodiment 29
Taking the 4th generation periphery as amino PAMAM dendritic G4-NH
2for template is prepared G4-NH
2(Au
5) nano particle, comprise the following steps:
Wherein, in the present embodiment, periphery used is that amino PAMAM dendritic is identical with structure in embodiment 1.
1) in 50ml eggplant-shape bottle, add successively 10ml water and amino-terminated polyamide-amide (PAMAM) dendritic 4 generations (G4) 1ml/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip KAuCl afterwards
4solution 250 μ L/0.01M, dropwise for 10 minutes, continue to stir half an hour, make AuCl
4 +with the abundant combination of acid amides;
2) there is AuCl to absorption
4 +g4-NH
2in the aqueous solution, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 30
Preparation G4-NH
2(Au
10) nano particle:
Preparation process is identical with embodiment 29, and difference is in step 1), will add amino-terminated polyamide-amide (PAMAM) dendritic G4-NH
2amount change 0.5ml/0.5mM into, the inventory of all the other materials is identical.
Embodiment 31
Preparation G4-NH
2(Au
20) nano particle:
Preparation process is identical with embodiment 29, and difference is in step 1), will add amino-terminated polyamide-amide (PAMAM) dendritic G4-NH
2amount change 250 μ L/0.5mM into, the inventory of all the other materials is identical.
Embodiment 32
Preparation G4-NH
2(Au
40) nano particle:
Preparation process is identical with embodiment 29, and difference is in step 1), will add amino-terminated polyamide-amide (PAMAM) dendritic G4-NH
2amount change 125 μ L/0.5mM into, the inventory of all the other materials is identical.
Embodiment 33
Utilize different nano particle prepared by embodiment 29-32 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G4-NH
2(Au
5), G4-NH
2(Au
10), G4-NH
2(Au
20), G4-NH
2(Au
40) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Table 13G4-NH
2(Au
5), G4-NH
2(Au
10), G4-NH
2(Au
20), G4-NH
2(Au
40) nano particle affects hydrogen output
Embodiment 34
Taking the 6th generation periphery prepare G6-OH (Pt as the PAMAM dendritic G6-OH of hydroxyl as template
100au
100) mix nano particle, comprise the following steps:
The PAMAM dendritic that in the present embodiment, periphery used is hydroxyl is identical with structure in embodiment 10.G6-OH (Pt
100au
100) hybrid particles preparation:
1) in 50ml eggplant-shape bottle, add successively respectively 10ml water and hydroxy-end capped polyamide-amide (PAMAM) dendritic G6-OH50 μ L/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, then add KAuCl
4solution 250 μ L/0.01M, dropwise for 10 minutes.Continue to stir half an hour, make the abundant combination of metal ion and acid amides;
2) in absorption has the G6-OH aqueous solution of metal ion, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, be concentrated into below 10ml, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 35
G6-OH (the Pt that utilizes embodiment 34 to prepare
100au
100) as catalyst, measure different pH values to G6-OH (Pt
100au
100) mix the impact of nano particle catalysis hydrogen generation efficiency:
Configure respectively I, II, III, IV, V, the mixed solvent (V of six parts of 10ml of VI
water: V
acetonitrile=3/2), add wherein respectively 200mM triethanolamine (TEOA), 1 × 10
-4the bromo-ethyl purpurine of M (EV-Br
2+), 5 × 10
-5m terpyridyl platinum complex (Pt-tpy
+) and 5 × 10
-5m (Pt or Au content) G6-OH (Pt
100au
100) mixing nano particle.By I, II, III, IV, V, it is 5,6,7,8,9,10 that six parts of solution of VI regulate pH value with watery hydrochloric acid or dilute sodium hydroxide respectively.After illumination 6 hours, hydrogen output is as following table:
The different pH of table 14 are to G6-OH (Pt
100au
100) impact of nano particle hydrogen output
Embodiment 36
Taking the 6th generation periphery prepare G6-OH ([Au as the PAMAM dendritic G6-OH of hydroxyl as template
100] Pt
100) coating structure nano particle (skin is Pt, and internal layer is Au), comprise the following steps:
The PAMAM dendritic that in the present embodiment, periphery used is hydroxyl is identical with structure in embodiment 10.
