CN103721708A - Silver/titanium dioxide composite heterostructure and preparation method thereof - Google Patents
Silver/titanium dioxide composite heterostructure and preparation method thereof Download PDFInfo
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- CN103721708A CN103721708A CN201410008189.9A CN201410008189A CN103721708A CN 103721708 A CN103721708 A CN 103721708A CN 201410008189 A CN201410008189 A CN 201410008189A CN 103721708 A CN103721708 A CN 103721708A
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Abstract
The invention discloses a silver/titanium dioxide composite heterostructure. The silver/titanium dioxide composite heterostructure comprises a silver nanowire component and a titanium dioxide component, wherein a titanium dioxide shell covered with the silver nanowire can form a nuclear shell heterostructure, and a titanium dioxide ball is bunched on the silver nanowire so as to form a bradde chain heterostructure. The heterostructure provided by the invention has the good electricity-conduction and heat-conduction property of the silver, the heterostructure of a noble metal and a semiconductor photocatalyst is formed, the effective separation of electrons and holes is benefited, the photocatalytic degradation organic matter property is enhanced, the disadvantages that the chemical stability of the silver is poor, the surface of the silver is easy to oxidize, and the silver/titanium dioxide composite heterostructure has the wide application prospect on the photocatalysis and new energy field. The invention also discloses a preparation method, the operation of the method is simple, the controllability is strong, the repeatability is good, the heterostructures of different shapes are obtained through adjusting the collocation of a reagent, the size of the diameter of a TiO2 ball and the thickness of a titanium dioxide shell layer are adjusted by virtue of adjusting the quantity of a titanium source, and the preparation method has strong practicability.
Description
Technical field
The composite heterogenous junction structure that the present invention relates to a kind of nano silver wire and titanium dioxide with and preparation method thereof, belong to metal and semiconductor composite heterogenous junction structure technical field of material.
Background technology
In recent years, because hud typed nanostructured all has potential advantage in research fields such as photoelectronics, catalysis and photocatalysis, got more and more people's extensive concerning.In these materials, Ag and TiO
2hud typed structural research particularly outstanding, not only because TiO
2at Optical Electro-Chemistry activity, solar energy conversion and photochemical catalyst, there is potential using value, and the surface-enhanced Raman effects of silver nano material, local surface plasma resonance and fluorescent effect, at chemistry and bio-sensing direction, shown the performance that some are unique.In addition, easily there is corrosion and decompose in independent noble metal granule, can limit the application of noble metal photocatalytic degradation effect, and Ag and TiO
2after material forms hud typed heterojunction structure, can make the stability of material be improved, and after compound, can effectively improve the photocatalysis performance of material.
At present, to Ag and TiO
2the compound research of nano particle is mostly gathered in noble metal nano particles is deposited on to TiO
2the surface of nano particle forms heterojunction structure, seldom finds that there is TiO
2deposition of material is at the heterojunction structure report on nano silver wire surface, wherein, and nano silver wire and TiO
2the bead chain shape heterojunction structure forming have not been reported.
Summary of the invention
The invention discloses a kind of silver/titanium dioxide composite heterogenous junction structure, this heterojunction structure combines silver and the advantage of titanium dioxide, has overcome silver-colored unstable, easy oxidized shortcoming, and catalytic effect is better.
The invention also discloses the preparation method of this composite heterogenous junction structure, the method can obtain hud typed and composite heterogenous junction structure pelletron type by the adjustment of technological parameter, can also adjust the diameter of titanium dioxide ball and the thickness of titanium dioxide shell, there is good practicality.
The present invention is usingd nano silver wire as carrier, is mixed to form precursor solution with dispersion with solvent, alcohol, bridging agent and titanium source, precursor solution is at high temperature reacted and makes titanium dioxide deposition on nano silver wire surface, thereby obtain nano silver wire and TiO
2compound heterojunction structure, disperses the collocation of solvent and the alcohol of nano silver wire by adjustment, can obtain the heterojunction structure of pelletron type and hud typed two kinds of different-shapes.By changing preparation condition, can also regulate the diameter of pelletron type titanium dioxide ball, and the thickness of hud typed titanium dioxide shell, there is very strong practicality.The nano silver wire structure of one dimension has excellent optics and electrical properties, therefore, on the surface of nano silver wire, forms TiO
2the heterojunction structure of hud typed and two kinds of patterns of pelletron type, has potential using value.
The concrete technical scheme of the present invention is as follows:
Nano silver wire of the present invention and titanium dioxide can form the composite heterogenous junction structure of two types, and a kind of is hud typed, and a kind of is pelletron type, specific as follows:
Hud typed silver/titanium dioxide composite heterogenous junction structure, is characterized in that: described silver is nano silver wire, is covered with layer of titanium dioxide shell on nano silver wire, and nano silver wire and titanium dioxide form hud typed composite heterogenous junction structure.
