CN108187720A - A kind of preparation method of the composite titanium dioxide nano wire of N-Au codopes - Google Patents
A kind of preparation method of the composite titanium dioxide nano wire of N-Au codopes Download PDFInfo
- Publication number
- CN108187720A CN108187720A CN201810011824.7A CN201810011824A CN108187720A CN 108187720 A CN108187720 A CN 108187720A CN 201810011824 A CN201810011824 A CN 201810011824A CN 108187720 A CN108187720 A CN 108187720A
- Authority
- CN
- China
- Prior art keywords
- solution
- titanium dioxide
- codopes
- dioxide nano
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 85
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 33
- 125000003368 amide group Chemical group 0.000 claims abstract description 25
- 235000019441 ethanol Nutrition 0.000 claims abstract description 25
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 96
- 239000010931 gold Substances 0.000 claims description 53
- 229910052737 gold Inorganic materials 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- YYAPGCGSUOZSNQ-UHFFFAOYSA-K ethanol;trichlorogold Chemical compound CCO.Cl[Au](Cl)Cl YYAPGCGSUOZSNQ-UHFFFAOYSA-K 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 7
- -1 compound titanium dioxide Chemical class 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- 239000000499 gel Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- 230000032683 aging Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000012149 noodles Nutrition 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation methods of the composite titanium dioxide nano wire of N Au codopes, are related to a kind of high-specific surface area, the preparation method of the multiple elements design titanium dioxide nano thread of high length-diameter ratio.The mixed solution of butyl titanate and ethyl alcohol is added in the aqueous solution of slant acidity, treats that it hydrolyzes to form colloidal sol and is aged as gel.Change the distribution of titanium dioxide surface hydroxyl using the alkaline condition that NaOH is provided, Hyperbranched Polymer with Terminal Amido complexing reducing metal ion obtains the common compound titanium dioxide nano thread photochemical catalysts of N Au so as to make its oriented growth.The present invention utilizes the synergistic effect of NaOH and Hyperbranched Polymer with Terminal Amido, the pattern and size of nano material is controlled, it is achieved thereby that the polynary codope of titanium dioxide nano thread.This doping method is simple, and uniform doping.
Description
Technical field
It is more particularly to a kind of to have that high visible is corresponding, height is urged the present invention relates to a kind of preparation method of catalysis material
Change the light-catalysed preparation method of composite titanium dioxide nano wire of the multi-element doping of efficiency.
Background technology
Nano-titanium dioxide has high catalytic activity, good as important inorganic transition metal oxide material
Against weather, excellent anti-uv-ray.In recent years, the research of titanium dioxide nano material is growing day by day, at waste water
The fields such as reason, sun-proof skin care, coating and sensor, photochemical catalyst receive the concern of people.Compared to other transition metal oxides,
Nano-titanium dioxide can absorb ultraviolet light, reflection ultraviolet light, can also penetrate visible ray, before being superior performance, great development
The ultra-violet protecting agent on way.Numerous studies show compared to titanium dioxide nanoparticle, the specific surface area of titanium dioxide nano thread
Bigger, surface electronic transmission speed faster, it is wider using area.But pure nano-titanium dioxide semi-conducting material is as catalyst
It comes with some shortcomings：Be first itself energy gap it is wider (Eg=3.2ev), it is ultraviolet less than 387nm to be only capable of absorbing wavelength
Light, and the visible ray to being in the great majority in sunlight does not act；Secondly the recombination probability of electron-hole is big, effectively
The photon time-to-live is short, quantity is few so that nano-titanium dioxide can not give full play to its catalytic.