1) in 50ml eggplant-shape bottle, add successively respectively 10ml water and hydroxy-end capped polyamide-amide (PAMAM) dendritic G6-OH50 μ L/0.5mM, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip KAuCl afterwards
4solution 250 μ L/0.01M, dropwise for 10 minutes, continue to stir half an hour, make the abundant combination of metal ion and acid amides;
2) in above-mentioned solution, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, be concentrated into 10ml;
3) above-mentioned 10ml solution is transferred in 50ml eggplant-shape bottle, in solution, slowly drips platinum acid chloride solution 250 μ L/0.01M, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
4) in above-mentioned solution, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 37
The G6-OH ([Au that utilizes embodiment 36 to prepare
100] Pt
100) coating structure nano particle is as catalyst, measures different pH values to G6-OH ([Au
100] Pt
100) impact of coating structure nano particle catalysis hydrogen generation efficiency:
Configure respectively I, II, III, IV, V, the mixed solvent (V of six parts of 10ml of VI
water: V
acetonitrile=3/2), add wherein respectively 200mM triethanolamine (TEOA), 1 × 10
-4the bromo-ethyl purpurine of M (EV-Br
2+), 5 × 10
-5m terpyridyl platinum complex (Pt-tpy
+) and 5 × 10
-5m (Pt or Au content) G6-OH ([Au
100] Pt
100) coating structure nano particle.By I, II, III, IV, V, it is 5,6,7,8,9,10 that six parts of solution of VI regulate pH value with watery hydrochloric acid or dilute sodium hydroxide respectively.After illumination 6 hours, hydrogen output is as following table:
The different pH of table 15 are to G6-OH ([Au
100] Pt
100) impact of coating structure nano particle hydrogen output
Embodiment 38
Taking the 4th generation periphery as the PAMAM dendritic G4-NHCOCH of acetamido
3for template is prepared G4-NHCOCH
3(Pt
5) nano particle, comprise the following steps:
Wherein, periphery is that 0 generation of PAMAM dendritic of acetamido is as follows to the molecular structure in 10 generations:
1) in 50ml eggplant-shape bottle, add successively daiamid (PAMAM) dendritic 4 generations (G4) 1ml/0.5mM of 10ml water and acetamido end-blocking, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
2) there is the G4-NHCOCH of chloroplatinic acid to absorption
3in the aqueous solution, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 39
Preparation G4-NHCOCH
3(Pt
10) nano particle:
Preparation process is identical with embodiment 38, difference is in step 1), change the amount of polyamide-amide (PAMAM) dendritic 4 generations (G4) that adds acetamido end-blocking into 0.5ml/0.5mM, the inventory of all the other materials is identical.
Embodiment 40
Preparation G4-NHCOCH
3(Pt
20) nano particle:
Preparation process is identical with embodiment 38, difference is in step 1), change the amount of polyamide-amide (PAMAM) dendritic 4 generations (G4) that adds acetamido end-blocking into 250 μ L/0.5mM, the inventory of all the other materials is identical.
Embodiment 41
Preparation G4-NHCOCH
3(Pt
40) nano particle:
Preparation process is identical with embodiment 38, difference is in step 1), change the amount of polyamide-amide (PAMAM) dendritic 4 generations (G4) that adds acetamido end-blocking into 125 μ L/0.5mM, the inventory of all the other materials is identical.
Embodiment 42
Utilize different nano particle prepared by embodiment 38-41 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G4-NHCOCH
3(Pt
5), G4-NHCOCH
3(Pt
10), G4-NHCOCH
3(Pt
20), G4-NHCOCH
3(Pt
40) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Table 16G4-NHCOCH
3(Pt
5), G4-NHCOCH
3(Pt
10), G4-NHCOCH
3(Pt
20), G4-NHCOCH
3(Pt
40)
The impact of nano particle on hydrogen output
Embodiment 43
Taking the 4th generation periphery prepare G4-COOH (Pt as the PAMAM dendritic G4-COOH of carboxyl as template
5) nano particle, comprise the following steps:
Wherein, periphery is that 0 generation of PAMAM dendritic of carboxyl is as follows to the molecular structure in 10 generations:
1) 10 DEG C, in 50ml eggplant-shape bottle, add successively polyamide-amide (PAMAM) dendritic 4 generations (G4) 1ml/0.5mM of 10ml water and carboxy blocking, stir 10 minutes, polymer is fully dissolved.In solution, slowly drip platinum acid chloride solution 250 μ L/0.01M afterwards, within 10 minutes, dropwise, continue to stir half an hour, make the abundant combination of chloroplatinic acid and acid amides;
2) in absorption has the G4-COOH aqueous solution of chloroplatinic acid, add 10ml methyl alcohol, stir simultaneously.Eggplant-shape bottle connects condenser pipe, to logical nitrogen half an hour in container, removes the oxygen in system.After degasification, the sealing of nitrogen balloon, adds hot reflux 4 hours.After be cooled to room temperature, the brown solution vacuum rotary steam of gained is concentrated, remove methyl alcohol and a small amount of water, remaining aqueous solution water is settled to 10ml, makes.
Embodiment 44
Preparation G4-COOH (Pt
10) nano particle:
Preparation process is identical with embodiment 43, and difference is in step 1), changes the amount of daiamid (PAMAM) dendritic 4 generations (G4) that adds carboxy blocking into 0.5ml/0.5mM, and the inventory of all the other materials is identical.
Embodiment 45
Preparation G4-COOH (Pt
20) nano particle:
Preparation process is identical with embodiment 43, and difference is in step 1), changes the amount of daiamid (PAMAM) dendritic 4 generations (G4) that adds carboxy blocking into 250 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 46
Preparation G4-COOH (Pt
40) nano particle:
Preparation process is identical with embodiment 43, and difference is in step 1), changes the amount of polyamide-amide (PAMAM) dendritic 4 generations (G4) that adds carboxy blocking into 125 μ L/0.5mM, and the inventory of all the other materials is identical.