In hud typed heterojunction structure, described nano silver wire can be mono-crystalline structures, can be also polycrystalline structure, and the diameter of nano silver wire is 10-60 nm.In this diameter range, gained composite heterogenous junction structure performance is all fine.
In hud typed heterojunction structure, described titanium dioxide is coated on nano silver wire substantially uniformly, and nano silver wire is wrapped in titanium dioxide shell, and titanium dioxide thickness of the shell is 5-100 nm.
Pelletron type silver/titanium dioxide composite heterogenous junction structure, is characterized in that: comprise nano silver wire, on described nano silver wire, string has at least one titanium dioxide ball, and described nano silver wire is chained together all titanium dioxide balls, forms pelletron type composite heterogenous junction structure.
In pelletron type composite heterogenous junction structure, nano silver wire runs through titanium dioxide ball along titanium dioxide ball diametric(al).
In pelletron type composite heterogenous junction structure, on every nano silver wire, can contain one or more titanium dioxide balls, generally all contain a plurality of titanium dioxide balls, the concrete number of titanium dioxide ball with the length of nano silver wire, between the diameter of titanium dioxide ball, two titanium dioxide balls the factors such as distance at interval relevant.
In pelletron type composite heterogenous junction structure, between each titanium dioxide ball, be closely connected or have certain interval; The gap location of two titanium dioxide balls (the nano silver wire place that there is no titanium dioxide ball) is also covered with layer of titanium dioxide, but the thinner thickness of this titanium dioxide is less than bulb diameter.
In pelletron type composite heterogenous junction structure, described nano silver wire can only be the nano silver wire of polycrystalline structure, and nano silver wire diameter is 10-60 nm.In this diameter range, gained composite heterogenous junction structure performance is all fine.
In pelletron type composite heterogenous junction structure, the titanium dioxide ball of string on nano silver wire varies, and has certain difference, and general, the average diameter of titanium dioxide ball is 200-600 nm.
The preparation of above-mentioned hud typed or pelletron type silver/titanium dioxide composite heterogenous junction structure, can form by the form at nano silver wire surface deposition titanium dioxide hud typed or pelletron type composite heterogenous junction structure.Specifically comprise the following steps:
(1) nano silver wire is dispersed in solvent, dipping a period of time makes solvent soak on the surface of nano silver wire, obtains nano silver wire suspension;
(2) in nano silver wire suspension, add alcohol and bridging agent, under room temperature, stir;
(3) in the suspension of step (2), add titanium source, under room temperature, stir;
(4) temperature of the suspension of rising step (3), makes titanium dioxide deposition on nano silver wire surface, and centrifugation after reaction, washing, obtain silver/titanium dioxide composite heterogenous junction structure.
In step (1), the object of dipping is that the solvent of peptizaiton is soaked on the surface of nano silver wire, makes solvent molecule on surface or grain boundaries absorption.Disperseing the solvent of nano silver wire can be deionized water, methyl alcohol, ethanol, propyl alcohol or butanols etc.The time of dipping is generally 4 hours-7 days.
In step (2), described alcohol is monohydric alcohol; Described bridging agent is TGA or mercaptopropionic acid.
In step (3), described titanium source is butyl titanate, metatitanic acid orthocarbonate or isopropyl titanate.
In step (4), suspension is risen to 120-200 ℃ and react, the reaction time is 4-20 h, preferably at 150 ℃ of reaction 10 h.
In above-mentioned preparation method, in order to obtain titanium dioxide shell and the titanium dioxide ball of corresponding pattern, respective thickness or diameter, control consumption and the concentration of the reagent such as titanium source, bridging agent, nano silver wire.
In above-mentioned preparation method, the mol ratio in nano silver wire and titanium source is 1:0.7 ~ 14, preferably nano silver wire (mmol): titanium source (ml)=0.1:0.1=1:1.
In above-mentioned preparation method, bridging agent can make titanium source connect in Ag nanowire surface, while preparing the heterojunction structure of pelletron type, must use bridging agent, while preparing hud typed heterojunction structure, can without bridging agent in the situation that, on the surface of nano silver wire, be covered with one deck TiO
2.Preferably, while preparing pelletron type composite heterogenous junction structure, the volume ratio of titanium source and bridging agent is (1 ~ 10): (0.4 ~ 2); While preparing hud typed composite heterogenous junction structure, the volume ratio of titanium source and bridging agent is (1 ~ 10): (0 ~ 2) (because titanium used source and bridging agent are liquid, so mol ratio can embody by volume ratio).
