CN101537354A - Preparation method of visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst and applications thereof - Google Patents
Preparation method of visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst and applications thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical class [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 30
- 239000002071 nanotube Substances 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 230000001699 photocatalysis Effects 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 13
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- 239000008367 deionised water Substances 0.000 claims description 10
- 229940090668 parachlorophenol Drugs 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
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- 239000003795 chemical substances by application Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000012010 growth Effects 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
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- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000008030 elimination Effects 0.000 claims description 3
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- 229910001651 emery Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
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- 229910052751 metal Inorganic materials 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- 238000002798 spectrophotometry method Methods 0.000 claims description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 241000944683 Bandara Species 0.000 description 1
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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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
- 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
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Abstract
The invention discloses a preparation method of a visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst and applications thereof, belonging to the technical field of environmental pollution control. The preparation of the catalyst comprises the following steps of: 1) carrying out electrochemical oxidation reaction under the action of hydrofluoric acid with the concentration of 0.2 percent by weight for preparing a titanium dioxide nanotube electrode, wherein the tube diameter of a nanotube is about 80nm, and the tube length is 550nm; and 2) adopting a photoreduction chemical method to prepare the cuprous oxide/titanium dioxide nano-composite photocatalyst. The prepared composite photocatalyst has the advantages of simple synthesis, stable performance, the synthesis process belonging to the field of green chemistry and the like. The composition of cuprous oxide can not only reduce the defect of high composite probability of photoproduced electron-hole pairs, but also expand the light response range of the titanium dioxide nanotube electrode and further improve the photocatalytic degradation efficiency thereof to organic pollutants in the visible light range, thereby having very high practical value and application prospect.
Description
Technical field
The invention belongs to the environmental pollution treatment technology field, relate to a kind of method of inorganic low energy gap width semiconductor composite titanium dioxide nanotube electrode, specially refer to the preparation method and the application thereof of cuprous oxide/titanium dioxide nano-composite photocatalyst with visible light activity.
Background technology
Energy shortage and environmental pollution are the common issue with that this century, the whole mankind was faced.How rationally utilizing the limited energy of occurring in nature, effectively controlling and solve problem of environmental pollution is the heat subject that new century various countries scientist is studied.In recent years, the conductor photocatalysis oxidation technology of Xing Qiing gradually, the Perfected process that a kind of reasonable energy utilization is provided and has curbed environmental pollution for us.Make us can really realize utilizing inexhaustible, nexhaustible solar energy to solve environmental pollution and energy shortage problem.
The conductor photocatalysis oxidation technology originates from the seventies in last century, from the TiO of Fujishima and Honda discovery illumination
2The monocrystalline electrode can decomposing H
2O utilizes semiconductor light-catalyst that luminous energy is changed into electric energy and chemical energy just becomes one of the most popular research topic.Recently, constantly increase about the application study report that utilizes aspects such as conductor photocatalysis oxidative degradation organic pollution, reducing heavy metal ion, antifog, deodorizing, sterilization, automatically cleaning.In numerous semiconductor light-catalysts, TiO
2Because of it has the chemical stability height, fast light burn into is harmless, cheap and have darker characteristics such as valence-band level, and become most active a kind of material in the conductor photocatalysis research field.Yet, Detitanium-ore-type TiO
2Energy gap be 3.2eV, its excitation wavelength is 387.5nm, belongs to ultraviolet region.And for solar spectrum, main concentration of energy is in the 460nm-600nm wave-length coverage, so ultraviolet light proportion less than 5%.And the energy of indoor light source also mainly concentrates on 550nm-600nm.From economical and practical angle, how to realize TiO
2Visible light activity, efficiently utilize in the sunshine abundant visible light and indoor weak light to carry out the emphasis that light-catalyzed reaction is current research, also be the challenging problem of tool.
