CN109678201A - A kind of method of titanium dioxide surface modification - Google Patents
A kind of method of titanium dioxide surface modification Download PDFInfo
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- CN109678201A CN109678201A CN201910080236.3A CN201910080236A CN109678201A CN 109678201 A CN109678201 A CN 109678201A CN 201910080236 A CN201910080236 A CN 201910080236A CN 109678201 A CN109678201 A CN 109678201A
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- Prior art keywords
- titanium dioxide
- surface modification
- electrolyte
- mixed liquor
- titanium oxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000004048 modification Effects 0.000 title claims abstract description 24
- 238000012986 modification Methods 0.000 title claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 14
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 241000790917 Dioxys <bee> Species 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000007547 defect Effects 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000011344 liquid material Substances 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 description 21
- 239000010936 titanium Substances 0.000 description 20
- 229910052719 titanium Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 8
- 229910001000 nickel titanium Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 230000004298 light response Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003081 TiO2−x Inorganic materials 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/043—Titanium sub-oxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The present invention relates to photocatalyst material synthesis technical fields, more particularly to a kind of method of titanium dioxide surface modification, it disperses titania powder in electrolyte, cathode glow discharging plasma is generated in the electrolytic solution, atmosphere of hydrogen is generated by cathode glow discharging plasma electrolysis water and hydro-reduction processing is carried out to titanium dioxide, after electric discharge, the titanium oxide with core-shell structure is obtained.The present invention realizes a step using cathode glow discharging plasma and quickly prepares visible light-responded reproducibility titanium oxide, and no any chemical reducing agent of addition in preparation process, is a kind of environmentally protective technology of preparing；Preparation process is simple, only consumes electric energy and a small amount of liquid, and raw material titanium dioxide is convenient for carrying out mass production without self-control, directly one step surface modification treatment of progress.The method of titanium dioxide surface modification of the invention is not necessarily to titanium oxide carrying out high temperature reduction processing under an atmosphere of hydrogen, improves the safety of preparation process, is convenient for industrialized production.
Description
Technical field
The present invention relates to photocatalyst material synthesis technical fields, and in particular to a kind of side of titanium dioxide surface modification
Method.
Background technique
Titanium dioxide (TiO2) it is used as a kind of most common semiconductor catalyst, because of its cheap, nontoxic, chemical property
The features such as stablizing, is widely used the fields such as air cleaning, sewage treatment.The principle of the titanium dioxide depollution of environment, i.e. light are urged
Change reaction, is that organic matter, such as dyestuff, formaldehyde etc. itself generate photoproduction electricity under illumination condition in titanium dioxide absorption environment
Sub- hole pair, and generation high active substance is induced, such as superoxide radical, hydroxyl radical free radical.These high active substances and oxidation
Redox reaction, product CO occur for the organic matter of titanium absorption2、H2O.Optically catalytic TiO 2 efficiency is mainly by two sides at present
Face limitation: being the limitation of optical response range first.Pure titinium dioxide has wider energy gap (anatase 3.2eV, rutile
3eV), which results in titanium dioxide can only absorb ultraviolet light, and ultraviolet light only occupies the energy of sunlight 7%, therefore how to increase
The visible light utilization efficiency for adding titanium dioxide, the photocatalysis performance for improving titanium dioxide have obtained people and have more and more paid close attention to.Separately
It on the one hand is the limitation of the separative efficiency of photo-generated carrier.The photo-generated carrier that titanium dioxide is generated by light radiation, significant portion
All compound in titanium dioxide intracell, only small part photo-generated carrier migrates to surface and redox reaction occurs, light
The separative efficiency of raw carrier is higher, and photocatalysis performance is better.Therefore current dioxy can effectively be solved from this two parts
Change the low problem of titanium photocatalysis efficiency.