In order to improve application of the nano-titanium dioxide in photocatalysis field, a large amount of report displays, to nano-titanium dioxide into
Row doping is a kind of effective ways to the absorption of visible ray to reduce its energy gap or improve.Doping method is related to metal and non-
Metal-doped, ion doping, semiconductors coupling and surface modification etc., wherein precious metal doping effect is best, and doping approach includes
Ultraviolet photoreduction met hod, chemical reduction method and electrochemical deposition method etc..After nano-titanium dioxide light excitation after modification, valence band
The electronics of middle generation flows to the metal that Fermi can be relatively low so that and the separation in light induced electron and hole improves quantum efficiency, and then
Improve the photocatalysis performance of nano-titanium dioxide.Common metal is doped with Pt, Ag, Pd and various rare metals, metal ion
And metal oxide, but the metal-doped utilization rate to visible ray is still relatively low.Based on nonmetal doping is mainly adulterated with N, but N
Doping also easily causes the compound of electrons and holes, reduces photocatalysis efficiency.Therefore, metal and nonmetallic co-doped are utilized
Titanium dioxide nano thread can act synergistically, and while visible light region is effectively expanded, improve photocatalysis efficiency, preparation can
Widely applied catalysis material.
The photocatalysis performance of nano-titanium dioxide and its form have very big relationship, at present its existence form have spherical shape, stick,
It is linear etc..The method of titanium dioxide nano thread includes sol-gel method, microemulsion method, solvent method and hydro-thermal reaction method, generally
It is first to prepare titanium dioxide granule, then titanium dioxide nano thread is made through alkaline condition hydro-thermal.Nanometer made from these methods
Size, Size Distribution and the reaction condition of titanium dioxide granule directly affect titanium dioxide nano thread surface topography and
Dimensional homogeneity, and the energy consumption of this two-step synthesis method is higher, seriously polluted, does not meet low energy consumption, " green " production requirement.
The photocatalytic of modified nano-titanium dioxide is also related with the state of dopant, structure, content, distribution etc..Such as mix
During miscellaneous gold simple substance, golden simple substance catalytic activity is influenced by nanogold particle size, load capacity etc..Research shows that work as gold
During particle size ＜ 10nm, higher catalytic activity is shown；During golden simple substance load capacity ＜ 5%, it is easier to obtain small size
Gold particle.In addition, the specific surface area of nano-titanium dioxide and also influencing composite catalyst with the interaction of gold particle
Activity.When load capacity is excessive, the compound of electrons and holes is accelerated instead, reduces catalytic efficiency.To sum up, in loaded metal particle
In the process, the size of metallic particles and the controlled distribution on nano-titanium dioxide are particularly important.In addition, using
Simply, the preparation process of convenience and high-efficiency shortens process time, cost-effective and WeiLai Technology developing direction.
Invention content
The purpose of the present invention is to overcome the deficiency in the prior art, provides a kind of simple for process, can realize N, Au codope, tool
There is the preparation method of the titanium dioxide nano thread compared with big L/D ratio.The titanium dioxide of the N-Au codopes prepared by this method is received
Rice noodles have high-specific surface area, high catalytic activity and environment friendly and pollution-free advantage, can be widely applied to gas purification, sewage disposal
With solar cell etc..
The present invention the first technical solution be：A kind of preparation side of the composite titanium dioxide nano wire of N-Au codopes
Method includes the following steps：
(a) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. dioxy after standing
Change titanium gel；
(b) alkalinity and solution containing golden simple substance and the solution of Hyperbranched Polymer with Terminal Amido are mixed；
(c) mixed solution that the titania gel that step (a) obtains is obtained with step (b) is sufficiently mixed, and kept
A period of time within the temperature range of 180~240 DEG C；Then pickling, drying are received to get the composite titanium dioxide of N-Au codopes
Rice noodles.
The present invention second of technical solution be：A kind of preparation side of the composite titanium dioxide nano wire of N-Au codopes
Method includes the following steps：
(I) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. dioxy after standing
Change titanium gel；
(II) chlorauric acid solution is added in the solution of dissaving polymer, and ebuillition of heated；
(III) solution containing golden simple substance in alkaline solution and step (II) is added to Hyperbranched Polymer with Terminal Amido
In solution, and it is uniformly mixed；
(IV) mixed solution that the titania gel that step (I) obtains is obtained with step (III) is sufficiently mixed, and protect
Hold a period of time within the temperature range of 180~240 DEG C；Then pickling, the dry composite titanium dioxide to get N-Au codopes
Nano wire.