In above-mentioned preparation method, titanium source amount in suspension in step (3) is unsuitable excessive, also unsuitable too small, through experimental verification, system volume mainly disperses to provide with the alcohol in solvent and step (2) in step (1), disperses with the ratio of the volume sum of alcohol in solvent and step (2) effective when 0.00125-0.025:1 scope in the volume in titanium source and step (1).
In above-mentioned preparation method, can make by controlling the collocation of reagent the composite heterogenous junction structure of different-shape.Solvent in step (1) is the alcohol in deionized water, step (2) while being methyl alcohol, ethanol or propyl alcohol, and products obtained therefrom is the pelletron type composite heterogenous junction structure of nano silver wire and titanium dioxide; Solvent in step (1) is that the alcohol in deionized water, step (2) is carbon chain lengths such as isopropyl alcohol or n-butanol, n-amyl alcohol while being more than or equal to four monohydric alcohol, and products obtained therefrom is the hud typed composite heterogenous junction structure of nano silver wire and titanium dioxide; Solvent in step (1) is the alcohol in methyl alcohol, ethanol, propyl alcohol or butanols, step (2) while being arbitrary monohydric alcohol, and products obtained therefrom is the hud typed composite heterogenous junction structure of nano silver wire and titanium dioxide.
In above-mentioned preparation method, when solvent is deionized water in step (1), with the volume ratio of alcohol in step (2) be 1:200 left and right.When solvent is alcohol in step (1), with the volume ratio of alcohol in step (2) be 1:3 left and right.
Key of the present invention is that nano silver wire and titanium oxide is compound, nano silver wire length used does not require, can adopt disclosed method in prior art to make the nano silver wire of required crystal formation and diameter, for example, can adopt disclosed method in following document to prepare nano silver wire:
(1) Changchao Jia, Ping Yang, Aiyu Zhang. Glycerol and ethylene glycol co-mediated synthesis of uniform multiple crystalline silver nanowires, Materials Chemistry and Physics, 2014, 143(2), 794-800.
(2) Linfeng Gou, Mircea Chipara, and Jeffrey M. Zaleski, Convenient, Rapid Synthesis of Ag Nanowires, Chem. Mater. 2007, 19, 1755-1760.
(3) Yugang Sun, Yadong Yin, Brian T. Mayers, Thurston Herricks, and Younan Xia, Uniform Silver Nanowires Synthesis by Reducing AgNO
3 with Ethylene Glycol in the Presence of Seeds and Poly(Vinyl Pyrrolidone). Chem. Mater. 2002, 14, 4736-4745.
Composite heterogenous junction structure of the present invention can be used as the catalyst of light-catalyzed reaction.In light-catalyzed reaction process, silver not only can be used as electron capture agent and reduces electronics and the right combined efficiency in hole, effectively carries out organic light degradation reaction, and can make full use of visible ray, expands TiO
2the response range of exciting light, simultaneously because optical excitation electronics is at TiO
2and between Ag, carry out electronics transfer, improve the photocatalysis efficiency of material.In pearl chain structure, TiO
2bulb diameter is excessive, can affect nano silver wire and excite photoelectronic, and the utilization rate of light declines and reduces TiO
2and the electronics transfer effect between Ag, if TiO
2the diameter of ball is too small, makes to rise in photocatalysis the TiO of degradation
2content reduces relatively, reduces photocatalysis effect.Bulb diameter of the present invention can be accomplished 200-600 nm, and during preferred diameter 450 nm, performance is better.In nucleocapsid structure, the thickness of titanium dioxide shell is similar to the impact of bead chain shape structure on the impact of heterojunction structure performance quality, and shell thickness can be adjusted in 5-100 nm scope, and during preferred thickness 30 nm, performance is better.
The present invention is at the coated TiO in the surface of nano silver wire
2, synthesized nano silver wire and TiO
2composite heterogenous junction structure, XRD characterization result proves, obtains TiO
2crystal formation belong to Detitanium-ore-type.This heterojunction structure can present hud typed and two kinds of different patterns of pelletron type.The method is simple to operate, and controllability is strong, reproducible, can obtain the heterojunction structure of different-shape by adjusting reagent collocation, by adjusting the amount in titanium source, can adjust TiO
2the thickness of the diameter of ball and titanium dioxide shell, has very strong practicality.At the coated TiO in the surface of nano silver wire
2, can effectively protect silver-colored surface not oxidized, there is excellent chemical stability, in addition, TiO
2as traditional photocatalyst material, be compounded to form heterojunction structure with nano silver wire, the photocatalysis that this heterojunction structure is superior and electrical properties have broad application prospects in photocatalysis and new energy field.