, there are a large amount of reports about synthesis grey or black in the recent period in the problem of for promoting photocatalytic titanium oxide response range
Reproducibility titanium oxide TiO2-xEnhance the absorption of its visible light, main method includes: (1) different reducing gas (H2、NH3) condition
Under TiO2Thermal reduction processing；(2) electronation is handled；(3) the methods of electrochemical reduction.These methods have something in common:
It requires titanium oxide carrying out high temperature reduction processing.Handled by high temperature reduction, the color of titanium oxide from white become grey or
Person's black, and form the Lacking oxygen defect or surface titanous Ti of unique shell-core structure and auto-dope3+, result in synthesis
Gray/black titanium oxide forbidden bandwidth narrow, it is seen that photoresponse enhancing, to improve the visible light catalytic of titanium oxide
Can, such as Chinese patent: application number: 201610651407.X；Application number: 201510093753.6.However prepared by the above method
Black/gray oxide titanium, surface Ti3+Or Lacking oxygen is very unstable in air, is easily oxidized in air or water,
Therefore the photocatalytic activity of titanium oxide is greatly reduced.Reproducibility titania photocatalyst is synthesized also with the above method, usually
Complicated synthesis step, harsh experiment condition, or expensive equipment are needed, this seriously inhibits black/gray oxide titaniums to answer
For actual industrial production.Because simple, feasible, the efficient method of the invention one kind carrys out the stable gray/black oxygen of synthesis performance
Change titanium to be of great significance.
Commercial titanium dioxide usually has excellent ultraviolet catalytic performance, and cheap and easy to get, but under visible light conditions,
Its degradation of organic substances ability is very little.Therefore, it is directly modified using commercial titanium oxide progress surface to develop one kind, it can with acquisition
The method of the titanium oxide of light-exposed response can shorten material preparation time to greatest extent, reduce energy consumption, save cost, have weight
Want meaning.
Cathode glow discharging technology has been found broad application as a kind of material processing technology of maturation.Cathode glow is put
Electricity generates plasma in a liquid, since there are a large amount of high energy electrons in plasma, so that liquid is decomposed and generated
Atmosphere of hydrogen then forms high temperature reduction environment in a liquid, this facilitates the reproducibility nanometer material that synthesis has lattice defect
Material, to show unique Wuli-Shili-Renli system approach.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of titanium dioxide tables
The modified method in face, preparation process are simple, environmentally protective, it is only necessary to consume electric energy and a small amount of liquid, exist without being in addition passed through hydrogen
It is sintered under high temperature, safe ready.
The purpose of the invention is achieved by the following technical solution: a kind of method of titanium dioxide surface modification: by titanium dioxide
Titanium powder is scattered in electrolyte, in the electrolytic solution generate cathode glow discharging plasma, by cathode glow discharging etc. from
Daughter electrolysis water generates atmosphere of hydrogen and carries out hydro-reduction processing to titanium dioxide, after electric discharge, obtains with shell core knot
The titanium oxide of structure.
The present invention realizes that only to need a step that can quickly prepare visible light-responded using cathode glow discharging plasma
Reproducibility titanium oxide without adding any chemical reducing agent in preparation process, therefore is a kind of environmentally protective technology of preparing.This
Invention only consumes electric energy and a small amount of liquid since preparation process is simple, and raw material titanium dioxide directly carries out one without self-control
Surface modification treatment is walked, therefore is easy to exploitation using this method and is equipped at industrialization production, carries out mass production.Of the invention
The method of titanium dioxide surface modification is not necessarily to titanium oxide carrying out high temperature reduction processing under an atmosphere of hydrogen, improves preparation process
Safety, be convenient for industrialized production.Temperature near plasma is up to 1,000 more to be spent, the temperature of general hydro-reduction reaction
It is 500 degree or more, temperature is higher, and shorter the time required to hydro-reduction reaction, plasma generates shock wave, titanium dioxide in water
Titanium powder irregular movement in the electrolytic solution, with the lengthening in reaction time, can make to divide in electrolyte similar to the effect of stirring
The cathode that scattered titanium dioxide can finally move nearby generates reaction.
Preferably, specific preparation process is as follows:
(1) it configures electrolyte: configuring the electrolyte of certain conductivity；
(2) titania powder of specified particle size the dispersion of titania powder: is poured into the electrolyte of step (1) configuration
In and stir evenly, obtain mixed liquor A；
(3) it configures discharge electrode: cathode electrode and anode electrode being placed in the mixed liquor A of step (2), and keep institute
The end for stating one end of cathode electrode is immersed in mixed liquor A, and the anode electrode is placed in mixed liquor A, cathode electrode with
The distance between anode electrode is >=5mm；
(4) discharge process: apply certain voltage between cathode electrode and anode electrode, plasma is in cathode electrode
End generates；Plasma electrolysis mixed liquor A generates atmosphere of hydrogen and hydrogenates to the titanium dioxide dispersed in mixed liquor A
Reduction treatment obtains mixed liquid B after certain discharge time；
(5) titanium oxide of core-shell structure is made: solid is taken after mixed liquid B centrifuge separation will be obtained in step (4), after dry
The titanium oxide of the core-shell structure is made.