In order to improve TiO
2Spectral response in visible-range and photocatalysis quantum efficiency thereof, people adopt various means to TiO
2Carry out modification, comprise that surperficial noble metal loading, metal ion mixing, rare earth metal doping, optical semiconductor sensitization, nonmetal doping and semiconductor thereof are compound.Wherein semiconductor is compound is to improve TiO
2The effective means of photocatalysis performance.The compound modification that comes down to a kind of particle to another kind of particle of semiconductor.Semiconductor composite Ti O
2Can improve the separation of charge effect of system, the spread spectrum response range has further improved the photo-quantum efficiency of catalyst.In recent years about TiO
2The compound architectural study of semiconductor mainly comprises: CdS-TiO
2, CdSe-TiO
2, ZnO-TiO
2, SnO
2-TiO
2, PbS-TiO
2, WO
3-TiO
2, Cu
2O-TiO
2Deng.People such as Yasomanee (Yasomanee, J.P.; Bandara, J.Sol.Energy Mater.Sol.Cells.2008,92,348-352) adopt colloidal sol sputtering method and electrodeposition process coupling to prepare Cu
2O-TiO
2Laminated film, under the condition of radiation of visible light successful realization decomposition water.People such as Siripala (Siripala, W; Ivanovskaya, A; Jaramillo, T; Baeck, S.H; EricW; McFarland.Sol.EnergyMater.Sol.Cells.2003,77,229-237) find Cu
2O-TiO
2There is photoelectric catalytically active preferably the visible region of laminated film in solar spectrum.People such as Zhang (Zhang, Y.G.; Ma, J.L; U, Y.Environ.Sci Technol.2007,41,6264-6269) utilize the method for electrolysis to synthesize Cu
2O-TiO
2Laminated film, under the auxiliary condition of Fenton reagent, Photocatalytic Activity for Degradation methylene blue.Foregoing TiO
2It all is report about its powder form.Yet, TiO
2Nanotube is TiO
2A kind of existence form arranged because nanotube has big specific area, thereby has stronger adsorption capacity, help to improve TiO
2Photocatalysis performance.And, photo-generated carrier than graininess easier from the ion internal migration to the surface, thereby reduced the right recombination probability in light induced electron-hole.So far, also find no about Cu
2The TiO of the compound crystal face preferential growth of O
2The report of nanometer pipe array electrode photo-catalysis capability.So having the photocatalysis characteristic of the cuprous oxide/titanium dioxide nano-composite photocatalyst of visible light activity is not also used better.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method and application thereof of novel photocatalysis agent, this photochemical catalyst can both improve the absorbability of titanium dioxide to visible light, reduce the recombination probability of electron-hole pair again, effectively improved degradation capability to organic pollution, overcome prior art and be difficult to both improve the TiO 2 visible light absorbability simultaneously, reduce the right shortcomings such as recombination probability in light induced electron-hole again.
The present invention addresses the above problem the technical scheme that is adopted to be:
This Preparation of catalysts method is as follows:
1) preparation of titanium dioxide nanotube electrode: at first with the preliminary treatment of titanium sheet, adopting constant current anode oxidation process afterwards, is anode with the metal titanium sheet, and platinized platinum is a negative electrode; Electrolyte is made up of hydrofluoric acid, and wherein the concentration of fluorine ion is 0.05wt%-1.0wt% in the electrolyte; Make lead with copper wire the two poles of the earth are connected on the D.C. regulated power supply, anodic oxidation voltage is a 20V voltage, and oxidization time is 30 minutes, and the temperature of electrolyte is 20 ℃; The titanium sheet for preparing is placed in the Muffle furnace, and 500 ℃ of down calcinings 1 hour after cooling off naturally, have promptly been made the uniform titanium dioxide nanotube electrode of structure, and crystal is along＜101〉the direction preferential growth of crystal face;
The preliminary treatment of described titanium sheet comprises: before using the titanium sheet, earlier the titanium sheet is cut into the sheet of 20mm * 40mm, successively with 240#, 400#, 800# and the polishing of 1500# emery paper, use washed with de-ionized water, be positioned over volume ratio afterwards and be 1: 4: 5 hydrofluoric acid, etching is 40 seconds in nitric acid and the deionized water mixed solution, more respectively through ethanol and deionized water ultrasonic cleaning 20 minutes.In the constant current anode oxidation process, anodic oxidation voltage and time are first under 0-20V, oxidation 5 minutes, and voltage is stabilized in 20V then, continues oxidation 25 minutes.
