CN104888780A - Cobalt, titanium oxide heterojunction material and preparation method thereof - Google Patents
Cobalt, titanium oxide heterojunction material and preparation method thereof Download PDFInfo
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- CN104888780A CN104888780A CN201510161822.2A CN201510161822A CN104888780A CN 104888780 A CN104888780 A CN 104888780A CN 201510161822 A CN201510161822 A CN 201510161822A CN 104888780 A CN104888780 A CN 104888780A
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- titanium
- ammonium carbonate
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010941 cobalt Substances 0.000 title claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 15
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 7
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000987 azo dye Substances 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 31
- 239000004408 titanium dioxide Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a heterojunction material and a preparation method thereof. The preparation method comprises the following steps: dissolving soluble divalent cobalt salt and titanium sulfate in deionized water, adding an ammonium carbonate solution under stirring condition, reacting for 90-120 DEG C, performing reflux condensation for 4-12 hours, centrifuging, washing, drying, and calcinating the product in a muffle furnace for 2-5 hours at temperature of 300-600 DEG C to obtain the cobalt, titanium oxide heterojunction material. The mass percentage content of cobalt in the material is 23-55%, the average particle size is 0.5-3mum, a structure is characterized in that anatase TiO2 (101)crystal face and Co3O4 (400)crystal face are connected to form a heterojunction structure. The material has absorption property to visible light and can be used for degrading an azo dye under visible light.
Description
Technical field
The present invention relates to a kind of heterojunction material preparation field, be specifically related to cobalt, titanium oxide heterojunction material and preparation method thereof, this cobalt, titanium oxide heterojunction material have absorption property to visible ray.
Background technology
Titanium dioxide (TiO
2) be also called titanium dioxide, its photocatalysis efficiency is high, chemical stability good, low toxicity, have with low cost, be easy to the advantages such as preparation.Can disinfection be realized by absorbing ultraviolet and be widely used in the aspects such as food, health, building materials, again because can ultraviolet be absorbed and be widely used in the sunscreen product in daily use chemicals industry.The titanium dioxide that occurring in nature exists has three kinds of crystal formations: rutile, anatase and brockite, rutile-type is uniquely stable crystalline phase, and sharp iron ore type and brookite type are all the low-temperature phases of titanium dioxide, be metastable, they all change stable rutile-type into after high-temperature heat treatment.Wherein Detitanium-ore-type and rutile-type can as photochemical catalysts.Generally speaking, the photocatalytic activity of anatase titanium dioxide is higher than the photocatalytic activity of rutile titanium dioxide.
Light-catalyzed reaction and light energy conversion are the process of chemical energy, are that semi-conducting material produces light induced electron and hole under the irradiation of light, utilize the Strong oxdiative reducing power in light induced electron and hole to impel compou nd synthesis or make the process of degradation.Due to natural daylight can be utilized to do energy contaminated solution problem, this technology receives to be paid close attention to widely, and acquisition develops rapidly, and the nearly more than ten years are applied to water treatment field.Titanium dioxide can only absorb the light of ultraviolet section, so lower to the utilization rate of sunshine, if can reduce the band gap of titanium dioxide, makes also have absorption in visible ray section, so just greatly can improve the utilization rate to sunshine.
Hetero-junctions refers to that the semiconductor single crystal material by contrary two kinds of conduction type are different is made, and according to the difference of the band structure of two kinds of semiconductor single crystal materials, can be divided into transoid hetero-junctions and homotype hetero-junctions.Transoid hetero-junctions refers to the hetero-junctions formed by the semiconductor single crystal material that contrary two kinds of conduction type are different, and homotype hetero-junctions is then the hetero-junctions formed by the semiconductor single crystal material that identical two kinds of conduction type are different.After two kinds of semiconductor single crystal materials form hetero-junctions, both band structures can change, and fermi level bends, the band gap of material is caused to narrow, valence-band electrons is easy to transit to conduction band, and can slow down the recombination rate of light induced electron and photohole, thus effectively improves photocatalysis efficiency.