The present invention the third technical solution be：A kind of preparation side of the composite titanium dioxide nano wire of N-Au codopes
Method includes the following steps：
(1) ethanol solution of butyl titanate is added dropwise in the aqueous solution of formic acid, continues stirring until solution presentation
It is light blue, form spawn after still aging a period of time；
(2) ethanol solution of gold chloride is added dropwise in the aqueous solution of dissaving polymer, ebuillition of heated to solution is in light
Pink colour；
(3) aqueous solution containing golden simple substance in NaOH aqueous solutions and step (2) is added to Hyperbranched Polymer with Terminal Amido
In ethanol solution, continue stirring until uniformly mixed；
(4) gel and the solution of step (3) obtained step (1) adds in poly- four after mixing using cell disruptor
In vinyl fluoride hydrothermal reaction kettle, kept for 24~36 hours at 180~240 DEG C, add in HCl after cooling, absolute ethyl alcohol and go from
Sub- water washing centrifugation is multiple, and the composite titanium dioxide nano wire of N-Au codopes is obtained after dry.
Further, in the step (1), a concentration of 50~150g/L of butyl titanate, in aqueous formic acid, formic acid
Volume ratio with deionized water is 1:1~2:1, the ethanol solution of butyl titanate and the volume ratio of aqueous formic acid are 2:1~
8:1。
Further, in the step (2) gold chloride ethanol solution a concentration of 0.02~0.30mol/L, Amino End Group surpasses
The concentration of aqueous solution of branched polymer is the molar ratio of 10~100g/L, gold chloride ethanol solution and Hyperbranched Polymer with Terminal Amido
It is 1:50~1:200.
Further, in the step (3) NaOH aqueous solutions a concentration of 8~18mol/L, golden simple substance solution, NaOH water
The volume ratio of the ethanol solution of solution and Hyperbranched Polymer with Terminal Amido is 1:1:2~1:4:4.
Further, the mass ratio of titania gel and mixed solution is 1 in the step (4):5~1:10.
Further, the diameter of the composite titanium dioxide nano wire of prepared N-Au codopes is in 10~80nm, Jin Han
Amount 0.001%~2%, 5~15nm of gold particle size.
Hyperbranched Polymer with Terminal Amido is that one kind has the spheroidal porous three-dimensional reticular structure of class, possesses a large amount of active ammonias
Base, highly dissoluble, highly viscous polymer.The polymeric inner has a large amount of gaps, may act as a nanometer reaction vessel control granule
Diameter is formed with the nano particle for stablizing pattern.Alkaline condition, particularly NaOH provide the growth soft template of nano wire so that nanometer
Line is grown along same crystal face.
Reduction gold chloride radical ion can be complexed using Hyperbranched Polymer with Terminal Amido in the present invention, while titanium dioxide is controlled to receive
The principle of the growth of rice noodles.In water-heat process, titanium dioxide gradually forms long harness under alkaline condition, on Amino End Group polymer
Cavity structure make nano-titanium dioxide that should not reunite, and form Sodium Titanate, by the ion exchange of HCl, flint dry, shape
Into titanium dioxide nano thread.In pyroprocess, abundant amino can be permeated to nano-titanium dioxide intracell, formed N and mixed
It is miscellaneous.And the heating of the Hyperbranched Polymer with Terminal Amido solution of gold chloride, when boiling, ammonia root is as reducing agent and amine-terminated hyperbrancedization
Polymer obtains homodisperse nanogold particle as dispersant with this.By hydrothermal high-temperature process, golden simple substance passes through hydrogen bond
Effect is adhered on titanium dioxide nano thread, and then obtain the composite titanium dioxide nano wire of N-Au codopes.