In step (3), the material of cathode electrode and anode electrode will not influence the titanium oxide of core-shell structure of the invention
Preparation, it is preferred that cathode electrode is stud, and anode electrode is platinized platinum, cathode electrode can be it is multiple, anode electrode only has one
A, multiple cathode electrodes are uniformly distributed in around anode electrode, can select the quantity of suitable cathode electrode as needed；Titanium
The diameter of stick is 2-4mm, and length 15-25cm, end has the length of 0.5-1cm to be immersed in mixed liquor A；The rule of anode platinized platinum
Lattice are 0.1*2*2cm3；Discharge time in step (4) is according to the reaction effect of titanium dioxide come fixed defined discharge time
0.1-72 hours；The titanium oxide of core-shell structure is made after solid natural air drying in step (5) after centrifugation.
Preferably, in the step (1), a certain amount of acid solution is uniformly mixed to obtain the acid of certain conductivity with water
Property electrolyte, the acid solution is at least one of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid solution, the electrolyte
Conductivity is 0.1-100ms/cm at 25 DEG C.
The conductivity of electrolyte is proportional to hydrogen ion concentration, and hydrogen ion concentration is bigger, and conductivity is bigger, the electricity of water
Hinder smaller, the amounts of hydrogen being electrolysed is about more, therefore the preferred present invention uses acidic electrolysis bath, when conductivity is in 0.1-100ms/
When cm range, the atmosphere of hydrogen of generation is enough to restore the titanium dioxide dispersed in electrolyte.
Preferably, in the step (2), the partial size of titania powder is 5-200nm；Titanium dioxide in mixed liquor A
Concentration is 0.1-1000mg/ml.
The titania powder that the present invention is 5-200nm by using partial size, the oxidation titanium products of core-shell structure obtained
Yield is higher, and the visible light catalytic effect of the titanium oxide of core-shell structure obtained significantly improves, the too big or too small dioxy of size
It is modified to change titanium, photocatalysis effect raising is unobvious, and cost is relatively low for the titanium dioxide of 5-200nm, and it is at high cost lower than 5nm, it is high
In 200nm, effect is without so good.More preferably, the partial size of titania powder is 10-30nm.
Preferably, in the step (3), the end of the cathode electrode is set as cone point, and cathode electrode is inserted in
In corundum set, only cone point exposes corundum and covers and be immersed in mixed liquor A.
By the way that cone point is arranged in the end of cathode electrode in the present invention, the length of cone point is 0.5-1cm, and will
Cathode electrode is inserted in corundum, and only cone point exposes corundum and covers and be immersed in mixed liquor A, and cathode glow discharging is enable to collect
Middle Yu Yidian, effect is more preferable, obtains more plasmas, restores titanium dioxide convenient for generating atmosphere of hydrogen, increases nucleocapsid knot
The yield of the titanium oxide of structure.Cone point discharge effect is better than thin stick discharge effect, and thin stick diameter is 2-4mm, and cone point is straight
Diameter is within 0.5mm.
Preferably, in the step (4), in discharge process, the temperature control of the electrolyte is 70-100 DEG C, described to put
Piezoelectric voltage is 200v-20kv, and the discharge power of the cathode electrode is 0.2-200KW.
In step (4) of the invention, the temperature of electrolyte is controlled in discharge process by the water-bath circulatory system, makes to be electrolysed
The temperature of liquid is maintained within the scope of 70-100 DEG C during discharge, and stablizing for discharge process is kept to carry out.When temperature is lower than 70
DEG C, cathode glow discharging plasma will not be generated, temperature is higher than 100 DEG C, and water comes to life, and influences experiment safety, is protecting
Under the premise of demonstrate,proving safety, temperature is higher, and obtained product catalyst performance is better.More preferably, the temperature of electrolyte is being put
It is maintained within the scope of 80-90 DEG C in electric process.When discharge power is lower than 0.2KW, electrolyte can not discharge.Plasma discharge electricity
Briquetting includes DC voltage, alternating voltage, pulse voltage, preferentially selects pulse voltage, and the pulse voltage is 200-1000V, arteries and veins
Rushing electric voltage frequency is 100-5000Hz.