At present for the band gap reducing titanium dioxide, mainly carry out around doping and formation hetero-junctions two aspect.Condition required for doping is Lattice Oxygen or the titanium that the element be doped into can replace titanium dioxide, this just requires that the ionic radius of doped chemical differs less with the ionic radius of original Lattice Oxygen or titanium, thus after making doping, the lattice structure not larger change of main body titanium dioxide, can maintain stable state.Co
3+ionic radius be 0.065nm, Ti
4+ionic radius be 0.068nm, ionic radius is close, therefore selects Co
3+as doped chemical.When increasing the amount of doped chemical, doped chemical removing being entered in titanium dioxide lattice and substitutes outside oxygen or titanium, remaining part and TiO
2define heterojunction structure, make obtained material have the performance absorbing visible ray.Doped chemical is mainly divided into nonmetalloid (as nitrogen, boron, sulphur etc.) and transition metal (as cobalt, nickel, iron, copper, zinc, chromium and rare earth metal etc.) two large classes.Doping method selects flame atomizing method, solvent-thermal method or infusion process usually, at Applied Catalysis B:Environmental, 2014, in 144:333-342, titanium tetraisopropylate mixes with two ethyl hexanoate cobalts by the people such as Siva Nagi Reddy Inturi, through a step flame atomizing method, entered by cobalt doped in titanium dioxide, wherein the doping percentage of cobalt can only reach 5%.At International Journal of Hydrogen Energy, 2013, in 38:9655-9664, the people such as Valluri Durga Kumari then utilize infusion process to be joined by titanium dioxide in four hydration cobalt acetates, slow intensification Keep agitation, to the complete distilled-to-dryness of moisture, obtain Co/Ti=0-5.26%, weighed the photocatalysis performance of product by the effect studying its photocatalysis water hydrogen under visible light; At ChemCatChem, 2014, in 6:339-347, Lei Sun etc. adopt solvent-thermal method iron series element (M) i.e. Fe, Co, Ni to be doped into respectively titanium dioxide nanoplate, when the ratio having investigated M/Ti changes between 0.25%-2.0%, the photocatalysis performance of the titania-doped degradation of methylene blue under visible light of iron series element, the content that the product that the method obtains only has probed into doped chemical is less than or equal to the situation of 2.0%, and does not study can there be what impact to the photocatalysis performance of product when the content of doped chemical is higher.There are two shortcomings in said method, the amount of first cation doping is lower; Second it be raw materials used for titanium tetraisopropylate, two ethyl hexanoate cobalts or four hydration cobalt acetates, and these materials belong to organic matter, and preparation process comparatively inorganic matter is complicated, and reaction terminate after more difficult, certain burden can be caused to environment.
For the process of azo dyes in dyeing waste water, current domestic main employing be charcoal absorption and titanium dioxide ultraviolet catalysis, all there is certain drawback in these two kinds of methods.Although charcoal absorption can adsorb some azo dyes fast and efficiently, but it is inoperative to some dyestuff, and can not finally be converted into nontoxic, harmless after absorption, to material that is biological and environmental nonpollution, so do not meet the requirement of industry, Ecological Sustainable Development.Titanium dioxide can absorb ultraviolet, contacts with organic matter, and light induced electron can be made to be separated with hole, thus oxidation Decomposition organic matter, but the structure of titanium dioxide self, physical property determine the light that it can only absorb ultraviolet section.Sunshine is the energy that content is huge, clean, but ultraviolet light only accounts for 5% of its total amount, and remaining 95% is almost visible ray entirely.Therefore research is a kind of has response to visible ray, and the photochemical catalyst that the utilization ratio of raising sunshine is high is imperative.
Summary of the invention
The object of this invention is to provide a kind of cobalt, titanium oxide heterojunction material and preparation method thereof, this material has the performance absorbing visible ray.
Cobalt provided by the invention, titanium oxide heterojunction material, adopt bath oiling, by soluble cobalt and titanium sulfate, high temperature oil bath under alkali effect is heated and is stirred, washing centrifugal to products therefrom, dry, and in Muffle furnace, high-temperature roasting obtains cobalt, titanium oxide hetero-junctions powder body material.This material can absorb visible ray, can be used for degrade azo dyestuff.
The concrete preparation process of cobalt, titanium oxide hetero-junctions is as follows:
A. be the ratio of 1:1-4 by soluble cobalt and titanium sulfate according to the mol ratio of Co:Ti ion, join in deionized water, wherein the concentration of cobalt salt is 0.001-0.05mol/L, and in 90-120 DEG C of oil bath heating, condensing reflux, stirs 5-20min, obtain solution A; Described soluble cobalt is Co (NO
3)
26H
2o, CoSO
47H
2one in O;
B. be dissolved in deionized water by ammonium carbonate, the concentration making ammonium carbonate is 0.5-2mol/L, obtains solution B; Solution B dropped in solution A, the mol ratio making cobalt ions and titanium ion sum in ammonium carbonate and solution A in solution B is 4-6:1, and time for adding is 0.25-1h; Condensing reflux 4-12h; Centrifugal, washing, dries, obtains cobalt, titanium oxide presoma;
C. the cobalt prepared by step B, titanium oxide presoma are in 300-600 DEG C in Muffle furnace, and roasting 2-5h, obtains cobalt, titanium oxide heterojunction material, and wherein the mass percentage of cobalt is 23-55%.
The present invention's titanium sulfate does titanium source, is because titanium sulfate is solid, is easy to weigh; And the convenient process of product containing sulfate radicals, little to environmental pressure.Adopt bath oiling to react, equipment requirement is simple, and reaction condition is easy to control.