Compared with prior art, the present invention has the advantage that：(1) pass through the controllable acquisition of Hyperbranched Polymer with Terminal Amido
With compared with big L/D ratio, the uniform titanium dioxide nano thread of forming；(2) preparation process is simple, and Au simple substance sizes are controllable, are conducive to
Production efficiency is improved, it is cost-effective；(3) it can effectively be controlled by adjusting the concentration ratio ratio of gold chloride and Hyperbranched Polymer with Terminal Amido
The size of the nanogold particle of system；(4) nanogold particle of doping is evenly distributed on the titanium dioxide, can preferably apply each
A field.
Description of the drawings
The present invention is further described with reference to the accompanying drawings and examples；
Fig. 1 is N-Au codoping titanium dioxide nano line transmission electron microscope pictures prepared by embodiment 5；
Fig. 2 is N-Au codoping titanium dioxide nano line XRD spectrums prepared by embodiment 5.
Specific embodiment
In order to clarify the technical solutions and technical objectives of the present invention, below in conjunction with the accompanying drawings and specific embodiment is the present invention
It is further to introduce.
Embodiment 1：
By the butyl titanate ethanol solution of a concentration of 125g/L of 80ml be added dropwise to by 10ml formic acid and 10ml go from
In the mixed solution of sub- water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.It will
The gold chloride ethanol solution of a concentration of 0.1mol/L of 0.25ml is added to the Hyperbranched Polymer with Terminal Amido of a concentration of 30g/L of 10ml
Aqueous solution in, ebuillition of heated to solution be in pale pink.By the NaOH solution of a concentration of 10mol/L of 20ml, 20ml is a concentration of
The ethanol solution of the Hyperbranched Polymer with Terminal Amido of 20g/L is mixed to join in the solution, is continued stirring until and is added after mixing
Enter 10g titania gels, be put into ptfe autoclave after mixing using cell disruptor, added at 200 DEG C
Heat 24 hours.After cooling, the HCl solution for adding in 0.1mol/L adjusts pH value of solution to 7 or so.Solution is washed three times with ethyl alcohol,
Centrifugation, deionized water are washed three times, are centrifuged, and average diameter are just can obtain after dry as 24.4nm, gold content is
0.6035%, the composite titanium dioxide nano-wire catalyst of the N-Au codopes of a diameter of 8.5nm of gold particle.
Embodiment 2：
By the butyl titanate ethanol solution of a concentration of 125g/L of 80ml be added dropwise to by 10ml formic acid and 10ml go from
In the mixed solution of sub- water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.It will
The gold chloride ethanol solution of a concentration of 0.1mol/L of 0.5ml is added to the Hyperbranched Polymer with Terminal Amido of a concentration of 30g/L of 10ml
Aqueous solution in, ebuillition of heated to solution be in pale pink.By the NaOH solution of a concentration of 10mol/L of 20ml, 20ml is a concentration of
The ethanol solution of the Hyperbranched Polymer with Terminal Amido of 60g/L is mixed to join in the solution, is continued stirring until and is added after mixing
Enter 10g titania gels, be put into ptfe autoclave after mixing using cell disruptor, added at 200 DEG C
Heat 24 hours.After cooling, the HCl solution for adding in 0.1mol/L adjusts pH value of solution to 7 or so.Solution is washed three times with ethyl alcohol,
Centrifugation, deionized water are washed three times, are centrifuged, and average diameter are just can obtain after dry as 36.5nm, gold content is
1.2680%, the composite titanium dioxide nano-wire catalyst of the N-Au codopes of a diameter of 10.9nm of gold particle.
