CN108906026B - Lanthanum-cerium co-doped titanium oxide material and preparation method based on mixed rare earth carbonate - Google Patents
Lanthanum-cerium co-doped titanium oxide material and preparation method based on mixed rare earth carbonate 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 67
- 229910052761 rare earth metal Inorganic materials 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 58
- -1 rare earth carbonate Chemical class 0.000 title claims abstract description 28
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 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 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 24
- 229910052746 lanthanum Inorganic materials 0.000 claims description 23
- 229910052684 Cerium Inorganic materials 0.000 claims description 22
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 12
- 238000003756 stirring Methods 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 10
- 238000001354 calcination Methods 0.000 claims description 9
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 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
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000002086 nanomaterial Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 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
- 238000003760 magnetic stirring Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002071 nanotube Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 239000000047 product Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 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
- 239000002351 wastewater Substances 0.000 description 2
- 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
- 238000002441 X-ray diffraction Methods 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
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005284 excitation Effects 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
- 238000002156 mixing Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000019614 sour taste Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明属于无机材料合成领域，具体涉及一种基于混合稀土碳酸盐的镧铈共掺杂氧化钛材料及制备方法。首先称取一定量含钛硫酸盐，溶解于蒸馏水中，控制比例掺入混合稀土碳酸盐溶液，随后将体系pH值调至酸性，水浴反应后，在马弗炉内煅烧，以实现氧化钛的水解生长、结晶化以及有效掺杂，所得纳米材料具有优异的可见光催化性能。该方法过程简单、原料廉价、不使用有机添加剂和有机钛源、环境成本低、产品性价比高，可实现大规模的工业化生产，所得产品在光催化降解、有机污染物处理等领域有广阔的应用前景。
The invention belongs to the field of inorganic material synthesis, in particular to a lanthanum-cerium co-doped titanium oxide material based on mixed rare earth carbonate and a preparation method. Firstly, a certain amount of titanium-containing sulfate is weighed, dissolved in distilled water, mixed with mixed rare earth carbonate solution in a controlled proportion, and then the pH value of the system is adjusted to acidity. After the water bath reaction, it is calcined in a muffle furnace to realize titanium oxide. The obtained nanomaterials have excellent visible light catalytic performance. The method has the advantages of simple process, cheap raw materials, no use of organic additives and organic titanium sources, low environmental cost, high product cost performance, and can realize large-scale industrial production. The obtained products have broad applications in the fields of photocatalytic degradation and organic pollutant treatment. prospect.
Description
Technical Field
The invention belongs to the field of inorganic nano materials, relates to a rare earth element co-doped titanium oxide photocatalytic functional material and a preparation method thereof, and particularly relates to a method for preparing lanthanum-cerium co-doped titanium oxide by using mixed rare earth carbonate, so that the titanium oxide has higher visible light catalytic capability.
Background
The nano-grade anatase titanium dioxide has large forbidden bandwidth and good effect of degrading organic pollutants by ultraviolet light catalysis, but the relative content of the ultraviolet light in natural light is less (only 3% -5%), and the utilization rate of solar energy is low. In addition, the anatase titanium dioxide powder has small specific surface area and poor dispersibility, electrons and holes generated by light excitation are easy to combine, so that the light quantum efficiency is very low, the visible light catalytic activity is not high, and the wide application of titanium oxide is greatly limited. The rare earth doping can form a capture center to inhibit the recombination of photo-generated electrons and holes; forming a doping energy level to reduce the band gap of the titanium oxide; the grain size is reduced, the specific surface area of the particles is increased, and the photocatalytic activity of the titanium oxide under visible light is greatly enhanced. Therefore, research on doping titanium oxide with rare earth has been receiving increasing attention.
The rare earth doped titanium dioxide nano material can be conveniently prepared by utilizing an organic titanium source, for example, Zhongping et al, in rare earth lanthanum and cerium doped mixed crystal titanium dioxide nano tube photocatalysis performance research, introduced that butyl titanate is used as a raw material, and a Sol-Gel (Sol-Gel) method is combined with a microwave method to prepare rare earth lanthanum and cerium doped TiO2A method for mixing crystal nanotubes. Prepared TiO2The outer diameter of the nano tube is 15nm, the inner diameter of the nano tube is 10nm, and the shape of the nano tube is uniform; when the lanthanum is doped by 0.5 percent and the cerium is doped by 0.5 percent (molar mass fraction), and the calcining temperature is 900 ℃, the photocatalytic activity is best. Such as Guo Li, Wang Danjun, Lidong Sheng, etc. in La-Ce-TiO2The synthesis of nano photocatalyst by sol-microwave method, the spectral characterization and the activity research thereof are successfully carried out by using tetrabutyl titanate as raw material and adopting the sol-microwave methodPreparing nanometer TiO co-doped with lanthanum and cerium2The powder has a continuous broadened absorption band under 400nm, the efficiency of light absorption is greatly improved, when the doping amount of lanthanum is 2% and the doping amount of cerium is 0.04% (mole fraction), the co-doping effect is good, and after 15 hours of natural illumination, the removal rate of COD in the wastewater can reach 86.11%. However, the cost of the organic titanium source and the organic modifier is high, and the organic groups dissociated from the raw materials bring great pressure to the later-stage wastewater treatment, so that the popularization and the application of the preparation method are limited.