Preferably, in the step (4), electrolytic buffer is filled into mixed liquor A during discharge, makes electrolyte
Conductivity maintains within the scope of ± the 0.5ms/cm of initial conductivity.
The present invention is slowly added to the acidic buffer of regulation conductivity into electrolytic cell in cathode plasma discharge process
Liquid to compensate the electrolyte and hydrogen ion that lose in discharge process, make the stable conductivity of electrolyte original conductivity+
Within the scope of 0.5mS/cm, stable discharging is kept.The conductivity of buffering electrolyte is 1.5-2 times of the conductivity of electrolyte.
Preferably, the titania powder is rutile titanium dioxide and/or anatase titanium dioxide.
The type of the above titanium dioxide is titanium dioxide common on the market, selects common money, is suitble to industrialized production, at
This is lower.
Preferably, the shell structure of the core-shell structure is unbodied sub- titanium oxide layer, with a thickness of 1-5nm.
The present invention control the unbodied sub- titanium oxide layer of shell structure of core-shell structure with a thickness of 1-5nm, prevent by air
It is oxidized to titanium dioxide, shell structure is thicker, and the stability of catalyst is made an appointment.The nuclear structure of affiliated core-shell structure is the dioxy of crystallization
Change titanium.
Preferably, the sub- titanium oxide of the sub- titanium oxide layer has lattice defect, and includes at least Lacking oxygen and/or trivalent
Titanium.
It include Lacking oxygen and/or titanous in sub- titanium oxide layer, visible light can be absorbed in such structure.
The beneficial effects of the present invention are: 1) raw material cheap and easy to get: the method for titanium dioxide surface modification of the invention
It is cheap using titanium oxide common on the market as titanium source.
2) preparation process is simple, environmentally protective: the method for titanium dioxide surface modification of the invention is put using cathode glow
Electro-plasma realizes a step and quickly prepares visible light-responded reproducibility titanium oxide, no addition anyization in preparation process
Reducing agent is learned, therefore is a kind of environmentally protective technology of preparing.
3) be easy to industrialization production: the method for titanium dioxide surface modification of the invention only disappears since preparation process is simple
Consuming electric power and a small amount of liquid, and raw material titanium dioxide directly carries out a step surface modification treatment without self-control, therefore utilizing should
Method is easy to exploitation and equips at industrialization production, carries out mass production.
4) safe and reliable: the method for titanium dioxide surface modification of the invention without carrying out titanium oxide under an atmosphere of hydrogen
High temperature reduction processing, improves the safety of preparation process, is convenient for industrialized production.
Detailed description of the invention
Fig. 1 is titanium dioxide surface modification process schematic；
Fig. 2 is cathode glow discharging plasma producing apparatus；
Fig. 3 is surface-modified titanium dioxide transmission electron microscope figure；
The UV, visible light of surface-modified titanium dioxide and surface unmodified commercial titanium dioxide that Fig. 4 is embodiment 1-4
Optical absorption spectra figure, the ultraviolet-visible absorption curve overlapping of the surface-modified titanium dioxide of embodiment 1-4 in figure, therefore can only see
See an absorption curve；
Fig. 5 is the surface-modified titanium dioxide of embodiment 1 and the visible light catalytic of surface unmodified commercial titanium dioxide
Degradation figure；
Fig. 6 is the surface-modified titanium dioxide of embodiment 2 and the visible light catalytic of surface unmodified commercial titanium dioxide
Degradation figure；
Fig. 7 is the surface-modified titanium dioxide of embodiment 3 and the visible light catalytic of surface unmodified commercial titanium dioxide
Degradation figure；
The visible light catalytic of the surface of Fig. 8 embodiment 4 modified dioxy titanium oxide and surface unmodified commercial titanium dioxide
Degradation figure.
Specific embodiment
For the ease of the understanding of those skilled in the art, the present invention is made below with reference to examples and drawings 1-5 further
Explanation, the content that embodiment refers to not is limitation of the invention.
Embodiment 1
It uses 5nm titania powder for raw material, prepares surface modified titanium oxide.
