CN108906026A - Lanthanum cerium codoping titanium oxide material and preparation method based on mischmetal carbonate - Google Patents
Lanthanum cerium codoping titanium oxide material and preparation method based on mischmetal carbonate Download PDFInfo
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- CN108906026A CN108906026A CN201810889953.6A CN201810889953A CN108906026A CN 108906026 A CN108906026 A CN 108906026A CN 201810889953 A CN201810889953 A CN 201810889953A CN 108906026 A CN108906026 A CN 108906026A
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- mischmetal
- titanium oxide
- carbonate
- lanthanum cerium
- cerium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001122 Mischmetal Inorganic materials 0.000 title claims abstract description 31
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 9
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000008236 heating water Substances 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052719 titanium Inorganic materials 0.000 abstract description 11
- 239000010936 titanium Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- 239000006259 organic additive Substances 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 206010001497 Agitation Diseases 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000003760 hair shine Effects 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 rare earth Titanium oxide Chemical class 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- JKCQFXPSEZFGIJ-UHFFFAOYSA-N [O-2].[Ce+3].[La+3].[Ti+4].[O-2].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ce+3].[La+3].[Ti+4].[O-2].[O-2].[O-2].[O-2] JKCQFXPSEZFGIJ-UHFFFAOYSA-N 0.000 description 1
- IPMADRXFMYUSIV-UHFFFAOYSA-N [O].[La].[Ce] Chemical compound [O].[La].[Ce] IPMADRXFMYUSIV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention belongs to inorganic material to synthesize field, and in particular to a kind of lanthanum cerium codoping titanium oxide material and preparation method based on mischmetal carbonate.A certain amount of titaniferous sulfate is weighed first, it is dissolved in distilled water, control ratio mixes mischmetal carbonate solution, system pH is then adjusted to acidity, after water-bath, it is calcined in Muffle furnace, to realize hydrolysis growth, crystallization and the Effective Doping of titanium oxide, gained nano material has excellent visible light catalytic performance.This method process is simple, raw material is cheap, low without using organic additive and organic titanium source, Environmental costs, product cost is high, large-scale industrial production can be achieved, products obtained therefrom has broad application prospects in fields such as photocatalytic degradation, organic pollutant processing.
Description
Technical field
The invention belongs to field of inorganic nano material, are related to a kind of rare earth element codoping titanium oxide Photocatalysis Function Material
And preparation method thereof, and in particular to it is a kind of to prepare lanthanum cerium codoping titanium oxide using mischmetal carbonate, to make titanium oxide
Obtain higher visible light catalytic ability.
Background technique
Nano-sized anatase type titanium dioxide body forbidden bandwidth is big, has good ultraviolet catalytic degradable organic pollutant
Effect, however relative amount of the ultraviolet light in natural light is less (only accounting for 3%~5%), very low to the utilization rate of solar energy.
In addition to this, anatase titanium dioxide powder specific-surface area detection is small, bad dispersibility, and the electronics and hole that light excitation generates are easy multiple
It closes, causes photo-quantum efficiency very low, it is seen that photocatalytic activity is not high, significantly limits titanium oxide extensive use.It is rear-earth-doped
Trap center can be formed, light induced electron and hole-recombination are inhibited；Doped energy-band is formed, the band gap of titanium oxide is reduced；Reduce brilliant
Particle size increases the specific surface area of particle, greatly enhances the photocatalytic activity of titanium oxide under visible light.Therefore, it is mixed with rare earth
Titanium oxide doped research more and more attention has been paid to.