For this reason, many researchers have considered the synthesis of rare earth doped titanium oxide nanomaterials using cheaper inorganic titanium sources. Chinese patent CN1631521 by naval university, zhao qinghua, tan hua qin et al discloses a technology for preparing rare earth doped titanium dioxide by coprecipitation-calcination of titanium tetrachloride, and finally obtains a modified nano titanium dioxide photocatalyst with high photocatalytic activity. However, titanium tetrachloride has irritant, toxic and sour taste, is easy to smoke in the air, is corrosive, has very high hydrolysis reaction speed, is inconvenient to take in the production process, is difficult to accurately control the hydrolysis process, and is easy to cause larger quality fluctuation of products.
In Chinese patent CN106621807A, the Shanghan Yihong, Zhang Dan and the like propose a flue gas treatment method of catalytic reduction of a titanium dioxide nanotube array doped with lanthanum-cerium oxide and simultaneous desulfurization and denitrification. The desulfurization efficiency is 96%; denitration efficiency of 99.9%, elemental sulfur recovery rate of 97%, and N2The recovery rate was 98%. However, cerium oxide is toxic, has too low solubility, and is difficult to control in proportion during doping, thereby bringing difficulty to production and application.
Although many progress has been made in the current research, the rare earth doped titanium oxide always faces the problems of expensive rare earth raw materials, high product cost and the like, and the rare earth oxide is often difficult to dissolve in a common acid environment, so that the large-scale application of the rare earth in the field of visible light type catalyst preparation is limited. China is a big rare earth country, besides high-purity rare earth oxides, a lot of cheap rare earth resources such as mixed rare earth carbonate are also available, the mixed rare earth carbonate is a primary product in the separation and purification process of rare earth concentrate, the price is lower (main rare earth components are La and Ce) because the separation of different rare earths is not realized, the mixed rare earth carbonate is active in chemical property, and is easy to react with dilute acid to generate rare earth ions for doping, so the mixed rare earth carbonate is an ideal cheap rare earth doping industrial raw material. If the mixed rare earth carbonate is used as the titanium oxide doped rare earth raw material, the raw material cost of the rare earth doped titanium oxide and the requirement on the acid resistance of equipment are obviously reduced, but no relevant report is found at present.
To solve the above problems, TiO is economically and efficiently upgraded2The invention provides a method for preparing a nano catalyst by utilizing lanthanum-cerium mixed rare earth carbonate co-doped titanium oxide, and the method has the advantages of high photocatalytic activity under visible light. The mixed rare earth carbonate is produced in city of autonomous region of inner Mongolia, wherein lanthanum and cerium rare earth exist in the form of carbonate, and the mixed rare earth carbonate is environment-friendly, cheap and easily available, easily soluble in water, convenient in regulation and control of doping proportion, and remarkably reduces difficulty in the production process. Meanwhile, the method uses inorganic titanium salt with moderate hydrolysis speed as a precursor, thereby obviously reducing the pressure of post-treatment of wastewater and improving TiO2The stability in the hydrolysis nucleation process can obtain ideal visible light catalytic performance, and the cost performance of the product is improved.
Disclosure of Invention
The invention aims to provide a brand-new preparation method of lanthanum-cerium rare earth element co-doped titanium oxide nano material aiming at the defects of the prior art. The invention overcomes the problems of expensive raw materials, inconvenient taking and use, complex preparation process, uneven nucleation and growth of titanium oxide, poor crystallinity and the like in the prior synthesis technology, and obtains the nano photocatalytic functional material with high degree of crystallization, uniform particle growth and positive response to visible light by selecting cheap mixed rare earth carbonate, regulating and controlling the constant temperature hydrolysis of inorganic titanium source, doping proportion of rare earth elements and calcining and activating processes.
The purpose of the invention is realized by the following technical scheme:
the lanthanum-cerium-rare earth element co-doped titanium oxide nano material has the advantages that the total amount of lanthanum and cerium in titanium oxide is within the range of 0.2-5 mol%, the preferable content of rare earth lanthanum is 1-2 mol%, and the content of rare earth cerium is 0.2-1 mol%.
