CN106466604A - A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof - Google Patents
A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof Download PDFInfo
- Publication number
- CN106466604A CN106466604A CN201611025221.XA CN201611025221A CN106466604A CN 106466604 A CN106466604 A CN 106466604A CN 201611025221 A CN201611025221 A CN 201611025221A CN 106466604 A CN106466604 A CN 106466604A
- Authority
- CN
- China
- Prior art keywords
- tio
- photocatalyst material
- composite photocatalyst
- preparation
- volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002131 composite material Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000010919 dye waste Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 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 15
- 229960000907 methylthioninium chloride Drugs 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 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
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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 kind of Cu2O/TiO2Composite photocatalyst material, this material is to prepare classification TiO in hydro-thermal method2On the basis of hollow micro structure, surface ornament Cu2O nano-particle is thus obtain bigger serface and mushy classification Cu2O/TiO2Composite photocatalyst material.Cu of the present invention2O/TiO2The preparation process is simple of composite photocatalyst material, appearance structure is unique, not only the range expansion of photoresponse has been arrived visible region, and has shown excellent light degradation effect and good stable circulation performance in the process of organic dye waste water.
Description
Technical field
The invention belongs to conductor photocatalysis material preparing technical field, particularly to a kind of Cu2O/TiO2Composite photocatalyst
Material and preparation method thereof.
Background technology
In recent years, metal-oxide semiconductor (MOS) is turned in wastewater treatment and solar energy due to its high heliosensitivity and nontoxic essence
The field of changing causes very big concern.As a kind of typical broad stopband n-type semiconductor, nano-TiO2Because of its photocatalytic activity
High, cheap and stable performance is considered to solve environmental pollution and global energy supplies the study hotspot of problem, is at present
A kind of conventional and the most promising photocatalyst.However, due to its wide energy gap (3.2ev), single TiO2Can only be in purple
Response in outer optical range, the photo-generate electron-hole that it produces simultaneously, to being easy to be combined, leads to low sun light utilization efficiency and amount
Sub- efficiency makes its practical application be very limited.
At present, a lot of methods are used to modify single TiO2Photocatalyst, such as：Composite semiconductor, dye sensitization, nonmetallic
Or metallic element doping etc..Wherein, the coupling of narrow gap semiconductor is a kind of very effective method.Research shows compound half
In conductor, narrow gap semiconductor by excited by visible light and can produce electron-hole pair.Due to different semiconductor conduction band and valence band
The difference of position, makes light induced electron be gathered in a kind of conduction band of quasiconductor, and the valence band of another kind of quasiconductor is then transferred in hole,
Electric charge carrier is sufficiently separated, and not only substantially increases photo-quantum efficiency, and by photoresponse range expansion to visible ray
Region, thus improve light-catalysed efficiency.Cu2O, as a kind of narrow band gap (2.2eV) p-type semiconductor, has excellent light, electricity
And catalysis characteristicses, if with broad stopband n-type semiconductor TiO2Compound, TiO will be improved most probably in terms of two above2Light urge
Change activity, and show potential application prospect in terms of as photocatalyst for degrading organic pollution.Application No.
200910229191.8 invention one-dimensional Cu is prepared for using alternate electrodepostion process2O/TiO2Nucleocapsid structure array film；Application number
Invention for 201010212628.X constructs Cu using impulse electrodeposition technology with reference to electroxidation method2O/TiO2Hetero-junctions is received
Mitron array is although these methods all achieve the response in visible region for the product, but its product is one-dimensional array shape
Looks, and operate route more complicated, it is related to apparatus expensive.Therefore, how to obtain pattern uniqueness, to have using easy syntheti c route
The excellent Cu of visible light-responded and photocatalysis performance2O/TiO2Composite photo-catalyst is its key issue urgently to be resolved hurrily.
Content of the invention
It is an object of the invention to proposing novel C u that a kind of syntheti c route is simple and photocatalysis performance is excellent2O/TiO2Multiple
Closing light catalysis material and preparation method thereof, the photocatalyst that it obtains not only can respond under visible light, and is applied
To in organic dye waste water, degradation effect is notable.
The purpose of the present invention is achieved in the following ways.
A kind of Cu2O/TiO2Composite photocatalyst material it is characterised in that：This catalysis material is in classification TiO2The micro- knot of hollow
Structure surface ornament Cu2O nano-particle obtains, wherein TiO2A diameter of 1-2 μm of hollow micro structure, Cu2The chi of O nano-particle
Very little for 50-200nm.