Heterojunction structure of the present invention has the good conductive and heat-conductive character of silver itself, formed again the heterojunction structure of noble metal and semiconductor light-catalyst, be conducive to the effectively separated of electronics and hole, strengthen photocatalysis to degrade organic matter performance, made up again easily oxidized shortcoming of silver-colored poor chemical stability, surface.In photocatalysis and new energy field, have broad application prospects.
Accompanying drawing explanation
Nano silver wire and TiO that Fig. 1 (a) embodiment of the present invention 1 is synthetic
2(AgNWsTiO
2) X-ray diffraction (XRD) collection of illustrative plates of pelletron type heterojunction structure.
Nano silver wire and TiO that Fig. 1 (b) embodiment of the present invention 1 is synthetic
2eSEM (SEM) photo of pelletron type heterojunction structure.
The nano silver wire that Fig. 2 embodiment of the present invention 5 is synthetic and TiO
2eSEM (SEM) photo of pelletron type heterojunction structure.
The nano silver wire that Fig. 3 embodiment of the present invention 6 is synthetic and TiO
2eSEM (SEM) photo of pelletron type heterojunction structure.
The nano silver wire that Fig. 4 embodiment of the present invention 11 is synthetic and TiO
2the ESEM of hud typed heterojunction structure (SEM) photo.
The nano silver wire that Fig. 5 embodiment of the present invention 12 is synthetic and TiO
2the ESEM of hud typed heterojunction structure (SEM) photo.
The nano silver wire that Fig. 6 embodiment of the present invention 15 is synthetic and TiO
2the ESEM of hud typed heterojunction structure (SEM) photo.
Nano silver wire and TiO that Fig. 7 (a) embodiment of the present invention 16 is synthetic
2the X-ray diffraction of hud typed structure (XRD) collection of illustrative plates.
Nano silver wire and TiO that Fig. 7 (b) embodiment of the present invention 16 is synthetic
2the ESEM of hud typed structure (SEM) photo.
The nano silver wire that Fig. 8 embodiment of the present invention 18 is synthetic and TiO
2the ESEM of hud typed heterojunction structure (SEM) photo.
The nano silver wire that Fig. 9 embodiment of the present invention 19 is synthetic and TiO
2the ESEM of hud typed heterojunction structure (SEM) photo.
The nano silver wire that Figure 10 embodiment of the present invention 27 is synthetic and TiO
2the ESEM of hud typed heterojunction structure (SEM) photo.
Nano silver wire used and TiO in Figure 11 embodiment of the present invention 28
2(AgNWsTiO
2) pelletron type and the degradation effect figure of hud typed heterojunction structure to methyl orange.
The specific embodiment
Below by embodiment, the present invention will be further elaborated, should be noted that following explanation is only in order to explain the present invention, does not limit its content.
The present invention's nano silver wire used can adopt disclosed any means in existing method to obtain, the diameter of nano silver wire requires between 10-60nm, the nano silver wire of polycrystalline structure can make by adjusting process condition the heterojunction structure of pelletron type, and the nano silver wire of monocrystalline or polycrystalline structure all can make hud typed heterojunction structure by adjusting process condition.In following embodiment, nano silver wire used is according to document (Changchao Jia, Ping Yang, Aiyu Zhang. Glycerol and ethylene glycol co-mediated synthesis of uniform multiple crystalline silver nanowires, Materials Chemistry and Physics, 2014,143 (2), 794-800.) in listed method make: by the AgNO of 0.034 g
3be dissolved in 5 mL glycerine, standby; The PVP of 0.067 g is dissolved in the mixed solution of 10 mL glycerine and 3 mL ethylene glycol, stirs standby; Above-mentioned two kinds of solution are mixed, stir, be then transferred to 200 ℃ of reaction 5 h of reactor, after reaction finishes, water centrifuge washing, 4000 turn per minute washing three times.Under this preparation parameter, averaging of income diameter is the polycrystalline structure nano silver wire of 40 nm, by adjusting PVP and AgNO
3mol ratio can obtain the nano silver wire of diameter 10-60 nm scope.
embodiment 1
1.1 are dispersed in 0.1 mmol nano silver wire in 0.1 mL deionized water, and dipping 12 h, obtain suspension;
1.2 add 20 mL ethanol in the nano silver wire suspension described in embodiment 1.1, and 100 μ L TGAs, stir;
1.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 1.2, are uniformly mixed;
1.4 are transferred to mixed liquor described in embodiment 1.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
1.5 by embodiment 1.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure (as shown in Figure 1), titanium dioxide mean diameter of a ball is 600 nm, nano silver wire diameter is 40 nm.