2) the configuration molar concentration is the copper-bath of 0.05mol/L: the above-mentioned titanium dioxide nanotube electrode for preparing is placed in the copper-bath that the molar concentration that has prepared is 0.05mol/L flooded 24 hours, make copper-bath contact absorption fully with titanium dioxide nanotube electrode.
3) preparation cuprous oxide/titanium dioxide nano-composite photocatalyst: add the hole agent for capturing in above-mentioned reaction system, its concentration of volume percent is 5%, and using the pH value of phosphate PBS regulator solution is 6; Under inert gas shielding, stir, under the high voltage mercury lamp radiation, photo-reduction deposition 40 minutes, light source is 15cm from the distance of reactor, has just obtained cuprous oxide/titanium dioxide nano-composite photocatalyst.The hole agent for capturing is methyl alcohol or isopropyl alcohol; The PBS that adopts is by being that molar concentration is that the dipotassium hydrogen phosphate 13.2mL of 1mol/L and the potassium dihydrogen phosphate 86.8mL of 1mol/L form.In addition, the volumetric usage of described hole agent for capturing is 1: 20 with the ratio of the volumetric usage of copper-bath.
Above-mentioned composite photo-catalyst is taken out, use washed with de-ionized water, last, place 60 ℃ vacuum drying chamber drying 2 hours, be cooled to room temperature, standby.
The application of cuprous oxide/titanium dioxide nano-composite photocatalyst in degradable organic pollutant, technical scheme is as follows:
The photocatalysis experiment is carried out in a hyaline-quartz reactor, and the xenon lamp that uses 500W is the following ultraviolet light of 410nm as light source with optical filtering elimination wavelength.Constantly feeding recirculated water is constant temperature with the temperature that keeps catalyst system and catalyzing.During light-catalyzed reaction, container bottom is magnetic agitation in addition, and the area that catalyst contacts with solution is approximately 6cm
2, organic matter such as degraded parachlorophenol etc. detects the variation of solution concentration with 721 type spectrophotometric determination solution absorbency, and xenon lamp is 15cm from the distance of reactor; Described organic pollution is dyestuff and phenols.
Effect of the present invention and benefit are:
(1) technology is simple, does not need expensive equipment, both can be used for experimental implementation, again can industrial large-scale production, and the process of preparation only need add DC voltage, calcining and ultraviolet light illumination and get final product.
(2) titanium dioxide nanotube electrode of preparing, its specific area is big, and high adsorption capacity has the quantization effect, and can significantly improve quantum efficiency, the growth of crystal is along＜101〉the crystal face preferential growth.The compound photoresponse scope of having widened titanium dioxide nanotube electrode of cuprous oxide, and the right separative efficiency in light induced electron-hole is improved greatly.
(3) Zhi Bei cuprous oxide/titanium dioxide nano-composite photocatalyst degradable organic pollutant, the visible light catalysis activity and the stability thereof of composite photo-catalyst all are greatly improved, and have better absorbing properties.
(4) in cuprous oxide composite titanium dioxide course of reaction, employing be ultraviolet light photo-reduction chemical method, compare with additive method, this kind method belongs to the category of Green Chemistry notion.The new and effective composite photo-catalyst of preparation can be used for handling trade effluent, degradation of dye waste water and indoor harmful gas etc., and applicable scope field is wider.
(5) the present invention has further enlarged the application of titanium dioxide nano material, for the exploitation of other semiconductor composite titanium dioxide nano materials provides brand-new thinking with using on a large scale.
(6) improvement of pollutant is the final radiation energy that requires with the sunshine, is conversion of solar energy that chemical energy is used.Because sunshine is inexhaustible for the mankind, therefore reduced processing cost greatly, be a kind of power-saving technology.
Description of drawings
Fig. 1 is the environmental scanning electronic microscope figure (ESEM) of the titanium dioxide nanotube electrode that obtained in 1 hour at 500 Fei temperature lower calcinations, and multiplication factor is 20000 times.Be that multiplication factor is 50000 times titanium dioxide nanotube electrode environmental scanning electronic microscope figure (ESEM) in the illustration wherein.