Rare earth doping titanium dioxide nano material is prepared using what organic titanium source can be convenient, such as all equality exists《Rare earth
Lanthanum, cerium dopping mixed crystal titania nanotube Photocatalytic Performance Study》One kind is described using butyl titanate as raw material, with colloidal sol-
Gel (Sol-Gel) method combination microwave method prepares the TiO of Rare Earth Lanthanum, cerium dopping2The method of mixed crystal nanotube.Prepared TiO2
Nanometer pipe outside diameter is 15nm, internal diameter 10nm, and form is more uniform；When doped lanthanum 0.5% and the doping (molal weight point of cerium 0.5%
Number), for calcination temperature at 900 DEG C, photocatalytic activity is best.Such as Guo Li, wangdan army, Li Dongsheng exist《La-Ce-TiO2Nanometer
The colloidal sol of photochemical catalyst-microwave method synthesis, Spectroscopic Characterization and its activity research》In using butyl titanate as raw material, using colloidal sol-
The nano-TiO that microwave method is successfully prepared lanthanum, cerium is co-doped with2Powder has the absorption band of continuous widthization, greatly at 400nm
The efficiency to light absorption is improved, when La doped amount is 2%, cerium dopping amount is 0.04% (molar fraction), is co-doped with effect
Preferably, under natural lighting after 15h, the removal rate of waste water COD can reach 86.11%.But organic titanium source and organic modifiers at
This is high, and the organic group that raw material middle reaches separate out can bring very big pressure to later period wastewater treatment, limit this preparation
The popularization and application of method.
For this purpose, Many researchers consider to use the more cheap synthetic rare earth doped titanium dioxide nano material of inorganic ti sources.Entirely
Learn military affairs, Zhao Qinghua, Tan Huaiqin et al. are in Chinese patent CN1631521, disclose and a kind of utilize titanium tetrachloride co-precipitation-calcining
Method prepares the technology of rare earth-doped titanium dioxide, finally obtains modified high catalytic active nanometer titania photocatalyst.
But the irritant toxic tart flavour of titanium tetrachloride, easy smoke in air are corrosive, hydrolysis speed is very fast, is producing
Inconvenience is taken in the process, is difficult accurately to control hydrolytic process, and product is easy to cause biggish quality fluctuation occur.
He Hanbing, Qin Yihong, Zhang Danglong et al. propose a kind of doped lanthanum cerium oxygen in Chinese patent CN106621807A
The Nano tube array of titanium dioxide of compound is catalyzed reduction, the flue gas processing method of simultaneous SO_2 and NO removal.Desulfuration efficiency is 96%；It is de-
Nitre efficiency 99.9%, simple substance sulfur recovery rate 97%, N2The rate of recovery 98%.But cerium oxide is toxic, soluble too low, doping
When, ratio is not easy to control, brings difficulty to production application.
Although current research has been achieved for much being in progress, it is high that rear-earth-doped type titanium oxide faces rare earths material always
Expensive, the problems such as goods cost is excessively high, and rare earth oxide is often insoluble in common acid environment, these all limit rare earth visible
The large-scale application of light type field of catalyst preparation.China is rare earth big country, and in addition to high purity rare earth oxides, there are also many honest and clean
The rare earth resources of valence, such as mischmetal carbonate, it is the primary product during rare earth ore concentrate separating-purifying, due to not having
Realizing the separation of different rare earths, thus price is lower (main rare earth composition be La and Ce), and chemical property is active, be easy with it is dilute
Acid reaction generates the rare earth ion for doping, is the ideal Cheap rare-earth doping raw material of industry.If using mischmetal carbon
Rare earths material of the hydrochlorate as titania addition will significantly reduce the cost of material of rear-earth-doped type titanium oxide and to the resistance to of equipment
Acid requirement, but yet there are no relevant report.