A kind of Cu2O/TiO2The preparation method of composite photocatalyst material is it is characterised in that comprise the following steps：
(1) predecessor TiO2Preparation：Titanium potassium oxalate and hydrogen peroxide are separately added in deionized water, are adjusted using hydrochloric acid
PH value, between 1～2, then reactant is added in hydrothermal reaction kettle, reacts 12h at 150 DEG C, product is cooled down, is centrifuged,
Wash, be dried.
(2)Cu2O/TiO2The preparation of composite photocatalyst material：By the TiO in step (1)2All it is distributed to 10mL deionization
In water, under conditions of magnetic agitation, make unit for uniform suspension, be then respectively adding acetic acid copper liquor, NaOH aqueous solution and lemon
Lemon aqueous acid, under 50 DEG C of water bath condition, then product is centrifuged, washs, is vacuum dried by continuing magnetic force stirring 30min.
In step (1), the quality of described titanium potassium oxalate is 1.56g；The concentration of described hydrogen peroxide is 30%, and volume is
2mL；The volume of described deionized water is 30-40mL：The concentration of described hydrochloric acid is 37%；Described hydrothermal reaction kettle is polytetrafluoroethyl-ne
The stainless steel cauldron of alkene inner bag, volume is 50mL；The temperature of described drying is 80-100 DEG C.
In step (2), the concentration of described acetic acid copper liquor is 0.062g/mL, and volume is 16mL；Described NaOH is water-soluble
The concentration of liquid is 0.28g/mL, and volume is 16mL；The concentration of described aqueous citric acid solution is 0.16g/mL, and volume is 10mL；Institute
State dry temperature and be 60-80 DEG C.
Compared with existing technology at present, Cu is prepared using the inventive method2O/TiO2Composite photocatalyst material has following
Advantage：
1st, the inventive method adopts two step liquid phase method synthesis Cu2O/TiO2Composite photocatalyst material, is sunk with the electricity of current report
Area method is compared, and preparation process is simple, is not related to the equipment of complicated loaded down with trivial details operation and costliness；Raw material is cheap and easily-available simultaneously, cost
Relatively low, and products collection efficiency is higher, suitable industrialized production.
2nd, the Cu of the inventive method preparation2O/TiO2Composite photocatalyst material, is by classification TiO2Hollow micro structure and growth
A large amount of Cu on its surface2O nano-particle assembles, and its unique structure makes it have big specific surface area and many holes
Gap, has the dispersion using hydroxyl radical free radical in organic molecule in quickening waste water and photochemical reaction and transport, thus significantly improving
Its photocatalysis performance.
3rd, the Cu of the inventive method preparation2O/TiO2Composite photocatalyst material, with single-phase TiO2Compare, the model of photoresponse
Enclose and extend to visible region from UV light region, improve the utilization rate of sunlight；Simultaneously because Cu2The conduction band of O and valency
Band position is above TiO2, narrow gap semiconductor Cu2O excites the electronics of generation to be easy to transfer to TiO under visible light2Lead
On band, and Cu is then stayed in hole2So that photo-generated carrier obtains very big separation in the valence band of O, effectively inhibit answering of the two
Close, and then significantly improve the photocatalysis performance of its complex.
4th, adopt the Cu of the inventive method preparation2O/TiO2Composite photocatalyst material, not only in the process of organic dye waste water
In there is good light degradation effect, and show preferable stable circulation performance, beneficial to being recycled for multiple times.
Brief description
Fig. 1 is X-ray diffraction (XRD) spectrogram of three kinds of different products：(a)Cu2O/TiO2, (b) TiO2, (c) Cu2O；
Fig. 2 is scanning electron microscope (SEM) picture of three kinds of different products：(a,b)Cu2O/TiO2, (c) TiO2, (d)
Cu2O；
Fig. 3 (a-c) is product Cu of the present invention2O/TiO2Transmission electron microscope (TEM) photo of composite photocatalyst material, (d) is figure
The energy dispersive spectrum (EDS) of roundel in 3a；
Fig. 4 is single TiO2、Cu2O and product Cu of the present invention2O/TiO2UV-visible absorption spectrum (a) and corresponding
The energy gap (b) of the three kinds of materials calculating；
Fig. 5 (a) is product Cu of the present invention2O/TiO2Purple as photocatalyst degradation of methylene blue solution under visible light
Outward-visible absorbance collection of illustrative plates, (b) is the disposal efficiency of the different products of blank experiment and three kinds degradation of methylene blue under visible light
Comparison diagram.