Fig. 2 is the environmental scanning electronic microscope figure (ESEM) of the cuprous oxide/titanium dioxide nano-composite photocatalyst with visible light activity of preparation, and multiplication factor is 80000 times.
Fig. 3 is the x-ray diffraction pattern (XRD) of titanium dioxide nanotube electrode and cuprous oxide/titanium dioxide nano-composite photocatalyst.Is abscissa the angle of diffraction (2 of twice?, ordinate is the intensity of diffraction maximum.
The x-ray photoelectron spectroscopy figure (XPS) of the cuprous oxide/titanium dioxide nano-composite photocatalyst that Fig. 4 is prepared with visible light activity.Abscissa is binding energy (eV), and ordinate is relative intensity (cps).
Fig. 5 is a photocatalytic degradation organic compound parachlorophenol schematic diagram.Abscissa is reaction time (min), and ordinate is the concentration (mg/L) of parachlorophenol.
Fig. 6 is the UV, visible light diffuse reflection figure (UV-vis-DRS) of the prepared cuprous oxide/titanium dioxide nano-composite photocatalyst with visible light activity.Abscissa is optical excitation wavelength (nm), and ordinate is an absorbance.
The specific embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Wherein embodiment 1-7 is that different condition prepares visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst.
Do you the industrially pure titanium sheet be cut into some 20mm? the titanium sheet of 0mm size.Earlier after the emery paper of 240#, 400#, 800# and 1500# polish repeatedly, smooth until cleaning surfaces, place the ultrasonic cleaning of sonic oscillation pond then, immerse HF: HNO after the cleaning again
3: H
2O=1: etching is 40 seconds in 4: 5 the mixed solution, and the titanium sheet of last etching was used ethanolic solution and washed with de-ionized water respectively 20 minutes.Titanium sheet after the processing is placed on natural air drying in the air, and is standby.Respectively titanium sheet and platinized platinum are connected in the both positive and negative polarity of D.C. regulated power supply, electrolyte is made up of hydrofluoric acid, and wherein the concentration of hydrofluoric acid is 0.2wt% in the electrolyte, makees lead with copper wire the two poles of the earth are connected on the D.C. regulated power supply.In the constant current anode oxidation process, anodic oxidation voltage and time are earlier under 0-20V, oxidation 5 minutes, voltage is stabilized in 20V then, continues oxidation 25 minutes, and whole experiment is carried out under lasting the stirring, the temperature of electrolyte is 20 ℃, the titanium sheet for preparing is placed in the Muffle furnace, calcined 1 hour down, promptly obtain TiO for 500 ℃
2Nanotube electrode.The TiO that makes
2The environmental scanning electronic microscope photo of nanotube electrode as shown in Figure 1.Titania nanotube open top is as can be seen arranged closely, is evenly distributed.From 50000 times ESEM figure, can clearly see TiO
2The about 80nm of nanotube average diameter, the about 15nm of thickness of pipe wall.X-ray diffractogram (XRD) is calculated crystal structure according to the goniometer of diffraction maximum correspondence and is＜101〉high preferred orientation preferential growths shown in the curve a of Fig. 3.The above-mentioned titanium dioxide nanotube array electrode for preparing was placed in the copper-bath that the molar concentration that has prepared is 0.05mol/L dipping 24 hours, makes copper-bath contact absorption fully with titanium dioxide nanotube electrode.In above-mentioned reaction system, add 5mL methyl alcohol hole agent for capturing then, its volumetric concentration is 5%, and using the pH value of the phosphate PBS regulator solution that molar concentration forms as the potassium dihydrogen phosphate 86.8mL of the dipotassium hydrogen phosphate 13.2mL of 1mol/L and 1mol/L is 6.Purge stirring under the protection at nitrogen, under the high voltage mercury lamp radiation, photo-reduction deposition 40 minutes, light source is 15cm from the distance of reactor, has just obtained cuprous oxide/titanium dioxide nano-composite photocatalyst.Above-mentioned composite photo-catalyst is taken out, use washed with de-ionized water, last, place 60 ℃ vacuum drying chamber drying 2 hours, be cooled to room temperature, standby.The environmental scanning electronic microscope photo of the cuprous