The nitric acid solution of 2mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 7mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at platinized platinum anode two sides, it is assembled into parallel discharge system,
The rodlike Ti cathode diameter of used two is 4mm, and length is 20cm.Two stud cathodes are inserted in alundum tube, and only
Having length is that 0.8cm tip portion is not coated by alundum tube, and a piece of plate Ni―Ti anode used, specification is 0.1*2*2cm3。
5nm titania powder 2g, electrolyte are poured into electrolytic cell, and are uniformly mixing to obtain mixed liquor, by cathode and
Anode is immersed in mixed liquor.Setting supply voltage be 600V, frequency be 1kHz pulse voltage, and be applied to stud cathode and
Ni―Ti anode both ends, the electric current of power supply is shown as 0.5A at this time.The water-bath circulatory system is opened, guarantees that cathode plasma stabilization is put
Electricity.Due to that can cause to be lost to electrolyte in discharge process, so being opened when the plasma that glow discharge generates reaches stable
Begin to be added buffer into electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min.
It discharges after 1h, stops electric discharge, be centrifuged mixed liquor using centrifuge to obtain gray precipitate things, the revolving speed of centrifuge is set
It is set to 10000 revs/min.
By gray precipitate things natural air drying 10h to get the business to surface modified titanium oxide, with surface unmodified processing
The UV-vis absorption spectrum of titanium dioxide compares figure and sees Fig. 4, it is seen that has carried out the modified dioxy in surface by the present embodiment
Big more of ultraviolet-visible absorption range for changing the titanium commercial titanium dioxide more modified than not carrying out surface, increase visible light
Response range.
Embodiment 2
It uses 50nm titania powder for raw material, prepares surface modified titanium oxide.
The nitric acid solution of 2mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 7mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at platinized platinum anode two sides, it is assembled into parallel discharge system,
The rodlike Ti cathode diameter of used two is 4mm, and length is 20cm.Two stud cathodes are inserted in alundum tube, and only
Having length is that 0.8cm tip portion is not coated by alundum tube, and a piece of plate Ni―Ti anode used, specification is 0.1*2*2cm3。
50nm titania powder 2g, electrolyte are poured into electrolytic cell, and are uniformly mixing to obtain mixed liquor, by cathode and
Anode is immersed in mixed liquor.Setting supply voltage be 600V, frequency be 1kHz pulse voltage, and be applied to stud cathode and
Ni―Ti anode both ends, the electric current of power supply is shown as 0.5A at this time.The water-bath circulatory system is opened, guarantees that cathode plasma stabilization is put
Electricity.Due to that can cause to be lost to electrolyte in discharge process, so being opened when the plasma that glow discharge generates reaches stable
Begin to be added buffer into electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min.
It discharges after 1h, stops electric discharge, be centrifuged mixed liquor using centrifuge to obtain gray precipitate things, the revolving speed of centrifuge is set
It is set to 10000 revs/min.
By gray precipitate things natural air drying 10h to get the business to surface modified titanium oxide, with surface unmodified processing
The UV-vis absorption spectrum of titanium dioxide compares figure and sees Fig. 4, it is seen that has carried out the modified dioxy in surface by the present embodiment
Big more of ultraviolet-visible absorption range for changing the titanium commercial titanium dioxide more modified than not carrying out surface, increase visible light
Response range.
Embodiment 3
It uses 100nm titania powder for raw material, prepares surface modified titanium oxide.
The nitric acid solution of 2mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 7mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at platinized platinum anode two sides, it is assembled into parallel discharge system,
The rodlike Ti cathode diameter of used two is 4mm, and length is 20cm.Two stud cathodes are inserted in alundum tube, and only
Having length is that 0.8cm tip portion is not coated by alundum tube, and a piece of plate Ni―Ti anode used, specification is 0.1*2*2cm3。
100nm titania powder 2g, electrolyte are poured into electrolytic cell, and is uniformly mixing to obtain mixed liquor, by cathode
It is immersed in mixed liquor with anode.Setting supply voltage is 600V, and frequency is the pulse voltage of 1kHz, and is applied to stud cathode
With Ni―Ti anode both ends, the electric current of power supply is shown as 0.5A at this time.The water-bath circulatory system is opened, guarantees that cathode plasma stabilization is put
Electricity.Due to that can cause to be lost to electrolyte in discharge process, so being opened when the plasma that glow discharge generates reaches stable
Begin to be added buffer into electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min.
It discharges after 1h, stops electric discharge, be centrifuged mixed liquor using centrifuge to obtain gray precipitate things, the revolving speed of centrifuge is set
It is set to 10000 revs/min.