Fig. 6 is product Cu of the present invention2O/TiO2The recycling performance test chart of composite photocatalyst material.
Specific implementation steps
Further describe the present invention below by embodiment.It will be appreciated, however, that described herein be embodied as
Example, only in order to explain the present invention, not limits the scope of the present invention.
Embodiment 1：
Weigh 1.56g K2TiO(C2O4)2It is dissolved in 30mL deionized water, be slowly added 2mL H2O2(30%) and constantly
Stirring makes solution fully react, and it is 2 that the dilute HCl of Deca (37%) adjusts PH；Then reaction solution is poured into 50mL rustless steel hydro-thermal
In reactor, react 12h at 150 DEG C.After question response terminates, product natural cooling carries out centrifugal treating using centrifuge, use
Deionized water and dehydrated alcohol repeatedly wash, and 12h is dried at 80 DEG C, that is, obtain single TiO2Predecessor.
TiO by above-mentioned acquisition2It is dispersed in 10mL deionized water, make even suspension under conditions of magnetic agitation
Liquid, is then respectively adding 16mL acetic acid copper liquor (0.062g/mL), 16mLNaOH aqueous solution (0.28g/mL) and 10mL anti-bad
Hematic acid aqueous solution (0.16g/mL), under 50 DEG C of water bath condition, then product is centrifuged, washs by continuing magnetic force stirring 30min,
60 DEG C of dryings under vacuum conditions, that is, obtain product Cu2O/TiO2Composite photocatalyst material.In order to as a comparison, without
TiO2Under conditions of predecessor, single Cu is prepared using similar synthetic route2O sample.
The product of acquisition is carried out performance test.Carry out the crystal structure of product using X-ray powder diffraction instrument (XRD)
Test；Observe the microscopic appearance of product using scanning electron microscope (SEM) and transmission electron microscope (TEM)；Using ultraviolet-
Visible spectrophotometer carries out optical property test to product；Come using degradating organic dye methylene blue solution under radiation of visible light
Evaluate the photocatalysis performance of product；Using the degradation rate to methylene blue solution for radiation of visible light 3 products of lower recycling
To evaluate the stability of product.Wherein, the specific experiment step of degradating organic dye methylene blue solution is as follows：Take 100mL,
5×10-5The methylene blue solution of mol/L, as target degradation product, weighs 50mg sample and is added in above-mentioned solution, hold at dark place
Continuous stirring 60min is balanced in the adsorption-desorption of catalyst surface with reaching methylene blue, then with 420nm filter plate
300W xenon lamp irradiates.Take a suspension (3mL) at illumination 30min interval, after centrifugation, use ultraviolet-uisible spectrophotometer
The absorbance of the methylene blue solution after measurement different time photocatalysis.Its fall is assessed by the resolution ratio calculating methylene blue
Solution effect, computing formula is as follows：
Resolution ratio (%)=(C0-C)/C0× 100, C0With the methylene blue solution absorbance before and after C respectively illumination.
In the XRD spectra of the different products of Fig. 1 be given three kinds, all diffraction maximums in Fig. 1 b and TiO2JCPDS card
(21-1276) consistent, the diffraction maximum in Fig. 1 c and Cu2The JCPDS card (05-0667) of O consistent it was demonstrated that produce
Thing is respectively cubic Rutile Type TiO2With Emission in Cubic Cu2O.The each diffraction peak intensity of in figure is higher, does not have other impurity peaks to occur,
Illustrate that the purity of product is very high, and there is good crystallinity.Diffraction maximum in Fig. 1 a then can be classified as Rutile Type
TiO2With Emission in Cubic Cu2O is it was demonstrated that this product is by Cu2O and TiO2The biphase complex of composition.
Fig. 2 gives the SEM picture of three kinds of different products.By with single-phase TiO2And Cu2O pattern contrast it can be seen that
Cu2O/TiO2Product is by classification hollow micro structure TiO of about 1-2 μm of diameter2It is 50- with the size being grown in its surfaces externally and internally
The Cu of 200nm2O nano-particle assembles so as to present big roughness and many pore structures.
Fig. 3 is Cu2O/TiO2The TEM picture of composite photocatalyst material and EDS picture.Picture further demonstrate that XRD and
Phenomenon what is observed in SEM：This product is by middle space stage TiO2With a large amount of Cu2O nano-particle assembles.