To solve the above-mentioned problems, TiO is efficiently and effectively promoted2Photocatalytic activity under visible light, the present invention mention
A kind of method for utilizing mixed rare earth of lanthanum and cerium carbonate codoping titanium oxide, nanocatalyst being made is gone out.Mischmetal used
Carbonate originates from Inner Mongolia Autonomous Region Baotou, and wherein lanthanum cerium mischmetal is existed in the form of carbonate, environmental-friendly, cheap
It is easy to get, is soluble easily in water, doping ratio conveniently regulating and controlling, significantly reducing the difficulty in production process.At the same time, this method uses
The moderate inorganic titanium salt of hydrolysis rate is presoma, significantly reduces the pressure of later period wastewater treatment, while also improving TiO2
Stability in hydrolysis nucleation process, can get ideal visible light catalytic performance, improves the cost performance of product.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of current above-mentioned technology, propose that a kind of completely new lanthanum cerium mischmetal element is co-doped with
The preparation method of titanium oxide doped nano material.The invention overcomes expensive starting materials in existing synthetic technology, takes inconvenience, prepared
The problems such as journey is complicated and titanium oxide nucleating growth is uneven, crystallinity is poor, by select cheap mischmetal carbonate,
Regulation inorganic ti sources determine warm water solution, rare earth element mixed ratio and calcining and activating process, and it is raw to obtain crystallization degree height, particle
It grows uniformly, to visible light-responded positive nano-photo catalytic functional material.
The purpose of the present invention is what is be achieved through the following technical solutions：
Lanthanum cerium mischmetal element codoping titanium oxide nano material of the present invention, in titanium oxide lanthanum cerium total amount 0.2~
Within the scope of 5mol%, preferred content Rare Earth Lanthanum is 1~2mol%, and cerium is 0.2~1mol%.
The preparation method for material of lanthanum cerium mischmetal element codoping titanium oxide nanometer material provided by the invention, according to the following steps into
Row：
(1) preparation of TiO 2 precursor：A certain amount of titaniferous sulfate is weighed, distilled water is added to be made into 0.1~1mol/
The titanium sulfate solution of L, magnetic agitation 30min.
(2) doping of lanthanum cerium mischmetal element：Under agitation, mischmetal carbonate solution is mixed into step (1) institute
In the precursor solution obtained, so that lanthanum cerium total amount and TiO in mixed liquor2Molar percentage be 0.2~5%, wherein lanthanum cerium rubs
The range that your ratio is 0.3~3, after being sufficiently stirred, is adjusted to 1~5 for the pH value of the mixing liquid using alkaline solution, then
1~3h of magnetic agitation.
(3) nano-TiO after adulterating2Crystallizing treatment：The emulsion that step (2) obtains is placed in water-bath, in constant temperature
Under the conditions of 30~90 DEG C of magnetic agitations, 2~8h of water bath processing.After cooling, emulsion removes free through multiple centrifuge washing
CO3 2-、SO4 2-Ion, gained white precipitate is through 80~120 DEG C of 3~5h of drying, gained powder-like after grinding, through Muffle furnace 300
Under the conditions of~700 DEG C, 1~6h is calcined, the titanium dioxide nano material of lanthanum cerium mischmetal element codope is obtained.
The titaniferous sulfate is limited to：Titanium sulfate or titanyl sulfate.
Beneficial effect
(1) present invention uses titaniferous sulfate as the presoma for preparing titanium oxide, avoids organic precursor and modification
The use of agent significantly reduces the difficulty of sewage treatment.Meanwhile the presoma is not only cheap, but also hydrolysis rate is more
It is gentle, will not be as some rapid titanium salts of hydrolysis, nucleation is uneven caused by occurring because of too fast hydrolysis, so as to cause TiO2It urges
Change the unstable problem of performance.These industrialized productions for being all conducive to this rear-earth-doped oxidation titanium nano material are answered with popularization
With.
(2) present invention uses mixed rare earth of lanthanum and cerium carbonate as the rare earth source of doping, and cheap and easy to get, non-toxic stable takes
It is easy to regulate and control with convenient, doping ratio, convenient for application is produced more efficiently.
