CN111841529A - Rare earth doped flaky Tb/Bi2WO6Nano material and preparation method and application thereof - Google Patents
Rare earth doped flaky Tb/Bi2WO6Nano material and preparation method and application thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 48
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title description 5
- 239000002086 nanomaterial Substances 0.000 claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- 150000001621 bismuth Chemical class 0.000 claims abstract description 11
- 150000001217 Terbium Chemical class 0.000 claims abstract description 10
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 105
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 238000003756 stirring Methods 0.000 claims description 68
- 230000007935 neutral effect Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000000926 separation method Methods 0.000 abstract description 12
- 239000000969 carrier Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000007788 liquid Substances 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 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 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a rare earth doped flaky Tb/Bi2WO6The nano material is prepared by mixing terbium salt, bismuth salt and tungstate, and the rare earth doped flaky Tb/Bi2WO6The nano material is in a sheet shape, so that the surface appearance of the photocatalyst is improved, the contact area between the photocatalyst and a target pollutant is enlarged, and the photocatalytic performance is improved. The invention also discloses a preparation method thereof, which is to prepare Bi by using the bismuth salt and the tungstate2WO6Then in Bi2WO6Doped into Tb unitThe element is reacted by a hydrothermal synthesis method to obtain the final rare earth doped flaky Tb/Bi2WO6And (3) nano materials. The invention also discloses the rare earth doped flaky Tb/Bi2WO6Application of nano material as photocatalyst in pollutant treatment, doping of Tb on Bi2WO6The photocatalytic activity of the rare earth doped Tb has a great influence, the separation efficiency of photon-generated carriers is enhanced, and the separation of photon-generated electrons and holes is effectively promoted, so that the photocatalytic performance is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to rare earth doped flaky Tb/Bi2WO6A nano material and a preparation method and application thereof.
Background
In recent years, with the rapid development of economic level, the industrialization level is accelerated, the living standard of people is obviously improved, and meanwhile, a series of environmental problems are inevitably generated, wherein the problem of organic pollution in water is particularly serious, and people are increasingly concerned about cleanly and efficiently treating the environmental problems. The photocatalysis technology has the advantages of low cost, wide application range, effective utilization of sunlight, small secondary pollution and the like, is widely applied and researched in recent years, and solves the environmental problem of living which puzzles human beings for a long time to a certain extent.
The doping of rare earth elements is widely applied to the field of semiconductor material photocatalytic property modification, great research progress is achieved, but the defects of low separation efficiency of photon-generated carriers and thick lamella exist, and at present, rare earth Tb is used for doping and modifying Bi2WO6The study of (2) is still blank.
Disclosure of Invention
One of the objects of the present invention is to provide a rare earth doped sheet Tb/Bi2WO6The nano material has high separation efficiency of photon-generated carriers and thinner lamella.
The second object of the present invention is to provide a rare earth doped sheet Tb/Bi2WO6The preparation method and the preparation process of the nano material are simpleAnd (3) the method is simple and easy to popularize.
It is another object of the present invention to provide a rare earth doped lamellar Tb/Bi2WO6The application of the nano material as a photocatalyst.
The invention is realized by the following technical scheme:
rare earth doped flaky Tb/Bi2WO6The preparation method of the nano material comprises the following steps:
(1) adding bismuth salt into a solvent, and uniformly stirring to form a solution A;
adding tungstate into deionized water, and uniformly stirring to form a solution B; wherein the ratio of the bismuth salt to the tungstate is (1-4) to 1;
dropwise adding the solution B into the solution A to obtain a mixed solution, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
(2) then dropwise adding terbium salt into the neutral solution to form a total reaction system; wherein the addition amount of the terbium salt accounts for 0.1 to 5 percent of the total reaction system;
(3) carrying out hydrothermal synthesis reaction on the total reaction system, wherein the reaction temperature is 120-180 ℃, and the reaction time is 6-12 h;
(4) after the reaction, naturally cooling to room temperature, pouring out the supernatant, collecting the solid precipitate, filtering, washing and drying to obtain the rare earth doped flaky Tb/Bi2WO6And (3) nano materials.