Embodiment 3：
By the butyl titanate ethanol solution of a concentration of 125g/L of 80ml be added dropwise to by 10ml formic acid and 10ml go from
In the mixed solution of sub- water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.It will
The gold chloride ethanol solution of a concentration of 0.1mol/L of 0.30ml is added to the Hyperbranched Polymer with Terminal Amido of a concentration of 50g/L of 10ml
Aqueous solution in, ebuillition of heated to solution be in pale pink.By the NaOH solution of a concentration of 16mol/L of 30ml, 20ml is a concentration of
The ethanol solution of the Hyperbranched Polymer with Terminal Amido of 15g/L is mixed to join in the solution, is continued stirring until and is added after mixing
Enter 10g titania gels, be put into ptfe autoclave after mixing using cell disruptor, added at 200 DEG C
Heat 30 hours.After cooling, the HCl solution for adding in 0.1mol/L adjusts pH value of solution to 7 or so.Solution is washed three times with ethyl alcohol,
Centrifugation, deionized water are washed three times, are centrifuged, and average diameter are just can obtain after dry as 43.1nm, gold content is
0.8911%, the composite titanium dioxide nano-wire catalyst of the N-Au codopes of a diameter of 6.6nm of gold particle.
Embodiment 4：
The butyl titanate ethanol solution of a concentration of 90g/L of 88ml is added dropwise to by 15ml formic acid and 10ml deionizations
In the mixed solution of water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.By 0.30ml
The gold chloride ethanol solution of a concentration of 0.2mol/L is added to the water-soluble of the Hyperbranched Polymer with Terminal Amido of a concentration of 80g/L of 10ml
In liquid, ebuillition of heated to solution is in pale pink.By the NaOH solution of a concentration of 12mol/L of 20ml, the end of a concentration of 15g/L of 30ml
The ethanol solution of amino dissaving polymer is mixed to join in the solution, continues stirring until addition 15g dioxies after mixing
Change titanium gel, be put into ptfe autoclave using cell disruptor, heated 28 hours at 230 DEG C after mixing.
After cooling, the HCl solution for adding in 0.1mol/L adjusts pH value of solution to 7 or so.By solution with ethyl alcohol wash three times, centrifugation, go from
Sub- water is washed three times, centrifugation, and average diameter is just can obtain after dry as 49.7nm, gold content 1.0273%, gold particle
The composite titanium dioxide nano-wire catalyst of the N-Au codopes of a diameter of 6.7nm.
Embodiment 5：
The butyl titanate ethanol solution of a concentration of 70g/L of 86ml is added dropwise to by 18ml formic acid and 10ml deionizations
In the mixed solution of water composition, and it is stirred continuously to solution and is light blue color.It is still aging until colloidal sol be in gel.By 0.30ml
The gold chloride ethanol solution of a concentration of 0.08mol/L is added to the water of the Hyperbranched Polymer with Terminal Amido of a concentration of 50g/L of 10ml
In solution, ebuillition of heated to solution is in pale pink.By the NaOH solution of a concentration of 12mol/L of 30ml, a concentration of 18g/L's of 30ml
The ethanol solution of Hyperbranched Polymer with Terminal Amido is mixed to join in the solution, continues stirring until addition 8g dioxies after mixing
Change titanium gel, be put into ptfe autoclave using cell disruptor, heated 36 hours at 220 DEG C after mixing.
After cooling, the HCl solution for adding in 0.1mol/L adjusts pH value of solution to 7 or so.By solution with ethyl alcohol wash three times, centrifugation, go from
Sub- water is washed three times, centrifugation, and average diameter is just can obtain after dry as 30.5nm, gold content 1.6037%, gold particle
The composite titanium dioxide nano-wire catalyst of the N-Au codopes of a diameter of 6.2nm.
By taking embodiment 5 as an example, Fig. 1 is the transmission electron microscope picture of composite titanium dioxide nano wire that embodiment 5 obtains, from figure
Good, uniform, diameter 30nm or so, it is evident that titanium dioxide nano thread becomes second nature, many gold particles of surface doping.Compares figure 2
XRD spectrum, ten diffraction maximums correspond to respectively the crystallographic plane diffraction peak (101) of anatase-type nanometer titanium dioxide, (004),
(200), (105), (211) and (204), and the crystallographic plane diffraction peak that (111), (200), (220) and (311) are Au simple substance, bring into
Scherrer formula is computed obtaining, the average-size of gold particle is 6.2nm.This result is consistent with transmission electron microscope observed result.