The preparation method of the lanthanum-cerium-rare earth element co-doped titanium oxide nano material provided by the invention comprises the following steps of:
(1) preparing a titanium dioxide precursor: weighing a certain amount of titanium-containing sulfate, adding distilled water to prepare 0.1-1 mol/L titanium sulfate solution, and magnetically stirring for 30 min.
(2) Doping lanthanum and cerium rare earth elements: under the condition of stirring, the mixed rare earth carbonate solution is doped into the precursor solution obtained in the step (1), so that the total amount of lanthanum and cerium and TiO in the mixed solution2The molar percentage of the lanthanum and the cerium is 0.2-5%, wherein the molar ratio of the lanthanum to the cerium is 0.3-3, after the mixture is fully stirred, the pH value of the mixed liquid is adjusted to 1-5 by using an alkaline solution, and then the mixture is magnetically stirred for 1-3 hours.
(3) Doped nano TiO2The crystallization treatment: and (3) placing the emulsion obtained in the step (2) into a water bath kettle, and carrying out water bath treatment for 2-8 h under the condition of magnetic stirring at the constant temperature of 30-90 ℃. After cooling, the emulsion is washed centrifugally several times to remove free CO3 2-、SO4 2-And (3) ionizing the obtained white precipitate, drying the white precipitate for 3-5 h at the temperature of 80-120 ℃, grinding the white precipitate to obtain a powder sample, and calcining the powder sample for 1-6 h in a muffle furnace at the temperature of 300-700 ℃ to obtain the lanthanum-cerium rare earth element co-doped titanium oxide nano material.
The titanium-containing sulfate salt is defined as: titanium sulfate or titanyl sulfate.
Advantageous effects
(1) The method uses the titanium-containing sulfate as the precursor for preparing the titanium oxide, avoids the use of an organic precursor and a modifier, and obviously reduces the difficulty of sewage treatment. Meanwhile, the precursor is low in price, the hydrolysis speed is relatively slow, and the phenomenon that nucleation is not uniform due to too fast hydrolysis, which is caused by the fact that some titanium salts which are hydrolyzed rapidly are not the same as the titanium salts which are hydrolyzed rapidly, is avoided, so that TiO is caused2The catalytic performance is unstable. Which are beneficial to the industrial production, popularization and application of the rare earth doped titanium oxide nano material.
(2) The invention uses lanthanum-cerium mixed rare earth carbonate as a doped rare earth source, is cheap and easy to obtain, has no toxicity and stability, is convenient to take and use, is easy to regulate and control the doping proportion, and is convenient for more efficient production and application.
(3) The lanthanum-cerium-rare earth element co-doped titanium oxide is used, and lanthanum doping can generate a capture trap in the catalyst to inhibit the recombination of titanium oxide photogenerated electrons and holes; the doped cerium can form an impurity energy level, reduce the band gap of the titanium oxide and enhance the response capability of the titanium oxide to visible light. According to the invention, titanium oxide is modified by regulating the doping proportion of lanthanum and cerium and utilizing the synergistic effect of lanthanum and cerium co-doping, so that a high-performance nano photocatalytic functional material is obtained, and the use effect of the catalyst is remarkably improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of lanthanum-cerium co-doped titanium oxide in the methods of examples 1, 2, 3 and 4 of the present invention.
FIG. 2 is a SEM image of lanthanum-cerium co-doped titanium oxide in the method of example 1 of the present invention.
FIG. 3 shows the UV-vis UV-visible diffuse reflectance spectra of pure titanium oxide and lanthanum-cerium co-doped titanium oxide in the methods of examples 1 and 4 of the present invention.
FIG. 4 is a graph showing the visible light catalytic performance of pure titanium oxide in the method of example 3 of the present invention and lanthanum-cerium co-doped titanium oxide in the methods of examples 1, 2, 3 and 4.
Detailed Description
The invention will be described in further detail below with reference to specific embodiments and the attached drawings:
example 1
(1) 3.6g of titanium sulfate is weighed, 50mL of distilled water is added to prepare 0.3mol/L titanium sulfate solution, and then magnetic stirring is carried out for 30 min.
(2) Under the condition of stirring, doping the mixed rare earth carbonate solution into the precursor solution obtained in the step (1) to ensure that lanthanum, cerium and TiO in the mixed solution2Are 1.5% and 0.5%, respectively, and after sufficient stirring, the pH of the mixed liquid is adjusted to 1 with 2mol/L sodium hydroxide solution, followed by magnetic stirring for 1 h.