2.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, and dipping 4 h, obtain suspension;
2.2 add 20 mL methyl alcohol in the nano silver wire suspension described in embodiment 2.1, and 20 μ L TGAs, stir;
2.3 add 0.5 mL metatitanic acid orthocarbonate in the mixed liquor described in embodiment 2.2, are uniformly mixed;
2.4 are transferred to mixed liquor described in embodiment 2.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
2.5 by embodiment 2.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure, titanium dioxide mean diameter of a ball is 560 nm, nano silver wire diameter is 10 nm.
embodiment 3
3.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, and dipping 8 h, obtain suspension;
3.2 add 20mL propyl alcohol in the nano silver wire suspension described in embodiment 3.1, and 50 μ L TGAs, stir;
3.3 add 0.025 mL isopropyl titanate in the mixed liquor described in embodiment 3.2, are uniformly mixed;
3.4 are transferred to mixed liquor described in embodiment 3.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
3.5 by embodiment 3.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure, titanium dioxide mean diameter of a ball is 200 nm, nano silver wire diameter is 60 nm.
embodiment 4
4.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, flood 3 days, obtain suspension;
4.2 add 20 mL ethanol in the nano silver wire suspension described in embodiment 4.1, and 50 μ L mercaptopropionic acids, stir;
4.3 add 0.5 mL isopropyl titanate in the mixed liquor described in embodiment 4.2, are uniformly mixed;
4.4 are transferred to mixed liquor described in embodiment 4.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
4.5 by embodiment 4.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure, titanium dioxide mean diameter of a ball is 580 nm, nano silver wire diameter is 40 nm.
embodiment 5
5.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, and dipping 12 h, obtain suspension;
5.2 add 20 mL ethanol in the nano silver wire suspension described in embodiment 5.1, and 20 μ L TGAs, stir;
5.3 add 0.1 mL butyl titanate in the mixed liquor described in embodiment 5.2, are uniformly mixed;
5.4 are transferred to mixed liquor described in embodiment 5.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
5.5 by embodiment 5.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure (as shown in Figure 2), titanium dioxide mean diameter of a ball is 450 nm, nano silver wire diameter is 40 nm.
embodiment 6
6.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, and dipping 12 h, obtain suspension;
6.2 add 20 mL ethanol in the nano silver wire suspension described in embodiment 6.1, and 20 μ L TGAs, stir;
6.3 add 0.05 mL butyl titanate in the mixed liquor described in embodiment 6.2, are uniformly mixed;
6.4 are transferred to mixed liquor described in embodiment 6.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
6.5 by embodiment 6.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure (as shown in Figure 3), titanium dioxide mean diameter of a ball is 300 nm, nano silver wire diameter is 40 nm.
embodiment 7
7.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, flood 7 days, obtain suspension;
7.2 add 20 mL ethanol in the nano silver wire suspension described in embodiment 7.1, and 20 μ L TGAs, stir;
7.3 add 0.15 mL butyl titanate in the mixed liquor described in embodiment 7.2, are uniformly mixed;
7.4 are transferred to mixed liquor described in embodiment 7.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
7.5 by embodiment 7.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2pelletron type heterojunction structure, titanium dioxide mean diameter of a ball is 480 nm, nano silver wire diameter is 40 nm.
embodiment 8
8.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, flood 2 days, obtain suspension;
8.2 add 20 mL n-butanols in the nano silver wire suspension described in embodiment 8.1, and 20 μ L TGAs, stir;
8.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 8.2, are uniformly mixed;
8.4 are transferred to mixed liquor described in embodiment 8.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
8.5 by embodiment 8.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 100 nm, nano silver wire diameter is 20 nm.
embodiment 9
9.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, flood 3 days, obtain suspension;
9.2 add 20 mL isopropyl alcohols in the nano silver wire suspension described in embodiment 9.1, and 20 μ L TGAs, stir;
9.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 9.2, are uniformly mixed;
9.4 are transferred to mixed liquor described in embodiment 9.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
9.5 by embodiment 9.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 95 nm, nano silver wire diameter is 30 nm.
embodiment 10
10.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, flood 4 days, obtain suspension;
10.2 add 20 mL n-amyl alcohols in the nano silver wire suspension described in embodiment 10.1, and 20 μ L TGAs, stir;
10.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 10.2, are uniformly mixed;
10.4 are transferred to mixed liquor described in embodiment 10.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
10.5 by embodiment 10.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 90 nm, nano silver wire diameter is 50 nm.