oxide/titanium dioxide nano-composite photocatalyst that makes as shown in Figure 2.The compound tubular structure that does not destroy titania nanotube of cuprous oxide as can be seen, x-ray photoelectron energy spectrogram (XPS) as shown in Figure 4, as can be seen from the figure mainly contain Ti, Cu, C and four kinds of elements of O in the sample and form, wherein Cu exists with the form of cuprous oxide.In addition, X-ray diffractogram (XRD) can draw the existence that cuprous oxide crystal is arranged in the composite photo-catalyst according to the angle of diffraction maximum correspondence shown in the curve b of Fig. 3, and the resulting result of XRD is consistent with XPS.UV, visible light diffuse reflection figure (UV-vis-DRS) as shown in Figure 6, as can be seen from the figure cuprous oxide/titanium dioxide composite Nano photochemical catalyst has stronger absorption at ultraviolet region, show higher photocatalytic activity, and tangible red shift has taken place, expanded TiO
2The photoresponse scope of nanotube electrode can improve the utilization rate of visible light.
According to the preparation method of the present invention of embodiment 1, just change electrolyte into hydrofluoric acid that concentration is 0.05wt%, make cuprous oxide/titanium dioxide nano-composite photocatalyst.
Embodiment 3
According to the preparation method of the present invention of embodiment 1, just change electrolyte into hydrofluoric acid that concentration is 1.0wt%, make cuprous oxide/titanium dioxide nano-composite photocatalyst.
Embodiment 4
According to the preparation method of the present invention of embodiment 1, just the pH value with phosphate PBS regulator solution is 3, makes cuprous oxide/titanium dioxide nano-composite photocatalyst.
Embodiment 5
According to the preparation method of the present invention of embodiment 1, just the pH value with phosphate PBS regulator solution is 8, makes cuprous oxide/titanium dioxide nano-composite photocatalyst.
Embodiment 6
According to the preparation method of the present invention of embodiment 1, just change the photo-reduction sedimentation time into 20 minutes, make cuprous oxide/titanium dioxide nano-composite photocatalyst.
Embodiment 7
According to the preparation method of the present invention of embodiment 1, just change the photo-reduction sedimentation time into 60 minutes, make cuprous oxide/titanium dioxide nano-composite photocatalyst.
Embodiment 8: the application of this composite photo-catalyst in degradable organic pollutant
Preparation method according to embodiment 1 makes the visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst of the present invention, has carried out the contrast experiment of photocatalysis degradation organic contaminant parachlorophenol, is reflected in the hyaline-quartz reactor and carries out.
Waste water quality: the parachlorophenol initial concentration is 20mg/L, and the water yield is 150mL.
The sheet cuprous oxide/titanium dioxide nano-composite photocatalyst of 20mm * 40mm is put into the waste water that contains parachlorophenol, at ambient temperature, can carry out light-catalyzed reaction, what light source used is the xenon lamp (but the elimination wavelength is the following ultraviolet light of 410nm) of 500W, continue in the course of reaction to stir, react after 2 hours, the degradation rate of parachlorophenol has reached 12.3%.
Photocatalytic degradation organic compound parachlorophenol effect schematic diagram gives the natural degradation of parachlorophenol, the curve and the TiO of direct photodissociation under the xenon lamp irradiation as shown in Figure 5 in Fig. 5
2The nanotube electrode photocatalytic degradation.
The composite photo-catalyst of example 1 preparation has visible light activity, is characterized in and can have also been reduced the right recombination probability in light induced electron-hole in addition by the excited by visible light of wavelength more than 410nm, has effectively improved the degradation capability to pollutant.The cuprous oxide/titanium dioxide nano-composite photocatalyst oxidability with visible light activity of the present invention's preparation is strong, the catalytic activity height, advantages such as nontoxic, biological, chemistry, photochemical stability are good can be used for fields such as sewage disposal, air cleaning, sterilization, energy and material.