(3) And (3) placing the emulsion obtained in the step (2) into a water bath kettle, and treating for 5 hours in a water bath under the condition of constant temperature of 90 ℃ and magnetic stirring. After cooling, the emulsionRemoving free CO by multiple centrifugal washing3 2-、SO4 2-And (3) ionizing, drying the obtained white precipitate at 80 ℃ for 3h, grinding to obtain a powder sample, and calcining the powder sample in a muffle furnace at 600 ℃ for 2h to obtain the lanthanum-cerium rare earth element co-doped titanium oxide nano material. After 6 hours of visible light illumination, the degradation rate of methyl orange MO can reach 97.99%, which is 71.67% higher than that of pure titanium oxide.
Example 2
(1) 1.6g of titanyl sulfate was weighed, 50mL of distilled water was added to prepare a 0.2mol/L solution of titanium sulfate, followed by magnetic stirring for 30 min.
(2) Under the condition of stirring, doping the mixed rare earth carbonate solution into the precursor solution obtained in the step (1) to ensure that lanthanum, cerium and TiO in the mixed solution2The molar percentages of (a) and (b) are 1% and 1%, respectively, and after sufficient stirring, the pH of the mixed liquid is adjusted to 3 with 2mol/L aqueous ammonia solution, followed by magnetic stirring for 2 hours.
(3) And (3) placing the emulsion obtained in the step (2) into a water bath kettle, and treating for 2 hours in a water bath under the condition of constant temperature of 60 ℃ and magnetic stirring. After cooling, the emulsion is washed centrifugally several times to remove free CO3 2-、SO4 2-And (3) ionizing, drying the obtained white precipitate at 100 ℃ for 4h, grinding to obtain a powder sample, and calcining the powder sample in a muffle furnace at 400 ℃ for 6h to obtain the lanthanum-cerium-rare earth element co-doped titanium oxide nano material. After 8 hours of visible light illumination, the degradation rate of methyl orange MO can reach 85.78%, which is improved by 56.94% compared with pure titanium oxide.
Example 3
(1) 8g of titanyl sulfate is weighed, 50mL of distilled water is added to prepare a 1mol/L titanium sulfate solution, and then the solution is magnetically stirred for 30 min.
(2) Under the condition of stirring, doping the mixed rare earth carbonate solution into the precursor solution obtained in the step (1) to ensure that lanthanum, cerium and TiO in the mixed solution2The molar percentages of (a) and (b) are 3% and 2%, respectively, and after sufficient stirring, the pH of the mixed liquid is adjusted to 5 with 2mol/L aqueous ammonia solution, followed by magnetic stirring for 3 hours.
(3) Placing the emulsion obtained in the step (2) into a water bath,under the condition of constant temperature of 30 ℃ and magnetic stirring, the mixture is treated in water bath for 8 hours. After cooling, the emulsion is washed centrifugally several times to remove free CO3 2-、SO4 2-And (3) ionizing, drying the obtained white precipitate at 120 ℃ for 5h, grinding to obtain a powder sample, and calcining the powder sample in a muffle furnace at 700 ℃ for 4h to obtain the lanthanum-cerium-rare earth element co-doped titanium oxide nano material. After 8 hours of visible light illumination, the degradation rate of methyl orange MO can reach 48.42%, which is 19.58% higher than that of pure titanium oxide.
Example 4
(1) 3.6g of titanium sulfate is weighed, 50mL of distilled water is added to prepare 0.3mol/L titanium sulfate solution, and then magnetic stirring is carried out for 30 min.
(2) Under the condition of stirring, doping the mixed rare earth carbonate solution into the precursor solution obtained in the step (1) to ensure that lanthanum, cerium and TiO in the mixed solution2Are 1.5% and 3.5%, respectively, and after sufficient stirring, the pH of the mixed liquid is adjusted to 1 with 2mol/L sodium hydroxide solution, followed by magnetic stirring for 1 h.
(3) And (3) placing the emulsion obtained in the step (2) into a water bath kettle, and treating for 5 hours in a water bath under the condition of constant temperature of 90 ℃ and magnetic stirring. After cooling, the emulsion is washed centrifugally several times to remove free CO3 2-、SO4 2-And (3) ionizing, drying the obtained white precipitate at 80 ℃ for 3h, grinding to obtain a powder sample, and calcining the powder sample in a muffle furnace at 600 ℃ for 2h to obtain the lanthanum-cerium rare earth element co-doped titanium oxide nano material. After 8 hours of visible light illumination, the degradation rate of methyl orange MO can reach 64.46 percent, which is 35.62 percent higher than that of pure titanium oxide.
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