embodiment 11
11.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, and dipping 12 h, obtain suspension;
11.2 add 20 mL n-butanols in the nano silver wire suspension described in embodiment 11.1, and 20 μ L TGAs, stir;
11.3 add 0.1 mL butyl titanate in the mixed liquor described in embodiment 11.2, are uniformly mixed;
11.4 are transferred to mixed liquor described in embodiment 11.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
11.5 by embodiment 11.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in Figure 4), titanium dioxide thickness of the shell is 25 nm, nano silver wire diameter is 40 nm.
embodiment 12
12.1 are dispersed in 0.1mmol nano silver wire in 0.1 mL deionized water, and dipping 12 h, obtain suspension;
12.2 add 20 mL n-butanols in the nano silver wire suspension described in embodiment 12.1, and 20 μ L TGAs, stir;
12.3 add 0.05 mL butyl titanate in the mixed liquor described in embodiment 12.2, are uniformly mixed;
12.4 are transferred to mixed liquor described in embodiment 12.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
12.5 by embodiment 12.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in Figure 5), titanium dioxide thickness of the shell is 5 nm, nano silver wire diameter is 40 nm.
embodiment 13
13.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 5 days, obtain suspension;
13.2 add 15 mL methyl alcohol in the nano silver wire suspension described in embodiment 13.1, and 20 μ L TGAs, stir;
13.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 13.2, are uniformly mixed;
13.4 are transferred to mixed liquor described in embodiment 13.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
13.5 by embodiment 13.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 80 nm, nano silver wire diameter is 30 nm.
embodiment 14
14.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL propyl alcohol, flood 3 days, obtain suspension;
14.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 14.1, and 20 μ L TGAs, stir;
14.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 14.2, are uniformly mixed;
14.4 are transferred to mixed liquor described in embodiment 14.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
14.5 by embodiment 14.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 75 nm, nano silver wire diameter is 20 nm.
embodiment 15
15.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 1 day, obtain suspension;
15.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 15.1, and 20 μ L TGAs, stir;
15.3 add 0.25 mL butyl titanate in the mixed liquor described in embodiment 15.2, are uniformly mixed;
15.4 are transferred to mixed liquor described in embodiment 15.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
15.5 by embodiment 15.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in Figure 6), titanium dioxide thickness of the shell is 80 nm, nano silver wire diameter is 40 nm.
embodiment 16
16.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 1 day, obtain suspension;
16.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 16.1, and 20 μ L TGAs, stir;
16.3 add 0.1 mL butyl titanate in the mixed liquor described in embodiment 16.2, are uniformly mixed;
16.4 are transferred to mixed liquor described in embodiment 16.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
16.5 by embodiment 16.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in Figure 7), titanium dioxide thickness of the shell is 30 nm, nano silver wire diameter is 40 nm.
embodiment 17
17.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL methyl alcohol, flood 7 days, obtain suspension;
17.2 add 15 mL propyl alcohol in the nano silver wire suspension described in embodiment 17.1, and 20 μ L TGAs, stir;
17.3 add 0.25 mL butyl titanate in the mixed liquor described in embodiment 17.2, are uniformly mixed;
17.4 are transferred to mixed liquor described in embodiment 17.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
17.5 by embodiment 17.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 45 nm, nano silver wire diameter is 10 nm.
embodiment 18
18.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 1 day, obtain suspension;
18.2 add 15 mL n-butanols in the nano silver wire suspension described in embodiment 18.1, and 20 μ L TGAs, stir;
18.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 18.2, are uniformly mixed;
18.4 are transferred to mixed liquor described in embodiment 18.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
18.5 by embodiment 18.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in Figure 8), titanium dioxide thickness of the shell is 90 nm, nano silver wire diameter is 40 nm.
embodiment 19
19.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, and dipping 12 h, obtain suspension;
19.2 add 15 mL n-butanols in the nano silver wire suspension described in embodiment 19.1, and 20 μ L TGAs, stir;
19.3 add 0.1 mL butyl titanate in the mixed liquor described in embodiment 19.2, are uniformly mixed;
19.4 are transferred to mixed liquor described in embodiment 19.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
19.5 by embodiment 19.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in Figure 9), titanium dioxide thickness of the shell is 30 nm, nano silver wire diameter is 40 nm.
20.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, and dipping 4 h, obtain suspension;
20.2 add 15 mL isopropyl alcohols in the nano silver wire suspension described in embodiment 20.1, and 50 μ L TGAs, stir;
20.3 add 0.025 mL butyl titanate in the mixed liquor described in embodiment 20.2, are uniformly mixed;
20.4 are transferred to mixed liquor described in embodiment 20.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
20.5 by embodiment 20.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 5 nm, nano silver wire diameter is 50 nm.
embodiment 21
21.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, and dipping 12 h, obtain suspension;
21.2 add 15 mL n-amyl alcohols in the nano silver wire suspension described in embodiment 21.1, and 20 μ L TGAs, stir;
21.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 21.2, are uniformly mixed;
21.4 are transferred to mixed liquor described in embodiment 21.3 in 50 mL reactors, and 150 ℃, reaction 10 h.