(3) present invention uses lanthanum cerium mischmetal element codoping titanium oxide, and doped lanthanum can generate capture in catalytic inner
Trap inhibits the compound of titanium oxide photoproduction electrons and holes；Doping cerium can form impurity energy level, reduce the band gap of titanium oxide,
Enhance its responding ability to visible light.The present invention utilizes the association of lanthanum cerium codope by the ratio of regulation lanthanum Ce elements doping
Same-action is modified titanium oxide, to obtain high performance nano-photo catalytic functional material, has been obviously improved catalyst
Using effect.
Detailed description of the invention
The X ray diffracting spectrum of lanthanum cerium codoping titanium oxide in 1,2,3,4 method of Fig. 1 embodiment of the present invention.
The Flied emission SEM figure of lanthanum cerium codoping titanium oxide in 1 method of Fig. 2 embodiment of the present invention.
Pure zirconia titanium, the UV-vis ultraviolet-visible of lanthanum cerium codoping titanium oxide are unrestrained in Fig. 3 embodiment of the present invention 1,4 methods
Reflectance spectrum.
Lanthanum cerium codope aoxidizes in 1,2,3,4 method of pure zirconia titanium and embodiment in 3 method of Fig. 4 embodiment of the present invention
The visible light catalytic performance atlas of titanium.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below：
Embodiment 1
(1) 3.6g titanium sulfate is weighed, 50mL distilled water is added, is made into the titanium sulfate solution of 0.3mol/L, magnetic force stirs later
Mix 30min.
(2) under agitation, mischmetal carbonate solution is mixed in step (1) resulting precursor solution, is made
Obtain lanthanum, cerium and the TiO in mixed liquor2Molar percentage be respectively 1.5% and 0.5%, after being sufficiently stirred, with the hydrogen of 2mol/L
The pH value of the mixing liquid is adjusted to 1 by sodium hydroxide solution, subsequent magnetic agitation 1h.
(3) emulsion that step (2) obtains is placed in water-bath, under the conditions of 90 DEG C of magnetic agitations of constant temperature, at water-bath
Manage 5h.After cooling, emulsion removes free CO through multiple centrifuge washing3 2-、SO4 2-Ion, gained white precipitate are dried through 80 DEG C
Dry 3h, gained powder-like after grinding calcine 2h, obtain lanthanum cerium mischmetal element codope through Muffle furnace under the conditions of 600 DEG C
Titanium dioxide nano material.After visible light shines lower 6h, 97.99% can be reached to the degradation rate of methyl orange MO, promoted than pure zirconia titanium
71.67%.
Embodiment 2
(1) 1.6g titanyl sulfate is weighed, 50mL distilled water is added, is made into the titanium sulfate solution of 0.2mol/L, later magnetic force
Stir 30min.
(2) under agitation, mischmetal carbonate solution is mixed in step (1) resulting precursor solution, is made
Obtain lanthanum, cerium and the TiO in mixed liquor2Molar percentage be respectively 1% and 1%, it is molten with the ammonium hydroxide of 2mol/L after being sufficiently stirred
The pH value of the mixing liquid is adjusted to 3 by liquid, subsequent magnetic agitation 2h.
(3) emulsion that step (2) obtains is placed in water-bath, under the conditions of 60 DEG C of magnetic agitations of constant temperature, at water-bath
Manage 2h.After cooling, emulsion removes free CO through multiple centrifuge washing3 2-、SO4 2-Ion, gained white precipitate is through 100 DEG C
4h is dried, gained powder-like after grinding calcines 6h, obtain lanthanum cerium mischmetal element codope through Muffle furnace under the conditions of 400 DEG C
Titanium dioxide nano material.After visible light shines lower 8h, 85.78% can be reached to the degradation rate of methyl orange MO, mentioned than pure zirconia titanium
Rise 56.94%.
Embodiment 3
(1) 8g titanyl sulfate is weighed, 50mL distilled water is added, is made into the titanium sulfate solution of 1mol/L, later magnetic agitation
30min。
(2) under agitation, mischmetal carbonate solution is mixed in step (1) resulting precursor solution, is made
Obtain lanthanum, cerium and the TiO in mixed liquor2Molar percentage be respectively 3% and 2%, it is molten with the ammonium hydroxide of 2mol/L after being sufficiently stirred
The pH value of the mixing liquid is adjusted to 5 by liquid, subsequent magnetic agitation 3h.