Fig. 1 is the diffraction maximum that embodiment 1 gained sample adopts the XRD-6000 type x-ray powder diffraction instrument of Japanese Shimadzu Corporation and obtains, and occurs Detitanium-ore-type TiO in figure
2characteristic diffraction peak, and less Co
3o
4characteristic diffraction peak.
Fig. 2 is SEM (SEM) photo of the sample that embodiment 1 obtains.As seen from the figure, the particle diameter of gained mixed oxide is about 0.5-3 μm.
Fig. 3 is high-resolution transmission microscopy (HRTEM) photo of embodiment 1 gained sample.As seen from the figure, that interplanar distance d=0.352nm is corresponding is Detitanium-ore-type TiO
2(101) crystal face, the corresponding Co of d=0.199nm
3o
4(400) crystal face, namely the interface that two kinds of crystal are connected defines heterojunction structure.
Fig. 4 is the XRD diffraction maximum that embodiment 2 obtains sample, occurs TiO in figure
2anatase and the characteristic diffraction peak of rutile two kinds of crystal formations.
Fig. 5 is SEM (SEM) photo of the sample that embodiment 2 obtains.As seen from the figure, the particle diameter of gained oxide is about 0.5-2 μm.
Show from above-mentioned test result, the material average grain diameter that step C obtains is 0.5-3 μm, and its design feature is Detitanium-ore-type TiO
2(101) crystal face and Co
3o
4(400) crystal face connects, and forms heterojunction structure.
The test of visible ray absorption property is carried out to cobalt, titanium oxide heterojunction material: take cobalt that 0.02g step C obtains, titanium oxide heterojunction material joins in the methylene blue solution of 100mL, 10mg/L, magnetic agitation, first dark absorption 6h, carry out radiation of visible light to it again, logical condensed water reduces the moisture evaporation that light radiation causes.Every 0.5h draws 4mL solution, filters out solid particle wherein, uses ultraviolet-visual spectrometer to measure gained solution concentration.The results are shown in Figure 6, as seen from the figure, after radiation of visible light 4h, the degradation rate of methylene blue reaches more than 65%, illustrates that this heterojunction material has good visible absorption performance, can be used for degrade azo dyestuff.
The invention has the beneficial effects as follows: the present invention's cobalt titanium oxide presoma that adopted bath oiling to synthesize, after carrying out high-temperature roasting to it, obtain cobalt, titanium oxide hetero-junctions, average grain diameter is about 0.5-3 μm, Detitanium-ore-type TiO
2(101) crystal face and Co
3o
4(400) crystal face connects, and forms heterojunction structure.This material has good visible absorption performance, can be used for degrade azo dyestuff.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction maximum of institute's sample in embodiment 1.
Fig. 2 is gained sample SEM photograph in embodiment 1.
Fig. 3 is high-resolution transmission microscopy (HRTEM) photo of embodiment 1 gained sample.
Fig. 4 is the XRD diffraction maximum of gained sample in embodiment 2.
Fig. 5 is the SEM photograph of gained sample in embodiment 2.
Fig. 6 is the design sketch of gained sample Visible Light Induced Photocatalytic methylene blue in embodiment 1.
Detailed description of the invention
Embodiment 1
Take 2.328g cabaltous nitrate hexahydrate, 2.880g titanium sulfate, be dissolved in 100mL deionized water, be transferred to by the solution dissolving cobalt nitrate and titanium sulfate completely in 500mL round-bottomed flask, 100 DEG C of oil bath heating, stir, condensing reflux, 30min obtains solution A.
Take 15.360g ammonium carbonate to be again dissolved in 50mL deionized water and to obtain B solution, the mol ratio of ammonium carbonate and cobalt ions and titanium ion sum is 4.9:1.
Dropwise solution A all instilled in sal volatile, reaction 5h, centrifugal filtration, washing, in 60 DEG C of dryings.
Roasting 4h at 400 DEG C in Muffle furnace, obtains cobalt, titanium oxide hetero-junctions.Wherein Co/Ti=2mol:3mol, the mass percentage of cobalt is 45%.
Take the above-mentioned cobalt of 0.020g, titanium oxide hetero-junctions joins in the methylene blue solution of 100mL10ppm, magnetic agitation, first dark absorption 6h, then carry out radiation of visible light to it, logical condensed water reduces the moisture evaporation that light radiation causes.Every 0.5h draws 4mL solution, filters out solid particle wherein, uses ultraviolet-visual spectrometer to measure gained solution concentration.The results are shown in Figure 6, degradation rate reaches 65%.