21.5 by embodiment 21.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 85 nm, nano silver wire diameter is 40 nm.
embodiment 22
22.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL butanols, and dipping 12 h, obtain suspension;
22.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 22.1, and 100 μ L TGAs, stir;
22.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 22.2, are uniformly mixed;
22.4 are transferred to mixed liquor described in embodiment 22.3 in 50 mL reactors, and 120 ℃, reaction 4 h.
22.5 by embodiment 22.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 65 nm, nano silver wire diameter is 30 nm.
embodiment 23
23.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 1 day, obtain suspension;
23.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 23.1, and 35 μ L TGAs, stir;
23.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 23.2, are uniformly mixed;
23.4 are transferred to mixed liquor described in embodiment 23.3 in 50 mL reactors, and 120 ℃, reaction 10 h.
23.5 by embodiment 23.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 90 nm, nano silver wire diameter is 50 nm.
embodiment 24
24.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 1 day, obtain suspension;
24.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 24.1, and 75 μ L TGAs, stir;
24.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 24.2, are uniformly mixed;
24.4 are transferred to mixed liquor described in embodiment 24.3 in 50 mL reactors, and 120 ℃, reaction 20 h.
24.5 by embodiment 24.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 90 nm, nano silver wire diameter is 40 nm.
embodiment 25
25.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, flood 1 day, obtain suspension;
25.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 25.1, and 50 μ L TGAs, stir;
25.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 25.2, are uniformly mixed;
25.4 are transferred to mixed liquor described in embodiment 25.3 in 50 mL reactors, and 200 ℃, reaction 4 h.
25.5 by embodiment 25.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 75 nm, nano silver wire diameter is 30 nm.
embodiment 26
26.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, and dipping 12 h, obtain suspension;
26.2 add 15 mL ethanol in the nano silver wire suspension described in embodiment 26.1, and 10 μ L TGAs, stir;
26.3 add 0.5 mL butyl titanate in the mixed liquor described in embodiment 26.2, are uniformly mixed;
26.4 are transferred to mixed liquor described in embodiment 26.3 in 50 mL reactors, and 200 ℃, reaction 20 h.
26.5 by embodiment 26.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure, titanium dioxide thickness of the shell is 95 nm, nano silver wire diameter is 60 nm.
embodiment 27
27.1 are directly dispersed in 0.1 mmol nano silver wire in 5 mL ethanol, and dipping 12 h, obtain suspension;
27.2 add 15 mL n-butanols in the nano silver wire suspension described in embodiment 27.1, stir;
27.3 add 0.1 mL butyl titanate in the mixed liquor described in embodiment 27.2, are uniformly mixed;
27.4 are transferred to mixed liquor described in embodiment 27.3 in 50 mL reactors, and 160 ℃, reaction 10 h.
27.5 by embodiment 27.4 gained samples, carry out centrifuge washing, make nano silver wire and TiO
2hud typed heterojunction structure (as shown in figure 10), titanium dioxide thickness of the shell is 70 nm, nano silver wire diameter is 40 nm.
embodiment 28
With embodiment 5,6,7 and 16 AgNWsTiO
2pelletron type and hud typed heterojunction structure be example, checking sample of the present invention catalytic effect, its step is as follows:
28.1 get the AgNWsTiO of 10 mg
2pelletron type (embodiment 5,6,7 samples) and AgNWsTiO
2hud typed sample (embodiment 16 samples), add respectively in the methyl orange solution of 20 mL 10 mg/L;
28.2 stir 30 min by methyl orange solution at dark place, make solution in adsorption equilibrium state, then in the lower irradiation of ultraviolet light (light source 12 W), every 30 min, take out 2 mL samples and absorb test, measure the absorbance of methyl orange in solution now, according to langbobier law, calculate concentration, calculate sampling concentration and initial methyl orange concentration ratio;
28.3 take the time as abscissa, and sampling concentration and initial concentration ratio are ordinate, curve plotting, as shown in figure 11; As can be seen from the figure: two kinds of heterojunction structures of the present invention all have photocatalysis effect, best (embodiment 5, and ultraviolet lighting 150 min degraded methyl orange degree are 50% for embodiment 5 and 16 catalytic effect; Embodiment 16, and ultraviolet lighting 150 min degraded methyl orange degree are 56%).
Claims (10)
1. a silver/titanium dioxide composite heterogenous junction structure, is characterized in that: described silver is nano silver wire, is covered with titanium dioxide shell on nano silver wire, and nano silver wire and titanium dioxide form hud typed composite heterogenous junction structure.