By gray precipitate things natural air drying 10h to get the business to surface modified titanium oxide, with surface unmodified processing
The UV-vis absorption spectrum of titanium dioxide compares figure and sees Fig. 4, it is seen that has carried out the modified dioxy in surface by the present embodiment
Big more of ultraviolet-visible absorption range for changing the titanium commercial titanium dioxide more modified than not carrying out surface, increase visible light
Response range.
Embodiment 4
It uses 200nm titania powder for raw material, prepares surface modified titanium oxide.
The nitric acid solution of 2mL 0.1mol/L is instilled in 50mL deionized water, is sufficiently stirred to obtain electrolyte.By 7mL
The nitric acid solution of 0.1mol/L instills in 60mL deionized water, is sufficiently stirred to obtain buffer.
As shown in Fig. 2, two stud cathodes are symmetrically disposed at platinized platinum anode two sides, it is assembled into parallel discharge system,
The rodlike Ti cathode diameter of used two is 4mm, and length is 20cm.Two stud cathodes are inserted in alundum tube, and only
Having length is that 0.8cm tip portion is not coated by alundum tube, and a piece of plate Ni―Ti anode used, specification is 0.1*2*2cm3。
200nm titania powder 2g, electrolyte are poured into electrolytic cell, and is uniformly mixing to obtain mixed liquor, by cathode
It is immersed in mixed liquor with anode.Setting supply voltage is 600V, and frequency is the pulse voltage of 1kHz, and is applied to stud cathode
With Ni―Ti anode both ends, the electric current of power supply is shown as 0.5A at this time.The water-bath circulatory system is opened, guarantees that cathode plasma stabilization is put
Electricity.Due to that can cause to be lost to electrolyte in discharge process, so being opened when the plasma that glow discharge generates reaches stable
Begin to be added buffer into electrolytic cell to supplement electrolyte, the flow velocity that buffer is added is 1mL/min.
It discharges after 1h, stops electric discharge, be centrifuged mixed liquor using centrifuge to obtain gray precipitate things, the revolving speed of centrifuge is set
It is set to 10000 revs/min.
By gray precipitate things natural air drying 10h to get the business to surface modified titanium oxide, with surface unmodified processing
The UV-vis absorption spectrum of titanium dioxide compares figure and sees Fig. 4, it is seen that has carried out the modified dioxy in surface by the present embodiment
Big more of ultraviolet-visible absorption range for changing the titanium commercial titanium dioxide more modified than not carrying out surface, increase visible light
Response range.
Embodiment 5
The experiment of degradation dye, rhodamine B (RhB) under visible light conditions.
Specific steps are as follows: (1) the surface modified titanium oxide for first respectively obtaining 50mg embodiment 1-4 is placed in 50ml concentration
Mixed liquor is obtained to stir 30min in the rhodamine B solution of 20ppm.Then mixing is placed in dark place and is sufficiently mixed 30min, with
Reach adsorption equilibrium；
(2) it using the 300W xenon lamp with 420nm edge filter as visible light source, is placed in above mixed liquor at 20cm,
Then photocatalytic degradation experiment is carried out；
(3) 1ml is sampled from mixed liquor every 10min, with the specific peak absorbance at UV-vis absorption spectrum 552nm
Intensity is sampling the concentration in liquid to characterize rhodamine B.It is bent to draw rhodamine B degradation, as viewed in figures 5-8, the results showed that table
Face modified titanium oxide catalytic effect is substantially better than unmodified commercial oxidation titanium.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of method of titanium dioxide surface modification, it is characterised in that: disperse titania powder in electrolyte, in electricity
It solves and generates cathode glow discharging plasma in liquid, atmosphere of hydrogen and right is generated by cathode glow discharging plasma electrolysis water
Titanium dioxide carries out hydro-reduction processing, after electric discharge, obtains the titanium oxide with core-shell structure.
2. the method for titanium dioxide surface modification according to claim 1, it is characterised in that: specific preparation process is as follows:
(1) it configures electrolyte: configuring the electrolyte of certain conductivity；
(2) dispersion of titania powder: the titania powder of specified particle size is poured into the electrolyte of step (1) configuration simultaneously
It stirs evenly, obtains mixed liquor A；
(3) it configures discharge electrode: cathode electrode and anode electrode being placed in the mixed liquor A of step (2), and keep the yin
The end of one end of pole electrode is immersed in mixed liquor A, and the anode electrode is placed in mixed liquor A, cathode electrode and anode
The distance between electrode is >=5mm；
(4) discharge process: apply certain voltage between cathode electrode and anode electrode, plasma is in the end of cathode electrode
Place generates；Plasma electrolysis mixed liquor A generates atmosphere of hydrogen and carries out hydro-reduction to the titanium dioxide dispersed in mixed liquor A
Processing obtains mixed liquid B after certain discharge time；
(5) titanium oxide of core-shell structure is made: taking solid after mixed liquid B centrifuge separation will be obtained in step (4), is made after dry
The titanium oxide of the core-shell structure.