Embodiment 2
Take 2.328g cabaltous nitrate hexahydrate, 7.680g titanium sulfate, be dissolved in 100mL deionized water, then take 28.260g ammonium carbonate and be dissolved in 50mL deionized water.Be transferred to by the solution dissolving cobalt nitrate and titanium sulfate completely in 500mL round-bottomed flask, 110 DEG C of oil bath heating, stir, condensing reflux, after 25min, dropwise instills sal volatile, and the mol ratio of ammonium carbonate and cobalt ions and titanium ion sum is 4.5:1.After reaction 5h, by solution centrifugal, washing, 60 DEG C of dryings.500 DEG C of not kiln roasting 5h that get down from horse, the mass percentage obtaining cobalt is the cobalt of 23%, titanium oxide hetero-junctions.
Embodiment 3
Take 2.328g cabaltous nitrate hexahydrate, 5.760g titanium sulfate, be dissolved in 100mL deionized water, then take 26.120g ammonium carbonate and be dissolved in 50mL deionized water.Be transferred to by the solution dissolving cobalt nitrate and titanium sulfate completely in 500mL round-bottomed flask, 100 DEG C of oil bath heating, stir, condensing reflux, after 15min, dropwise instills sal volatile, and the mol ratio of ammonium carbonate and cobalt ions and titanium ion sum is 5.2:1.After reaction 7h, by solution centrifugal, washing, 60 DEG C of dryings.450 DEG C of not kiln roasting 2h that get down from horse, obtain Co/Ti=1mol:3mol, and the mass percentage of cobalt is cobalt, the titanium oxide of 29%.
Embodiment 4
Take 2.328g cabaltous nitrate hexahydrate, 1.920g titanium sulfate, be dissolved in 100mL deionized water, then take 13.816g ammonium carbonate and be dissolved in 50mL deionized water.Be transferred to by the solution dissolving cobalt nitrate and titanium sulfate completely in 500mL round-bottomed flask, 105 DEG C of oil bath heating, stir, condensing reflux, after 20min, dropwise instills sal volatile, and the mol ratio of ammonium carbonate and cobalt ions and titanium ion sum is 5.5:1.After reaction 10h, by solution centrifugal, washing, 60 DEG C of dryings.550 DEG C of not kiln roasting 3h that get down from horse, obtain Co/Ti=1mol:1mol, and the mass percentage of cobalt is cobalt, the titanium oxide of 55%.
Claims (2)
1. a preparation method for cobalt, titanium oxide heterojunction material, concrete steps are as follows:
A. be the ratio of 1:1-4 by soluble cobalt and titanium sulfate according to the mol ratio of Co:Ti ion, join in deionized water, wherein the concentration of cobalt salt is 0.001-0.05mol/L, and in 90-120 DEG C of oil bath heating, condensing reflux, stirs 5-20min, obtain solution A; Described soluble cobalt is Co (NO
3)
26H
2o or CoSO
47H
2o;
B. be dissolved in deionized water by ammonium carbonate, the concentration making ammonium carbonate is 0.5-2mol/L, obtains solution B; Solution B dropped in solution A, the mol ratio making cobalt ions and titanium ion sum in ammonium carbonate and solution A in solution B is 4-6:1, and time for adding is 0.25-1h; Condensing reflux 4-12h; Centrifugal, washing, dries, obtains cobalt, titanium oxide presoma;
C. the cobalt prepared by step B, titanium oxide presoma are in 300-600 DEG C in Muffle furnace, and roasting 2-5h, obtains cobalt, titanium oxide heterojunction material, and wherein the mass percentage of cobalt is 23-55%.
2. cobalt, the titanium oxide heterojunction material prepared of method according to claim 1, is characterized in Detitanium-ore-type TiO
2(101) crystal face and Co
3o
4(400) crystal face connects, and forms heterojunction structure; The average grain diameter of this material is 0.5-3 μm, and wherein the mass percentage of cobalt is 23-55%.
Priority Applications (1)
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| US20120152335A1 (en) * | 2010-12-20 | 2012-06-21 | Shiu Hui-Ying | Full-spectrum absorption solar cell |
| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN104091930A (en) * | 2014-07-17 | 2014-10-08 | 华南师范大学 | Preparation method of TiO2-Co3O4 nano composite with dual-composite characteristic structure |
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| US20120152335A1 (en) * | 2010-12-20 | 2012-06-21 | Shiu Hui-Ying | Full-spectrum absorption solar cell |
| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN104091930A (en) * | 2014-07-17 | 2014-10-08 | 华南师范大学 | Preparation method of TiO2-Co3O4 nano composite with dual-composite characteristic structure |
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| BENJAMIN KUPFER,ET AL: "Thin Film Co3O4/TiO2 Heterojunction Solar Cells", 《ADVANCED ENERGY MATERIALS》 * |
| HENGGUO WANG,ET AL: "General and controllable synthesis strategy of metal oxide/TiO2 hierarchical heterostructures with improved lithium-ion battery performance", 《SCIENTIFIC REPORTS》 * |
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