(3) emulsion that step (2) obtains is placed in water-bath, under the conditions of 30 DEG C of magnetic agitations of constant temperature, at water-bath
Manage 8h.After cooling, emulsion removes free CO through multiple centrifuge washing3 2-、SO4 2-Ion, gained white precipitate is through 120 DEG C
5h is dried, gained powder-like after grinding calcines 4h, obtain lanthanum cerium mischmetal element codope through Muffle furnace under the conditions of 700 DEG C
Titanium dioxide nano material.After visible light shines lower 8h, 48.42% can be reached to the degradation rate of methyl orange MO, mentioned than pure zirconia titanium
Rise 19.58%.
Embodiment 4
(1) 3.6g titanium sulfate is weighed, 50mL distilled water is added, is made into the titanium sulfate solution of 0.3mol/L, magnetic force stirs later
Mix 30min.
(2) under agitation, mischmetal carbonate solution is mixed in step (1) resulting precursor solution, is made
Obtain lanthanum, cerium and the TiO in mixed liquor2Molar percentage be respectively 1.5% and 3.5%, after being sufficiently stirred, with the hydrogen of 2mol/L
The pH value of the mixing liquid is adjusted to 1 by sodium hydroxide solution, subsequent magnetic agitation 1h.
(3) emulsion that step (2) obtains is placed in water-bath, under the conditions of 90 DEG C of magnetic agitations of constant temperature, at water-bath
Manage 5h.After cooling, emulsion removes free CO through multiple centrifuge washing3 2-、SO4 2-Ion, gained white precipitate are dried through 80 DEG C
Dry 3h, gained powder-like after grinding calcine 2h, obtain lanthanum cerium mischmetal element codope through Muffle furnace under the conditions of 600 DEG C
Titanium dioxide nano material.After visible light shines lower 8h, 64.46% can be reached to the degradation rate of methyl orange MO, promoted than pure zirconia titanium
35.62%.
Claims (3)
1. a kind of lanthanum cerium codoping titanium oxide material based on mischmetal carbonate, which is characterized in that the rare earth is co-doped with
Miscellaneous material, be 0.3~3 using lanthanum cerium molar ratio mischmetal carbonate as raw material, and in the salt acidic presoma of titaniferous sulfuric acid
Effective Doping is realized in middle experience hydrolytic precipitation, crystallization calcining, and the total doping of lanthanum cerium is in 0.2~5mol% range in gained titanium oxide
It is interior, preferred lanthanum content 1~2mol%, 0.2~1mol% of cerium content.
2. a kind of lanthanum cerium codoping titanium oxide material based on mischmetal carbonate described in accordance with the claim 1, feature
It is, the titaniferous sulfate is any one of titanium sulfate and titanyl sulfate or two kinds.
3. a kind of preparation side of lanthanum cerium codoping titanium oxide material based on mischmetal carbonate described in accordance with the claim 1
Method, which is characterized in that include the following steps：
Take titaniferous sulfate starting material, according to concentration be 0.1~1mol/L be dissolved in distilled water, be sufficiently stirred, obtain it is colorless and transparent before
Liquid solution is driven, the mischmetal carbonate solution of appropriate 0.15mol/L is added dropwise, so that lanthanum cerium total content accounts for TiO in mixed liquor2's
0.2~5mol% is added dropwise alkaline solution for the pH value of mixed liquor and is adjusted to 1~5 under agitation, slurries then 30~
90 DEG C of progress heating water baths handle 2~8h and finally forge in 300~700 DEG C of crystallization through washing, separation, drying, grinding after cooling
It burns, lanthanum cerium mischmetal element codoping titanium oxide material is made.
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