3. the method for titanium dioxide surface modification according to claim 2, it is characterised in that: in the step (1), by one
Quantitative acid solution is uniformly mixed to obtain with water the acidic electrolysis bath of certain conductivity, the acid solution be nitric acid, sulfuric acid,
At least one of hydrochloric acid and hydrofluoric acid solution, the conductivity of the electrolyte are 0.1-100ms/cm at 25 DEG C.
4. the method for titanium dioxide surface modification according to claim 2, it is characterised in that: in the step (2), dioxy
The partial size for changing titanium powder is 5-200nm；The concentration of titanium dioxide is 0.1-1000mg/ml in mixed liquor A.
5. the method for titanium dioxide surface modification according to claim 2, it is characterised in that: described in the step (3)
The end of cathode electrode is set as cone point, cathode electrode is inserted in corundum set, only cone point exposes corundum and covers and soak
Not in mixed liquor A.
6. the method for titanium dioxide surface modification according to claim 2, it is characterised in that: in the step (4), electric discharge
In the process, the temperature control of the electrolyte is 70-100 DEG C, and the discharge voltage is 200v-20kv, the cathode electrode
Discharge power is 0.2-200KW.
7. the method for titanium dioxide surface modification according to claim 2, it is characterised in that: in the step (4), putting
Electrolytic buffer is filled into electric process into mixed liquor A, the conductivity of electrolyte is made to maintain ± the 0.5ms/ of initial conductivity
Within the scope of cm.
8. the method for titanium dioxide surface modification according to claim 1, it is characterised in that: the titania powder is
Rutile titanium dioxide and/or anatase titanium dioxide.
9. the method for titanium dioxide surface modification according to claim 1, it is characterised in that: the shell knot of the core-shell structure
Structure is unbodied sub- titanium oxide layer, with a thickness of 1-5nm.
10. the method for titanium dioxide surface modification according to claim 9, it is characterised in that: the Asia titanium oxide layer
Sub- titanium oxide has lattice defect, and includes at least Lacking oxygen and/or titanous.
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| CN110937664A (en) * | 2019-11-26 | 2020-03-31 | 江西省科学院应用物理研究所 | Preparation method of titanium-based titanium suboxide electrode |
| CN112387264A (en) * | 2020-11-16 | 2021-02-23 | 西南石油大学 | TiO based on plasma treatment2Method of modifying TiO2Photocatalyst and application |
| CN112694120A (en) * | 2019-10-23 | 2021-04-23 | 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 | Semiconductor nano particle with composite structure, preparation method and application thereof |
| CN113351194A (en) * | 2021-05-26 | 2021-09-07 | 厦门大学 | Oxygen-rich vacancy titanium dioxide material, preparation and application thereof in lithium-oxygen battery |
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| CN107988614A (en) * | 2017-10-31 | 2018-05-04 | 华东师范大学 | The preparation method of Grey Reduction type nano titania mixed crystal |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112694120A (en) * | 2019-10-23 | 2021-04-23 | 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 | Semiconductor nano particle with composite structure, preparation method and application thereof |
| CN110937664A (en) * | 2019-11-26 | 2020-03-31 | 江西省科学院应用物理研究所 | Preparation method of titanium-based titanium suboxide electrode |
| CN112387264A (en) * | 2020-11-16 | 2021-02-23 | 西南石油大学 | TiO based on plasma treatment2Method of modifying TiO2Photocatalyst and application |
| CN113351194A (en) * | 2021-05-26 | 2021-09-07 | 厦门大学 | Oxygen-rich vacancy titanium dioxide material, preparation and application thereof in lithium-oxygen battery |
| CN113351194B (en) * | 2021-05-26 | 2023-09-05 | 厦门大学 | Oxygen-enriched vacancy titanium dioxide material, preparation and application thereof in lithium-oxygen battery |
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