Fig. 4 is the UV-visible absorption spectrum of three kinds of different products and corresponding energy gap.Can from figure
Go out, product Cu of the present invention2O/TiO2The energy gap (2.69eV) of composite photocatalyst material is different from single-phase TiO2(2.87eV)
With single-phase Cu2O (2.2eV), and all have the absorption of light in ultraviolet light and visible region, photoresponse scope substantially extends.
Fig. 5 (a) shows under visible light illumination, product Cu of the present invention2O/TiO2Make methylene blue molten as photocatalyst
Characteristic absorption peak intensity at 665nm for the liquid constantly reduces with the prolongation of light application time, vanishes from sight, say after irradiating 120min
Methylene blue in bright now solution is completely degraded.In Fig. 5 (b), after radiation of visible light 120min, single-phase TiO2With
Cu2The degradation rate respectively 26% and 32% to methylene blue for the O, and Cu2O/TiO2The degraded to methylene blue for the composite photo-catalyst
Rate nearly reaches 100%.This result shows, with single photocatalyst (TiO2、Cu2O) compare, Cu2O/TiO2Composite photocatalyst
Agent has the excellent photocatalysis performance being remarkably reinforced.
Recycle performance test chart 6 and show in the degraded of methylene blue solution under visible light, this product Cu2O/
TiO2After composite photo-catalyst recycles three times, its photocatalytic degradation efficiency has almost no change, and implys that product has good
Good stability and recycling performance.
Claims (4)
1. a kind of Cu2O/TiO2Composite photocatalyst material it is characterised in that：This catalysis material is in classification TiO2Hollow micro structure
Surface ornament Cu2O nano-particle obtains, wherein TiO2A diameter of 1-2 μm of hollow micro structure, Cu2The size of O nano-particle
For 50-200nm.
2. a kind of preparation method of composite photocatalyst material described in claim 1 is it is characterised in that comprise the following steps：
(1) predecessor TiO2Preparation：Titanium potassium oxalate and hydrogen peroxide are separately added in deionized water, pH value is adjusted using hydrochloric acid
To between 1～2, then reactant is added in hydrothermal reaction kettle, reacts 12h at 150 DEG C, product is cooled down, be centrifuged, wash
Wash, be dried.
(2)Cu2O/TiO2The preparation of composite photocatalyst material：By the TiO in step (1)2All it is distributed to 10mL deionized water
In, make unit for uniform suspension under conditions of magnetic agitation, be then respectively adding acetic acid copper liquor, NaOH aqueous solution and Fructus Citri Limoniae
Aqueous acid, under 50 DEG C of water bath condition, then product is centrifuged, washs, is vacuum dried by continuing magnetic force stirring 30min.
3. composite photocatalyst material according to claim 2 preparation method it is characterised in that：In step (1), described
The quality of titanium potassium oxalate is 1.56g；The concentration of described hydrogen peroxide is 30%, and volume is 2mL；The volume of described deionized water is
30-40mL：The concentration of described hydrochloric acid is 37%；Described hydrothermal reaction kettle is the stainless steel cauldron of polytetrafluoroethylliner liner, body
Amass as 50mL；The temperature of described drying is 80-100 DEG C.
4. composite photocatalyst material according to claim 2 preparation method it is characterised in that：In step (2), described
The concentration of acetic acid copper liquor is 0.062g/mL, and volume is 16mL；The concentration of described NaOH aqueous solution is 0.28g/mL, volume
For 16mL；The concentration of described aqueous citric acid solution is 0.16g/mL, and volume is 10mL；The temperature of described drying is 60-80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611025221.XA CN106466604A (en) | 2016-11-22 | 2016-11-22 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611025221.XA CN106466604A (en) | 2016-11-22 | 2016-11-22 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106466604A true CN106466604A (en) | 2017-03-01 |
Family
ID=58230969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611025221.XA Pending CN106466604A (en) | 2016-11-22 | 2016-11-22 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106466604A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824233A (en) * | 2017-03-27 | 2017-06-13 | 曲靖师范学院 | The method of photocatalysis antibacterial or degradation of organic substances |