Basic principle, main feature and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of preparation method of the composite titanium dioxide nano wire of N-Au codopes, which is characterized in that include the following steps：
(a) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. titanium dioxide after standing
Gel；
(b) alkalinity and solution containing golden simple substance and the solution of Hyperbranched Polymer with Terminal Amido are mixed；
(c) mixed solution that the titania gel that step (a) obtains is obtained with step (b) is sufficiently mixed, and is maintained at 180
A period of time within the temperature range of~240 DEG C；Then pickling to get N-Au codopes composite titanium dioxide nano wire.
2. a kind of preparation method of the composite titanium dioxide nano wire of N-Au codopes, which is characterized in that include the following steps：
(I) solution of tetrabutyl titanate is added in acid solution, stirring is converted into spawn, i.e. titanium dioxide after standing
Gel；
(II) chlorauric acid solution is added in the solution of dissaving polymer, and ebuillition of heated；
(III) solution containing golden simple substance in alkaline solution and step (II) is added to the solution of Hyperbranched Polymer with Terminal Amido
In, and be uniformly mixed；
(IV) mixed solution that the titania gel that step (I) obtains is obtained with step (III) is sufficiently mixed, and be maintained at
A period of time within the temperature range of 180~240 DEG C；Then pickling, the dry composite titanium dioxide nanometer to get N-Au codopes
Line.
3. a kind of preparation method of the composite titanium dioxide nano wire of N-Au codopes, which is characterized in that include the following steps：
(1) ethanol solution of butyl titanate is added in acid aqueous solution, and stir, stand a period of time after be converted into
Spawn；
(2) ethanol solution of gold chloride is added drop-wise in the aqueous solution of dissaving polymer, ebuillition of heated to solution is in pale pink；
(3) ethyl alcohol that the aqueous solution containing golden simple substance in acidic aqueous solution and step (2) is added in Hyperbranched Polymer with Terminal Amido is molten
In liquid, continue stirring until uniformly mixed；
(4) titania gel obtained in step (1) is added in the mixed solution of step (3), it is made using agitating device
It is thoroughly mixed and is placed in thermostat, 24~36h is heated at 180~240 DEG C；Hydrochloric acid, anhydrous is utilized after being cooled to room temperature
Ethyl alcohol, deionized water wash centrifugation removal impurity repeatedly, and the composite titanium dioxide nano wire of N-Au codopes is obtained after dry.
4. the preparation method of the composite titanium dioxide nano wire of the N-Au codopes according to claims 1 or 2 or 3, special
Sign is：A concentration of 50~150g/L of the solution of tetrabutyl titanate.
5. the preparation method of the composite titanium dioxide nano wire of the N-Au codopes according to claims 1 or 2 or 3, special
Sign is：A concentration of 0.02~0.30mol/L of the gold chloride ethanol solution.
6. the preparation method of the composite titanium dioxide nano wire of the N-Au codopes according to claims 1 or 2 or 3, special
Sign is：The Hyperbranched Polymer with Terminal Amido solution concentration is 10~100g/L.
7. the preparation method of the composite titanium dioxide nano wire of the N-Au codopes according to claims 1 or 2 or 3, special
Sign is：A concentration of 8~18mol/L of the alkaline aqueous solution, golden simple substance solution, alkaline solution polymerize with amine-terminated hyperbrancedization
The volume ratio of object solution is 1:1:2~1:4:4.
8. the preparation method of the titanium dioxide nano thread of the N-Au codopes according to claims 1 or 2 or 3, feature exist
In：The mass ratio of the titania gel and mixed solution is 1:5~1:10.
9. the preparation method of the titanium dioxide nano thread of the N-Au codopes according to claims 1 or 2 or 3, feature exist
In：The diameter of the composite titanium dioxide nano wire of prepared N-Au codopes is in 10~80nm, gold content 0.001%~2%,
5~15nm of gold particle size.