Further, in the step (1), HNO is adopted as a solvent3The molar concentration is 1 mol/L.
Further, in the step (1), the two solutions were stirred for 30 min.
Further, in the step (2), terbium salt is added and then stirred for 1-2 hours.
Further, in the step (4), the drying temperature is 60-80 ℃, and the drying time is 10 hours.
Further, terbium salt is terbium nitrate.
Further, bismuth nitrate is used as the bismuth salt.
Further, sodium tungstate is used as the tungstate.
The invention also discloses the preparation methodPrepared rare earth doped flaky Tb/Bi2WO6Nano material, said rare earth doped type sheet Tb/Bi2WO6The nano-material is in the form of a flake.
The invention also discloses the rare earth doped flaky Tb/Bi2WO6The application of the nano material as a photocatalyst in the aspect of pollutant treatment.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a rare earth doped flaky Tb/Bi2WO6A nano-class material is prepared from Bi salt and tungstate2WO6Then in Bi2WO6Doping Tb, reacting by hydrothermal synthesis to obtain final rare earth doped sheet Tb/Bi2WO6And (3) nano materials. The preparation process is simple and easy to popularize. Bi derived from bismuth salts and tungstates2WO6The nano material has excellent photocatalytic performance due to the unique two-dimensional layered structure and proper forbidden band width, and has the advantages of high photocatalytic performance and high photocatalytic performance of the traditional photocatalyst TiO2Compared with the prior art, the photocatalyst has higher photocatalytic efficiency and visible light utilization rate; from XRD (X-ray diffraction) pattern, the rare earth doped flaky Tb/Bi of the invention2WO6The diffraction peak of the nanomaterial is slightly shifted to the right (high diffraction angle direction) because a part of Tb atoms enter Bi2WO6Crystal lattice, resulting in the formation of defects in the original crystal structure and the formation of a new solid solution structure, Tb3 +Ionic radius less than Bi3+Ionic radius, therefore Tb3+Ionic substitution of Bi in the original lattice3+The distance between crystal planes after ions becomes small, the diffraction angle becomes large, and the phenomenon of shifting to a high diffraction angle direction appears in an XRD spectrogram. However, in this experiment, the doping amount of Tb is small, so that no characteristic diffraction peak of Tb appears in the XRD spectrum. The separation efficiency of photoproduction electrons and holes can be improved, and meanwhile, the introduction of terbium can play a role in refining grains, so that the lamella is thinned, and the photocatalysis effect is improved. Rare earth element Tb Bi due to its unfilled f-orbital2WO6Quilt lightElectrons generated by excitation can be captured by the rare earth element Tb, so that separation of photo-generated electrons and holes is promoted, the rare earth element Tb is doped with the semiconductor photocatalyst, and the effect of grain refinement can also be achieved, so that the original sheet structure of the photocatalyst is thinner, the surface morphology of the photocatalyst can be improved, the contact area between the photocatalyst and target pollutants is enlarged, the photocatalytic performance is further improved, and the defects of low separation efficiency of photo-generated carriers and thicker sheets are overcome.
The rare earth doped flaky Tb/Bi prepared by the invention2WO6The nano photocatalyst has higher photocatalytic degradation capability to methyl orange under visible light, and doping of visible Tb can be used for Bi2WO6The photocatalytic activity of the rare earth doped Tb has a great influence, the separation efficiency of photon-generated carriers is enhanced, and the separation of photon-generated electrons and holes is effectively promoted, so that the photocatalytic performance is improved. From the aspect of morphology, the rare earth doping refines crystal grains, so that the sheet shape is thin, the contact area between the rare earth doping and target pollutants is increased, and the photocatalytic performance is further improved.
Drawings
FIG. 1 shows doped sheet Tb/Bi according to example 2 of the present invention2WO6Photocatalyst and pure Bi2WO6XRD spectrum of (1);
FIG. 2 shows doped sheet Tb/Bi according to example 2 of the present invention2WO6Photocatalyst and pure Bi2WO6XRD partial enlargement of (1);
FIG. 3 shows pure Bi flakes of example 2 of the present invention2WO6SEM image of photocatalyst;
FIG. 4 shows doped sheet Tb/Bi according to example 2 of the present invention2WO6SEM image of photocatalyst;
FIG. 5 shows doped sheet Tb/Bi according to example 2 of the present invention2WO6A spectrum of the photocatalyst;
FIG. 6 shows pure Bi2WO6Doped sheet Tb/Bi of the invention example 22WO6Degradation of photocatalyst to methyl orange is compared with graph.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a rare earth doped flaky Tb/Bi2WO6The nano material is prepared by mixing terbium salt, bismuth salt and tungstate, and the rare earth doped flaky Tb/Bi2WO6The nano-material is in the form of a flake.
Specifically, Tb (NO) is used as terbium salt3)3·6H2O。
The bismuth salt is Bi (NO)3)3·5H2O。
The tungstate is Na2WO4·2H2O。
The present invention will be described in further detail with reference to specific embodiments below:
example 1
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 1.86mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 0.91mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution; the pH was adjusted to neutral in order to maintain the platelet morphology of the sample.
2) Then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 2
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.00mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 3
1) Taking 40mL of 1mol/L HNO at room temperature3Adding 2.06 mmoleBi (NO) into the beaker3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.06mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL reaction kettle with a stainless lining, sealing, and then putting the reaction kettle into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 4
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 0.1 percent of the total mole fraction of the reaction system, and the mixture is continuously stirred vigorously for 1-2 hours;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 5
1) Taking 40mL of 1mol/L HNO at room temperature3Adding 2.0mmol Bi (NO) into the beaker3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 0.2 percent of the total mole fraction of the reaction system, and the mixture is continuously stirred vigorously for 1-2 hours;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 6
1) Taking 40mL of 1mol/L HNO at room temperature3Adding 2.0mmol Bi (NO) into the beaker3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 2% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 7
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 5% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 8
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 120 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 9
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO6·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 140 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 10
1) Taking 40mL of 1mol/L HNO at room temperature3Adding 2.0mmol Bi (NO) into the beaker3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 10 hours at 180 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 11
1) Taking 40mL of 1mol/L HNO at room temperature3Adding 2.0mmol Bi (NO) into the beaker3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 6h at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 12
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 8 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
Example 13
1) Taking 40mL of 1mol/L HNO at room temperature3In a beaker, 2.0mmol of Bi (NO) was added3)3·5H2Continuously stirring for 30min until a transparent solution A is formed; another 30mL of deionized water was placed in a beaker, and 1.0mmol of Na was added2WO4·2H2Continuously stirring to form a transparent solution B;
dropwise adding the solution B into the solution A, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
2) then, continuously and vigorously stirring the neutral solution for 2-3 h, and dropwise adding Tb (NO)3)3·6H2O, forming a total reaction system; wherein Tb (NO)3)3·6H2The adding amount of O accounts for 1% of the total mole fraction of the reaction system, and stirring for 1-2 h continuously and vigorously;
3) stopping stirring, transferring the obtained solution into a 40mL stainless steel lining reaction kettle, sealing, and then putting into an oven to react for 12 hours at 160 ℃;
4) and naturally cooling the reaction kettle to room temperature, pouring out liquid in the reaction kettle, collecting solid precipitate, washing with deionized water and ethanol for 3 times respectively, and drying at 60 ℃ for 10 hours to obtain a sample.
As shown in FIGS. 1-2, the diffraction peak of the sample is slightly shifted to the right (in the direction of high diffraction angle) because some Tb atoms enter Bi2WO6Crystal lattice, resulting in the formation of defects in the original crystal structure and the formation of a new solid solution structure, Tb3+The ionic radius (0.092nm) is less than Bi3+Ionic radius (0.103nm), hence Tb3+Ionic substitution of Bi in the original lattice3+Rear crystal face of ionThe distance is reduced, the diffraction angle is increased, and the phenomenon of deviation towards the direction of high diffraction angle appears in the XRD spectrogram. However, in this experiment, the doping amount of Tb is small, so that no characteristic diffraction peak of Tb appears in the XRD spectrum. The separation efficiency of photo-generated electrons and holes can be improved, and meanwhile, as shown in 3-4, the introduction of terbium can play a role in refining grains, so that the lamella is thinned, and the photocatalysis effect is improved.
As shown in figure 5, an EDS diagram of a terbium-doped sample shows that terbium element is successfully doped into a bismuth tungstate crystal lattice, and the doped composite photocatalyst is successfully prepared by combining figure 1.
The invention degrades methyl orange by simulation to rare earth doped flaky Tb/Bi2WO6The photocatalytic performance of the nano material is researched, and the rare earth doped flaky Tb/Bi prepared in the embodiments 1-13 of the invention2WO6And pure Bi2WO6Putting the mixture into methyl orange solution, respectively measuring the absorbance of the mixture, and calculating the degradation rate of the methyl orange to obtain the rare earth doped flaky Tb/Bi prepared by the invention as shown in Table 12WO6The degradation rate of the nano material to methyl orange can reach 82 percent at most (see figure 6), and pure Bi2WO6The degradation rate of methyl orange is only 45 percent, and the doping of Tb on Bi can be seen2WO6The photocatalytic activity of the rare earth doped Tb has a great influence, the separation efficiency of photon-generated carriers is enhanced, and the separation of photon-generated electrons and holes is effectively promoted, so that the photocatalytic performance is improved. From the aspect of morphology, the rare earth doping refines crystal grains, so that the sheet shape is thin, the contact area between the rare earth doping and target pollutants is increased, and the photocatalytic performance is further improved.
TABLE 1 degradation rate of methyl orange by samples prepared in each example
Claims (10)
1. Rare earth doped flaky Tb/Bi2WO6A method for preparing a nanomaterial, comprisingThe following steps:
(1) adding bismuth salt into a solvent, and uniformly stirring to form a solution A;
adding tungstate into deionized water, and uniformly stirring to form a solution B; wherein the ratio of the bismuth salt to the tungstate is (1-4) to 1;
dropwise adding the solution B into the solution A to obtain a mixed solution, and adjusting the pH value of the mixed solution to 7 to obtain a neutral solution;
(2) then dropwise adding terbium salt into the neutral solution to form a total reaction system; wherein the addition amount of the terbium salt accounts for 0.1 to 5 percent of the total reaction system;
(3) carrying out hydrothermal synthesis reaction on the total reaction system, wherein the reaction temperature is 120-180 ℃, and the reaction time is 6-12 h;
(4) after the reaction, naturally cooling to room temperature, pouring out the supernatant, collecting the solid precipitate, filtering, washing and drying to obtain the rare earth doped flaky Tb/Bi2WO6And (3) nano materials.
2. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that in the step (1), HNO is adopted as a solvent3The molar concentration is 1 mol/L.
3. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that in the step (1), the stirring time of the two solutions is 30 min.
4. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that in the step (2), terbium salt is added and then stirred for 1-2 hours.
5. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that in the step (4), the drying temperature is 60-80 ℃, and the drying time is 10 hours.
6. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that terbium nitrate is adopted as terbium salt.
7. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that bismuth salt adopts bismuth nitrate.
8. The rare earth doped sheet Tb/Bi of claim 12WO6The preparation method of the nano material is characterized in that sodium tungstate is adopted as tungstate.
9. Rare earth doped flaky Tb/Bi prepared by adopting preparation method of any one of claims 1 to 82WO6Nanomaterial characterized in that the rare earth doped flaky Tb/Bi2WO6The nano-material is in the form of a flake.
10. The rare earth doped platelet Tb/Bi of claim 92WO6The application of the nano material as a photocatalyst in the aspect of pollutant treatment.
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