Claims (6)
1. the preparation method of a visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst is characterized in that following steps:
1) preparation of titanium dioxide nanotube electrode: at first with the preliminary treatment of titanium sheet, adopting constant current anode oxidation process afterwards, is anode with the metal titanium sheet, and platinized platinum is a negative electrode; Electrolyte is made up of hydrofluoric acid, and wherein the concentration of fluorine ion is 0.05wt%-1.0wt% in the electrolyte; Make lead with copper wire the two poles of the earth are connected on the D.C. regulated power supply, anodic oxidation voltage is a 20V voltage, and oxidization time is 30 minutes, and the temperature of electrolyte is 20 ℃; The titanium sheet for preparing is placed in the Muffle furnace, and 500 ℃ of down calcinings 1 hour after cooling off naturally, have promptly been made the uniform titanium dioxide nanotube electrode of structure, and crystal is along＜101〉the direction preferential growth of crystal face;
The preliminary treatment of described titanium sheet comprises: before using the titanium sheet, earlier the titanium sheet is cut into the sheet of 20mm * 40mm, successively with 240#, 400#, 800# and the polishing of 1500# emery paper, use washed with de-ionized water, be positioned over volume ratio afterwards and be 1: 4: 5 hydrofluoric acid, etching is 40 seconds in nitric acid and the deionized water mixed solution, more respectively through ethanol and deionized water ultrasonic cleaning 20 minutes.
2) the configuration molar concentration is the copper-bath of 0.05mol/L: the above-mentioned titanium dioxide nanotube electrode for preparing is placed in the copper-bath that the molar concentration that has prepared is 0.05mol/L flooded 24 hours, make copper-bath contact absorption fully with titanium dioxide nanotube electrode.
3) preparation cuprous oxide/titanium dioxide nano-composite photocatalyst: add the hole agent for capturing in above-mentioned reaction system, its concentration of volume percent is 5%, and using the pH value of phosphate PBS regulator solution is 6; Under inert gas shielding, stir, under the high voltage mercury lamp radiation, photo-reduction deposition 40 minutes, light source is 15cm from the distance of reactor, has just obtained cuprous oxide/titanium dioxide nano-composite photocatalyst; The hole agent for capturing is methyl alcohol or isopropyl alcohol;
Above-mentioned composite photo-catalyst is taken out, use washed with de-ionized water, last, place 60 ℃ vacuum drying chamber drying 2 hours, be cooled to room temperature, standby.
2. the preparation method of composite photo-catalyst according to claim 1, its feature also is: in the constant current anode oxidation process, anodic oxidation voltage and time are oxidation 5 minutes under 0-20V earlier, and voltage is stabilized in 20V then, continues oxidation 25 minutes.
3. the preparation method of composite photo-catalyst according to claim 1, its feature also is: employed inert gas is a nitrogen.
4. the preparation method of composite photo-catalyst according to claim 1, its feature also is: the PBS of employing is by being that molar concentration is that the dipotassium hydrogen phosphate 13.2mL of 1mol/L and the potassium dihydrogen phosphate 86.8mL of 1mol/L form.
5. the preparation method of composite photo-catalyst according to claim 1, its feature also is: the volumetric usage of described hole agent for capturing is 1: 20 with the ratio of the volumetric usage of copper-bath.
6. the application of the described composite photo-catalyst of claim 1 is characterized in that:
The photocatalysis experiment is carried out in a hyaline-quartz reactor, and the xenon lamp that uses 500W is the following ultraviolet light of 410nm as light source with optical filtering elimination wavelength; The temperature that constantly feeds recirculated water maintenance catalyst system and catalyzing is a constant temperature; During light-catalyzed reaction, container bottom is magnetic agitation in addition, and the area that catalyst contacts with solution is approximately 6cm2, organic matters such as degraded parachlorophenol, detect the variation of solution concentration with 721 type spectrophotometric determination solution absorbency, xenon lamp is 15cm from the distance of reactor; Described organic pollution is dyestuff and phenols.
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