2. silver/titanium dioxide composite heterogenous junction structure according to claim 1, is characterized in that: described nano silver wire diameter is 10-60 nm; Described titanium dioxide thickness of the shell is 5-100 nm, is preferably 30nm.
3. a silver/titanium dioxide composite heterogenous junction structure, is characterized in that: comprise nano silver wire, on described nano silver wire, string has at least one titanium dioxide ball, and described nano silver wire is chained together all titanium dioxide balls, forms pelletron type composite heterogenous junction structure.
4. silver/titanium dioxide composite heterogenous junction structure according to claim 3, is characterized in that: between each titanium dioxide ball, be closely connected or have certain interval.
5. silver/titanium dioxide composite heterogenous junction structure according to claim 3, is characterized in that: described nano silver wire is polycrystalline nano silver wire, and diameter is 10-60 nm; The average diameter of described titanium dioxide ball is 200-600 nm, is preferably 450nm.
6. a preparation method for silver/titanium dioxide composite heterogenous junction structure, is characterized in that: thus at nano silver wire surface deposition titanium dioxide, form hud typed or pelletron type composite heterogenous junction structure, comprise the following steps:
(1) nano silver wire is dispersed in solvent, dipping a period of time makes solvent soak on the surface of nano silver wire, obtains nano silver wire suspension;
(2) in nano silver wire suspension, add alcohol and bridging agent, under room temperature, stir;
(3) in the suspension of step (2), add titanium source, under room temperature, stir;
(4) temperature of the suspension of rising step (3), makes titanium dioxide deposition on nano silver wire surface, and centrifugation after reaction, washing, obtain silver/titanium dioxide composite heterogenous junction structure.
7. preparation method according to claim 6, is characterized in that: in step (1), disperseing the solvent of nano silver wire is deionized water, methyl alcohol, ethanol, propyl alcohol or butanols; In step (2), described alcohol is monohydric alcohol; Described bridging agent is TGA or mercaptopropionic acid; In step (3), described titanium source is butyl titanate, metatitanic acid orthocarbonate or isopropyl titanate.
8. preparation method according to claim 6, is characterized in that: the solvent in step (1) is the alcohol in deionized water, step (2) while being methyl alcohol, ethanol or propyl alcohol, and products obtained therefrom is the pelletron type composite heterogenous junction structure of nano silver wire and titanium dioxide; Solvent in step (1) is that the alcohol in deionized water, step (2) is isopropyl alcohol or carbon chain lengths while being more than or equal to four monohydric alcohol, and products obtained therefrom is the hud typed composite heterogenous junction structure of nano silver wire and titanium dioxide; Solvent in step (1) is the alcohol in methyl alcohol, ethanol, propyl alcohol or butanols, step (2) while being arbitrary monohydric alcohol, and products obtained therefrom is the hud typed composite heterogenous junction structure of nano silver wire and titanium dioxide.
9. preparation method according to claim 6, is characterized in that: in step (1), the time of dipping is 4h-7 days; In step (4), suspension is risen to 120-200 ℃ and react, the reaction time is 4-20 h.
10. according to the preparation method described in claim 6,7 or 8, it is characterized in that: the mol ratio in nano silver wire and titanium source is 1:0.7 ~ 14; Described titanium source and bridging agent are liquid, while preparing pelletron type composite heterogenous junction structure, the volume ratio of titanium source and bridging agent is (1 ~ 10): (0.4 ~ 2), while preparing hud typed composite heterogenous junction structure, the volume ratio of titanium source and bridging agent is (1 ~ 10): (0 ~ 2).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110112232A1 (en) * | 2008-06-24 | 2011-05-12 | Vijay Krishna | Enhancement of electron scavenging by water-soluble fullerenes |
| CN103316673A (en) * | 2013-06-27 | 2013-09-25 | 中国空间技术研究院 | Silver-carbon-codoped bicrystal mesoporous titanium dioxide visible light photocatalyst and preparation method thereof |
-
2014
- 2014-01-08 CN CN201410008189.9A patent/CN103721708B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110112232A1 (en) * | 2008-06-24 | 2011-05-12 | Vijay Krishna | Enhancement of electron scavenging by water-soluble fullerenes |
| CN103316673A (en) * | 2013-06-27 | 2013-09-25 | 中国空间技术研究院 | Silver-carbon-codoped bicrystal mesoporous titanium dioxide visible light photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| PARTHIBAN RAMASAMY等: ""Effects of TiO2 shells on optical and thermal properties of silver nanowires"", 《J.MATER.CHEM.》 * |
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