10. the preparation method of the titanium dioxide nano thread of the N-Au codopes according to claims 1 or 2 or 3, feature exist
In：The agitating device is cell disruptor, and the thermostat is hydrothermal reaction kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810011824.7A CN108187720B (en) | 2018-01-05 | 2018-01-05 | Preparation method of N-Au co-doped composite titanium dioxide nanowire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810011824.7A CN108187720B (en) | 2018-01-05 | 2018-01-05 | Preparation method of N-Au co-doped composite titanium dioxide nanowire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108187720A true CN108187720A (en) | 2018-06-22 |
| CN108187720B CN108187720B (en) | 2020-04-21 |
Family
ID=62587903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810011824.7A Active CN108187720B (en) | 2018-01-05 | 2018-01-05 | Preparation method of N-Au co-doped composite titanium dioxide nanowire |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108187720B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110743585A (en) * | 2019-11-20 | 2020-02-04 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332737A (en) * | 2013-07-11 | 2013-10-02 | 苏州大学 | Preparation method of titanium dioxide nano-powder |
-
2018
- 2018-01-05 CN CN201810011824.7A patent/CN108187720B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332737A (en) * | 2013-07-11 | 2013-10-02 | 苏州大学 | Preparation method of titanium dioxide nano-powder |
Non-Patent Citations (1)
| Title |
|---|
| 邵享文等: "银氮共掺杂二氧化钛的制备及其抗菌性能", 《环境工程学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110743585A (en) * | 2019-11-20 | 2020-02-04 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
| CN110743585B (en) * | 2019-11-20 | 2022-02-18 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108187720B (en) | 2020-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107126944B (en) | A kind of more doping titanium dioxide nano particles of more defects with high visible light catalytic activity and preparation method | |
| CN106824248A (en) | A kind of pattern and the controllable WO of composition3Nanometer sheet/g C3N4The preparation method of nano composite material | |
| CN108786792B (en) | Metal/semiconductor composite photocatalyst and preparation and application thereof | |
| CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
| CN102600857A (en) | Preparation method of carbon ball-loaded CuO-BiVO4 heterojunction compound photocatalyst | |
| CN106914236A (en) | The amorphous state plasma hetero-junctions nano-TiO of efficient visible light response2Colloidal sol | |
| CN103272592B (en) | One dimension carries the preparation method of silver-colored titanium dioxide nano-rod photo-catalyst | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN110227453A (en) | A kind of preparation method of Ag/ZnO/GO composite visible light catalyst | |
| CN102873337A (en) | Poly-allylamine oriented platinum nano cube preparation method | |
| CN105540640A (en) | Preparation method of flower-shaped nanometer zinc oxide | |
| CN102515244A (en) | Hollow cuprous oxide nanometre material and preparation method for same | |
| CN105195143A (en) | Mesoporous photocatalytic material and preparation method thereof | |
| CN108339574A (en) | A kind of titanium matrix composite of visible light photocatalytic degradation rhodamine B and its preparation | |
| Ren et al. | Novel ternary Ag/CeVO 4/gC 3 N 4 nanocomposite as a highly efficient visible-light-driven photocatalyst | |
| CN104511280B (en) | A kind of visible light catalyst and preparation method thereof | |
| CN114618537B (en) | Red phosphorus/strontium titanate heterojunction photocatalyst, and preparation method and application thereof | |
| CN111701583A (en) | Ultrathin hexagonal BiO2-x platelet photocatalyst and preparation method thereof | |
| CN114522709B (en) | Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof | |
| CN102580720B (en) | Visible light response nano zinc oxide-bismuth oxide composite photocatalyst and preparation method thereof | |
| CN105749908B (en) | A kind of Au@TiO2Hollow core-shell structure photochemical catalyst and preparation method thereof | |
| CN109133169B (en) | Bismuth vanadate and preparation method and application thereof | |
| CN104437457A (en) | Preparation method of full-spectrum sunlight catalyst | |
| CN108607536B (en) | Method for preparing bismuth-doped nano titanium dioxide photocatalyst | |
| CN108579775B (en) | Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |