CN106423136A - Cerium and lanthanum double-doped titanium dioxide nano rod light catalyst, and preparation method and application thereof - Google Patents
Cerium and lanthanum double-doped titanium dioxide nano rod light catalyst, and preparation method and application thereof Download PDFInfo
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- CN106423136A CN106423136A CN201610979220.2A CN201610979220A CN106423136A CN 106423136 A CN106423136 A CN 106423136A CN 201610979220 A CN201610979220 A CN 201610979220A CN 106423136 A CN106423136 A CN 106423136A
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- lanthanum
- cerium
- titanium dioxide
- dioxide nano
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 26
- 239000002073 nanorod Substances 0.000 title claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 22
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- -1 rare earth ions Chemical class 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000000703 Cerium Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 239000004744 fabric Substances 0.000 claims abstract description 6
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000012456 homogeneous solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a cerium and lanthanum double-doped titanium dioxide nano rod light catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: mixing and stirring TBOT or TIPO, 37 percent by weight of HCl and water H2O to obtain a homogeneous clarified precursor solution A; adding cerium salt and lanthanum salt in the solution A and stirring to obtain a solution B; taking the solution B as a reaction solution, taking carbon fiber cloth as a reaction substrate, putting in a polytetrafluoroethylene-lined stainless steel high-pressure hydrothermal reactor and performing hydrothermal reaction for 10-24 hours at a temperature of 150-180 DEG C; after the end of reaction, washing an obtained product with distilled water and absolute ethanol and then drying for 6-24 hours at a temperature of 60-80 DEG C to obtain the cerium and lanthanum double-doped titanium dioxide nano rod light catalyst. According to the preparation method disclosed by the invention, various rare earth ions can be successfully doped in a crystal lattice made of a titanium dioxide nano rod material, are dispersed on the surface of the material and inside the material and are high in dispersibility in a titanium dioxide nano rod, and the product has stronger stability. The preparation method of the material is simple and low in cost and can be applied to the field of photocatalysis.
Description
Technical field
The invention belongs to nano composite material preparing technical field is and in particular to a kind of cerium, lanthanum codope titanium dioxide are received
Rice rod photo-catalyst and preparation and application.
Background technology
In the research field of catalysis material, being continually striving to researchers, increasing semiconductor light is urged
Change material to be reported, such as TiO2, the metal oxide semiconductor nano material such as ZnO.And wherein with to titanium dioxide nano material
Research pay close attention to the most, be because the excellent performance of nano titanium oxide, there is the characteristics such as specific surface area is big, diffusibility is high, quilt
It is widely used in the fields such as sensing, catalysis, photoelectricity.Nanometer titanic oxide material, as the active high, selectivity of photocatalyst
Good, high hydroxyl radical free radical yield, can excite in wider energy spectrum, acid and alkali-resistance, there is biochemistry inertia, to environment and
The advantages of human body has no side effect, becomes with low cost, thus be widely studied.TiO2It is a kind of n-type semiconductor, sharp under room temperature
Titanium ore type TiO2Band gap width be about 3.2 eV, can band wider, can only be right using accounting for the ultraviolet light that solar energy is less than 5%
The utilization rate of sunlight is relatively low, and therefore, study hotspot is just fallen efficiently utilize sunlight how improving by people.
Usually right to improve its catalysis activity, people for strengthening the internal electric charge transfer and granular boundary between of photocatalyst
TiO2Optionally it is surface-treated.For improving TiO2Photocatalytic activity, to TiO2It is a kind of for carrying out selectivity impurity
Common method.Research shows, has the rare earth element of special 4f electronic structure, itself has polymorphic, strong adsorptivity, stability
High the features such as, and the doping of appropriate rare earth ion can effectively improve TiO2Semiconductor property, rare earth ion can be replaced
TiO2In Ti so that TiO2Expand its spectral response range to sunlight under not reducing ultraviolet light while activity, from
And its utilization rate to visible ray can be improved.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of cerium, lanthanum codope titanium dioxide nano-rod
Photocatalyst and preparation method.
Another object of the present invention is：The application of described catalyst is provided.
Combined with hydro-thermal method using original position double dope method, doping cerium, two kinds of elements of lanthanum in nano-titanium oxide material, from
And obtain cerium, lanthanum codope titanium dioxide nano-rod material.Comprise the following steps that：
A kind of cerium, the preparation method of lanthanum codope titanium dioxide nano-rod photo-catalyst are it is characterised in that the concrete step of the method
Suddenly it is：
（1）By butyl titanate TBOT or tetraisopropyl titanate TIPO, 37 wt% hydrochloric acid HCl and water H2O three mixes, and stirs
To uniform clarification precursor liquid A；
（2）Add cerium salt, lanthanum salt, stirring in above-mentioned solution A, obtain homogeneous solution B；
（3）By step（2）In the solution B that obtains as reaction solution, and using carbon cloth as reactive group bottom, insert polytetrafluoro
In the rustless steel high-pressure hydrothermal reaction kettle of vinyl liner, hydro-thermal reaction 10～24 hours at 150 DEG C～180 DEG C；
（4）After reaction terminates, then the product obtaining distilled water, absolute ethanol washing are dried 6 at 60 DEG C～80 DEG C
～24 hours, that is, obtain cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst.
Titanium source, hydrochloric acid HCl（37 wt%）And water H2The volume ratio of O three is 1:15~60:30~100.
Step（2）Described in the addition of rare earth cerous nitrate and step（1）In titanium source, the mol ratio of titanium is Ce3+:Ti4+=
1:50~600.
Step（3）Described in the addition of rare earth Lanthanum (III) nitrate and step（1）In titanium source, the mol ratio of titanium is La3+:Ti4+=
1:60~600.
A kind of cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst are it is characterised in that prepare according to any of the above-described methods described
Obtain.
A kind of cerium, application in terms of catalysis for the lanthanum codope titanium dioxide nano-rod photo-catalyst.
The present invention has following advantage：
Multiple rare earth ions successfully can be entrained in the lattice of titanium dioxide nano-rod material for this preparation method, be scattered in material
The surface of material and inside, dispersibility in titanium dioxide nano-rod for the rare earth ion is high, and product has compared with stiff stability.This material
Preparation method simple, cost price is cheap, can be applicable to photocatalysis field.
Specific embodiment
The present invention is described in detail by following instantiation, but protection scope of the present invention is not only restricted to these in fact
Apply example.
Embodiment 1：
（1）By 1 ml butyl titanate TBOT, 20 ml hydrochloric acid HCl（37 wt%）With 60 ml water H2O mixes, stirring obtains all
Even clarification precursor liquid A；
（2）0.002 g cerium salt, 0.017 g lanthanum salt is added in above-mentioned solution A, stirring, obtain homogeneous solution B；
（3）Using the solution B obtaining in step 2 as reaction solution, and using carbon cloth as reactive group bottom, insert polytetrafluoroethyl-ne
In the rustless steel high-pressure hydrothermal reaction kettle of alkene lining, hydro-thermal reaction 24 hours at 150 DEG C；
（4）After reaction terminates, then the product obtaining distilled water, absolute ethanol washing are dried 24 hours at 60 DEG C,
Obtain cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst.
Embodiment 2：
（1）By 1.5 ml tetraisopropyl titanate TIPO, 22.5 ml hydrochloric acid HCl（37 wt%）And 90 ml water H2O three mixes, and stirs
Mix and uniformly clarified precursor liquid A；
（2）0.043 g cerium salt, 0.036 g lanthanum salt is added in above-mentioned solution A, stirring, obtain homogeneous solution B；
（3）Using the solution B obtaining in step 2 as reaction solution, and using carbon cloth as reactive group bottom, insert polytetrafluoroethyl-ne
In the rustless steel high-pressure hydrothermal reaction kettle of alkene lining, hydro-thermal reaction 10 hours at 180 DEG C；
（4）After reaction terminates, by the product obtaining distilled water, absolute ethanol washing, at 80 DEG C, then it is dried 6 hours, that is,
Obtain cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst.
Embodiment 3：
（1）By 1.2 ml butyl titanate TBOT, 36 ml hydrochloric acid HCl（37 wt%）With 84 ml water H2O three mixes, and stirs
To uniform clarification precursor liquid A；
（2）0.004 g cerium salt, 0.003 g lanthanum salt is added in above-mentioned solution A, stirring, obtain homogeneous solution B；
（3）Using the solution B obtaining in step 2 as reaction solution, and using carbon cloth as reactive group bottom, insert polytetrafluoroethyl-ne
In the rustless steel high-pressure hydrothermal reaction kettle of alkene lining, hydro-thermal reaction 18 hours at 160 DEG C；
（4）After reaction terminates, then the product obtaining distilled water, absolute ethanol washing are dried 12 hours at 70 DEG C,
Obtain cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst.
Claims (6)
1. a kind of cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst preparation method it is characterised in that the method concrete
Step is：
（1）By butyl titanate TBOT or tetraisopropyl titanate TIPO, 37 wt% hydrochloric acid HCl and water H2O three mixes, and stirs
To uniform clarification precursor liquid A；
（2）Add cerium salt, lanthanum salt, stirring in above-mentioned solution A, obtain homogeneous solution B；
（3）By step（2）In the solution B that obtains as reaction solution, and using carbon cloth as reactive group bottom, insert polytetrafluoro
In the rustless steel high-pressure hydrothermal reaction kettle of vinyl liner, hydro-thermal reaction 10～24 hours at 150 DEG C～180 DEG C；
（4）After reaction terminates, then the product obtaining distilled water, absolute ethanol washing are dried 6 at 60 DEG C～80 DEG C
～24 hours, that is, obtain cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst.
2. a kind of cerium according to claim 1, the preparation method of lanthanum codope titanium dioxide nano-rod photo-catalyst, its
It is characterised by：Titanium source, hydrochloric acid HCl（37 wt%）And water H2The volume ratio of O three is 1:15~60:30~100.
3. a kind of cerium according to claim 1, the preparation method of lanthanum codope titanium dioxide nano-rod photo-catalyst, it is special
Levy and be：Step（2）Described in the addition of rare earth cerous nitrate and step（1）In titanium source, the mol ratio of titanium is Ce3+:Ti4+=
1:50~600.
4. a kind of cerium according to claim 1, the preparation method of lanthanum codope titanium dioxide nano-rod photo-catalyst, it is special
Levy and be：Step（3）Described in the addition of rare earth Lanthanum (III) nitrate and step（1）In titanium source, the mol ratio of titanium is La3+:Ti4+=
1:60~600.
5. a kind of cerium, lanthanum codope titanium dioxide nano-rod photo-catalyst are it is characterised in that according to the arbitrary institute of claim 1-4
The method of stating prepares.
6. cerium, application in terms of catalysis for the lanthanum codope titanium dioxide nano-rod photo-catalyst according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610979220.2A CN106423136A (en) | 2016-11-08 | 2016-11-08 | Cerium and lanthanum double-doped titanium dioxide nano rod light catalyst, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610979220.2A CN106423136A (en) | 2016-11-08 | 2016-11-08 | Cerium and lanthanum double-doped titanium dioxide nano rod light catalyst, and preparation method and application thereof |
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Family
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| CN201610979220.2A Pending CN106423136A (en) | 2016-11-08 | 2016-11-08 | Cerium and lanthanum double-doped titanium dioxide nano rod light catalyst, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331808A (en) * | 2018-11-27 | 2019-02-15 | 黄冈师范学院 | A kind of microwave synthesis method of lanthanum/nano titania compound photochemical catalyst |
| CN109865511A (en) * | 2017-12-04 | 2019-06-11 | 天津发洋环保科技有限公司 | A kind of preparation method of doped nano photo-catalytic emulsion |
| CN112023938A (en) * | 2020-07-28 | 2020-12-04 | 南京航空航天大学 | Bimetallic ion doped nano composite photocatalyst and preparation method thereof |
| CN115518637A (en) * | 2022-11-02 | 2022-12-27 | 中国科学院长春应用化学研究所 | Preparation method of precious metal composite catalyst and application of catalytic oxidation of formaldehyde at room temperature |
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| CN109331808A (en) * | 2018-11-27 | 2019-02-15 | 黄冈师范学院 | A kind of microwave synthesis method of lanthanum/nano titania compound photochemical catalyst |
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| CN115518637A (en) * | 2022-11-02 | 2022-12-27 | 中国科学院长春应用化学研究所 | Preparation method of precious metal composite catalyst and application of catalytic oxidation of formaldehyde at room temperature |
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