Embodiment 47
Utilize different nano particle prepared by embodiment 43-46 to produce hydrogen system for visible light catalytic, prepare hydrogen:
Configure respectively I, II, III, the mixed solvent (V of four parts of 10ml of IV
water: V
acetonitrile=3/2), add wherein respectively the triethanolamine (TEOA) of 200mM, 1 × 10
-4the bromo-ethyl purpurine (EV-Br of M
2+) and 5 × 10
-5terpyridyl platinum complex (the Pt-tpy of M
+).To I, II, III, adds respectively 5 × 10 in four parts of solution of IV
-5m(Pt content) G4-COOH (Pt
5), G4-COOH (Pt
10), G4-COOH (Pt
20), G4-COOH (Pt
40) as proton reducing catalyst.The pH value of each solution is adjusted to 8 with watery hydrochloric acid.After illumination 6 hours, hydrogen output is as shown in the table:
Table 17G4-COOH (Pt
5), G4-COOH (Pt
10), G4-COOH (Pt
20), G4-COOH (Pt
40) impact of nano particle on hydrogen output
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (4)
1. a purposes for the metal nanoparticle that polyamide-amide base polymer disperses, is characterized in that, the application that the metal nanoparticle that described polyamide-amide base polymer disperses produces in hydrogen in catalysis comprises the following steps:
1) by the mixed solution of water-soluble metal nanoparticle of sensitising agent, sacrificial body, electron carrier and the dispersion of polyamide-amide base polymer and acetonitrile, mix, regulate pH to 3～13;
2), to reaction vessel deoxygenation, squeeze into methane as interior gas;
3) with visible ray illumination 0.5 hour～1000 hours;
The preparation of the metal nanoparticle that described polyamide-amide base polymer disperses comprises the following steps:
1) polyamide-amide class dendritic is added to the water, stirs and make abundant dispersion;
2) to step 1) obtain containing adding metal ion in the aqueous solution of polyamide-amide class dendritic, continue to stir and make both abundant combinations;
3) continue to stir, to step 2) absorption that obtains has in the polyamide-amide class dendritic aqueous solution of metal ion and adds methyl alcohol, under oxygen free condition, add hot reflux 4 hours, be down to room temperature, remove the methyl alcohol in reactant liquor, obtain the metal nanoparticle that polyamide-amide base polymer disperses.
2. the purposes of the metal nanoparticle that a kind of polyamide-amide base polymer according to claim 1 disperses, is characterized in that described step 1) in, described sensitising agent, sacrificial body, electron carrier are respectively terpyridyl platinum complex (Pt-tpy
+), triethanolamine (TEOA), bromo-ethyl purpurine (EV-Br
2+), they have following structure:
3. the purposes of the metal nanoparticle that a kind of polyamide-amide base polymer according to claim 1 disperses, is characterized in that described step 1) in, in the mixed solution of described water and acetonitrile, the volume ratio (V of water and acetonitrile
water: V
acetonitrile) be 3:2.
4. the purposes of the metal nanoparticle that a kind of polyamide-amide base polymer according to claim 1 disperses, is characterized in that described step 1) in, described adjusting pH regulates with watery hydrochloric acid or dilute sodium hydroxide aqueous solution.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005042135A (en) * | 2003-07-23 | 2005-02-17 | Sumitomo Electric Ind Ltd | Reducing agent solution, method of producing metal powder by using the same, and method of forming metal film |
| CN101264526A (en) * | 2008-05-13 | 2008-09-17 | 上海师范大学 | Preparation of nano copper particle |
| CN101524762A (en) * | 2009-04-14 | 2009-09-09 | 上海师范大学 | Method for preparing ferroplatinum nano-particle |
| CN102039131A (en) * | 2011-01-07 | 2011-05-04 | 华东理工大学 | Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof |
-
2011
- 2011-05-27 CN CN201310004140.1A patent/CN103071530B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005042135A (en) * | 2003-07-23 | 2005-02-17 | Sumitomo Electric Ind Ltd | Reducing agent solution, method of producing metal powder by using the same, and method of forming metal film |
| CN101264526A (en) * | 2008-05-13 | 2008-09-17 | 上海师范大学 | Preparation of nano copper particle |
| CN101524762A (en) * | 2009-04-14 | 2009-09-09 | 上海师范大学 | Method for preparing ferroplatinum nano-particle |
| CN102039131A (en) * | 2011-01-07 | 2011-05-04 | 华东理工大学 | Catalyst for generating hydrogen by visible light photocatalytic reduction of water, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ***等."9，10-二氰基蒽敏化的氧化还原体系中取代苯的化学反应".《科学通报》.1990,(第23期), * |
| ***等."9,10-二氰基蒽敏化的氧化还原体系中取代苯的化学反应".《科学通报》.1990,(第23期), * |
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