| CN106944052A (en) * | 2017-03-27 | 2017-07-14 | 曲靖师范学院 | Cu2+1O/Cu2Cl(OH)3/TiO2Ternary complex and preparation method thereof |
| CN107233922A (en) * | 2017-06-19 | 2017-10-10 | 天津城建大学 | A kind of stone-like C2O7Ti2·3H2O photochemical catalysts and preparation method thereof |
| CN108169308A (en) * | 2017-12-28 | 2018-06-15 | 中南大学 | A kind of preparation method and applications of clay modified electrode |
| CN109865514A (en) * | 2019-03-26 | 2019-06-11 | 武汉工程大学 | A kind of preparation method of copper/titanic oxide composite photochemical catalyst material |
| CN109876809A (en) * | 2019-04-01 | 2019-06-14 | 中国科学院过程工程研究所 | A kind of hollow more Shell Materials of metal composite oxide and its preparation method and application |
| CN110882699A (en) * | 2019-12-06 | 2020-03-17 | 四川源景绿能科技有限公司 | Photocatalyst based on triple heterojunction structure and preparation method thereof |
| CN112823881A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院兰州化学物理研究所 | Sea urchin-like titanium dioxide/cuprous oxide composite material, and preparation method and application thereof |
| CN113181912A (en) * | 2021-03-26 | 2021-07-30 | 南京信息工程大学 | Cu2O-TiO2Composite photocatalyst and preparation method and application thereof |
| CN113368854A (en) * | 2021-06-10 | 2021-09-10 | 西南林业大学 | Nano TiO (titanium dioxide)2/Cu2Preparation method of O porous composite material |
| CN116351417A (en) * | 2023-03-17 | 2023-06-30 | 陕西净豹新材料有限公司 | Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444723A (en) * | 2008-08-04 | 2009-06-03 | 华东师范大学 | Method for preparing TiO2 hollow micro-sphere material |
| CN103933979A (en) * | 2014-04-30 | 2014-07-23 | 国电科学技术研究院 | Preparation method for controlling valence state of metal loaded on TiO2 nanotube |
| CN104843779A (en) * | 2015-04-29 | 2015-08-19 | 浙江大学 | Hollow spherical rutile titanium dioxide mesocrystal and preparation method thereof |
| CN105032468A (en) * | 2015-08-03 | 2015-11-11 | 中南大学 | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof |
| CN105540657A (en) * | 2016-01-14 | 2016-05-04 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
| CN105879887A (en) * | 2016-05-31 | 2016-08-24 | 南开大学 | Cu2O@Cu/AgBr composite light catalyst and preparation method thereof |
-
2016
- 2016-11-22 CN CN201611025221.XA patent/CN106466604A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444723A (en) * | 2008-08-04 | 2009-06-03 | 华东师范大学 | Method for preparing TiO2 hollow micro-sphere material |
| CN103933979A (en) * | 2014-04-30 | 2014-07-23 | 国电科学技术研究院 | Preparation method for controlling valence state of metal loaded on TiO2 nanotube |
| CN104843779A (en) * | 2015-04-29 | 2015-08-19 | 浙江大学 | Hollow spherical rutile titanium dioxide mesocrystal and preparation method thereof |
| CN105032468A (en) * | 2015-08-03 | 2015-11-11 | 中南大学 | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof |
| CN105540657A (en) * | 2016-01-14 | 2016-05-04 | 浙江大学 | Nanosheet-assembling core-shell structure anatase titanium dioxide microsphere and preparation method thereof |
| CN105879887A (en) * | 2016-05-31 | 2016-08-24 | 南开大学 | Cu2O@Cu/AgBr composite light catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘漫红等: "《纳米材料及其制备技术》", 31 August 2014 * |
| 王续龙: "新型TiO2复合材料制备及光催化性能研究", 《万方数据知识服务平台》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944052B (en) * | 2017-03-27 | 2020-01-31 | 曲靖师范学院 | Cu2+1O/Cu2Cl(OH)3/TiO2Ternary complex and preparation method thereof |
| CN106944052A (en) * | 2017-03-27 | 2017-07-14 | 曲靖师范学院 | Cu2+1O/Cu2Cl(OH)3/TiO2Ternary complex and preparation method thereof |
| CN106824233A (en) * | 2017-03-27 | 2017-06-13 | 曲靖师范学院 | The method of photocatalysis antibacterial or degradation of organic substances |
| CN106824233B (en) * | 2017-03-27 | 2019-07-19 | 曲靖师范学院 | The method of photocatalysis antibacterial or degradation of organic substances |
| CN107233922A (en) * | 2017-06-19 | 2017-10-10 | 天津城建大学 | A kind of stone-like C2O7Ti2·3H2O photochemical catalysts and preparation method thereof |
| CN107233922B (en) * | 2017-06-19 | 2019-08-30 | 天津城建大学 | A kind of stone-like C2O7Ti2·3H2O photochemical catalyst and preparation method thereof |
| CN108169308A (en) * | 2017-12-28 | 2018-06-15 | 中南大学 | A kind of preparation method and applications of clay modified electrode |
| CN108169308B (en) * | 2017-12-28 | 2020-11-06 | 中南大学 | Preparation method and application of clay modified electrode |
| CN109865514A (en) * | 2019-03-26 | 2019-06-11 | 武汉工程大学 | A kind of preparation method of copper/titanic oxide composite photochemical catalyst material |
| CN109876809B (en) * | 2019-04-01 | 2020-10-09 | 中国科学院过程工程研究所 | Composite metal oxide hollow multi-shell material and preparation method and application thereof |
| CN109876809A (en) * | 2019-04-01 | 2019-06-14 | 中国科学院过程工程研究所 | A kind of hollow more Shell Materials of metal composite oxide and its preparation method and application |
| CN112823881A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院兰州化学物理研究所 | Sea urchin-like titanium dioxide/cuprous oxide composite material, and preparation method and application thereof |
| CN112823881B (en) * | 2019-11-21 | 2022-04-08 | 中国科学院兰州化学物理研究所 | Sea urchin-like titanium dioxide/cuprous oxide composite material, and preparation method and application thereof |
| CN110882699A (en) * | 2019-12-06 | 2020-03-17 | 四川源景绿能科技有限公司 | Photocatalyst based on triple heterojunction structure and preparation method thereof |
| CN113181912A (en) * | 2021-03-26 | 2021-07-30 | 南京信息工程大学 | Cu2O-TiO2Composite photocatalyst and preparation method and application thereof |
| CN113368854A (en) * | 2021-06-10 | 2021-09-10 | 西南林业大学 | Nano TiO (titanium dioxide)2/Cu2Preparation method of O porous composite material |
| CN116351417A (en) * | 2023-03-17 | 2023-06-30 | 陕西净豹新材料有限公司 | Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106466604A (en) | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof | |
| Chen et al. | Enhanced photoelectrochemical properties of ZnO/ZnSe/CdSe/Cu2-xSe core–shell nanowire arrays fabricated by ion-replacement method | |
| CN106861744B (en) | A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures | |
| CN106861742A (en) | A kind of zinc oxide nano rod/g C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| CN106732617B (en) | A kind of ZnO/Cu2O heterojunction photocatalysis material and preparation method thereof | |
| CN106881079B (en) | A kind of two dimensional oxidation tungsten/niobic acid tin nanometer sheet-piece composite material preparation method | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN108855140B (en) | CuS/Bi2WO6Heterojunction photocatalyst and preparation method and application thereof | |
| CN106582595B (en) | A kind of blue TiO2The preparation method of catalyst | |
| CN106799222B (en) | A kind of preparation method of titanium dioxide/niobium acid tin composite nano materials | |
| CN103881709B (en) | A kind of multi-stage porous TiO2The preparation method of/quantum dot composite material | |
| CN102553568A (en) | Method for preparing bismuth tungstate powder with high photocatalytic activity by adopting high-temperature microwave hydrothermal method | |
| CN102974373A (en) | Visible-light photocatalytic material and preparation method thereof | |
| CN105478142A (en) | Indium-sulfide mesoporous hollow microsphere photocatalyst, and preparation method and uses thereof | |
| CN107159273A (en) | A kind of preparation method of BiOCl nano-photocatalysts and obtained photochemical catalyst and application | |
| CN104785280A (en) | Flaky titanium dioxide/bismuth oxybromide composite photocatalyst and preparation method thereof | |
| CN104511293A (en) | Bismuth oxychloride-iron bismuth titanate composite photocatalyst and preparation method thereof | |
| CN102671674A (en) | Magnetically supported silver bromide photochemical catalysis material and preparation method thereof | |
| CN106431005B (en) | A kind of strontium titanates-titanium dioxide composite nano tube array film and the preparation method and application thereof | |
| CN103191725A (en) | BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof | |
| CN105771962A (en) | Near-infrared response carbon quantum dots/Bi2MoO6 photocatalyst and preparing method thereof | |
| CN107626331B (en) | Mn (manganese)3O4/BiOCl heterojunction photocatalyst and preparation method thereof | |
| CN103785429B (en) | A kind of silver orthophosphate/Graphene/titanic oxide nano compound material and preparation method | |
| CN106362742B (en) | A kind of Ag/ZnO nano-complex and its preparation method and application | |
| CN105457656A (en) | Preparation method and application of heterojunction photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170301 |
|
| RJ01 | Rejection of invention patent application after publication |