CN112337471A - Photocatalysis nano material capable of being magnetically separated and preparation method thereof - Google Patents
Photocatalysis nano material capable of being magnetically separated and preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 145
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 title claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000010410 layer Substances 0.000 claims abstract description 105
- 239000012792 core layer Substances 0.000 claims abstract description 47
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 30
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002127 nanobelt Substances 0.000 claims description 100
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims description 90
- 239000002074 nanoribbon Substances 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 51
- 238000009987 spinning Methods 0.000 claims description 41
- 230000003197 catalytic effect Effects 0.000 claims description 34
- 239000011550 stock solution Substances 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 238000010041 electrostatic spinning Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 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 claims description 8
- 238000001523 electrospinning Methods 0.000 claims description 5
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 7
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 14
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 12
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 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 8
- 229940012189 methyl orange Drugs 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a magnetically separable photocatalytic nano material and a preparation method thereof2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is CeO2、Bi2MoO6、Bi2WO6At least one of (1). The nano material takes a magnetic substance as a core layer, the surface of the core layer is coated with a first photocatalytic shell layer and a second photocatalytic shell layer, the material has photocatalytic performance, and can be separated and recovered through an external magnetic field, so that the material is convenient to recycle, and the secondary pollution to water is reduced. By selecting the raw materials of the nuclear layer material, the first photocatalytic layer and the second photocatalytic layer, the photocatalyst which has the advantages of high nuclear layer resistivity, good magnetic spectrum characteristic, high magnetic response intensity, easy recovery, good photocatalytic performance of the photocatalytic layer and capability of effectively reducing organic pollutants in sewage is obtained. The preparation method has simple process and mild conditions, and the prepared nano material has high magnetic response intensity and photocatalytic efficiency.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a magnetically separable photocatalytic nano material and a preparation method thereof.
Background
With the development of society, the treatment of environmental pollution and water pollution is more and more emphasized, and as a semiconductor photocatalytic material which can directly utilize sunlight to carry out photocatalytic degradation on pollutants, the semiconductor photocatalytic material can degrade organic pollutants into nontoxic carbon dioxide and water without causing secondary pollution, so that the semiconductor photocatalytic material gradually receives wide attention.
TiO2The photocatalytic nano material is a semiconductor photocatalytic nano material with excellent performance, in order to improve the photoelectric characteristic and obtain a photocatalyst with high-efficiency photocatalytic performance, researchers apply TiO to2The photocatalytic nano material is continuously improved, and the photocatalytic performance is improved through the modes of shape regulation, precious metal modification, transition metal doping, nonmetal doping and the like. The construction of the surface heterostructure is most effective for improving the photocatalytic performance of the semiconductorThe method combines all the advantages of the second phase nano material and the matrix material on the surface of the nano structure, expands the photoresponse range of the photocatalyst, promotes the separation of photo-generated charges and improves the photocatalytic efficiency. Thus, the TiO is constructed2The research on the surface heterostructure of the photocatalytic nano material has important significance.
Conventional TiO-containing2The powdery photocatalyst has the problems of difficult separation and recovery in the sewage treatment process, the photocatalyst which can not be recovered has adverse effect on the environment, the product can not be recycled, and the treatment cost is higher.
Disclosure of Invention
Therefore, the technical problems to be solved by the invention are that the traditional photocatalyst is not easy to recover in the sewage treatment process, pollutes the environment and has high use cost, so that the invention provides a recyclable and recyclable magnetic-separation photocatalytic nano material and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a magnetically separable photocatalytic nano material, which comprises a magnetic core layer, a first photocatalytic shell layer coated on the surface of the magnetic core layer, and a second photocatalytic shell layer coated on the surface of the first photocatalytic shell layer, wherein the magnetic core layer is CoFe2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is CeO2、Bi2MoO6、Bi2WO6At least one of (1).
Preferably, the magnetic core layer is CoFe2O4The first catalytic shell layer is made of CoFe2O4TiO with coaxial nanoribbons2The second catalytic shell layer is made of CoFe2O4Nanobelt, TiO2The nano-belt is coaxial with the photocatalysis nano-belt.
Preferably, the thickness of the nano material is 100-200nm, and the width is 2-6 μm; the CoFe2O4Nanobelt and the TiO2The mass ratio of the nano-belt is 1:1-5, soThe above TiO2The mass ratio of the nanobelts to the photocatalytic nanobelts is 1: 1-4.
In another aspect, the present invention provides a method for preparing the magnetically separable photocatalytic nanomaterial, comprising the steps of:
s1, preparing a magnetic core layer @ first photocatalytic shell layer coaxial nanobelt by an electrostatic spinning method;
s2, growing a second photocatalytic shell layer nanobelt on the surface of the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt by a hydrothermal method, namely the magnetic core layer @ first photocatalytic shell layer @ second photocatalytic shell layer coaxial nanobelt;
s3, roasting the coaxial nanobelts obtained in the step S2 to obtain the magnetically separable photocatalytic nanomaterial.
Preferably, the step S1 of preparing the magnetic core layer @ first photocatalytic shell layer coaxial nanoribbon by the electrospinning method includes:
s11, mixing Co (NO)3)2And Fe (NO)3)3Preparing a nuclear layer spinning solution according to a proportion;
s12, preparing tetrabutyl titanate into a first shell spinning solution;
s13, carrying out electrostatic spinning on the core layer spinning solution and the first shell layer spinning solution, and roasting at 500 ℃ for 3h to obtain the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt.
Preferably, the step S2 of preparing the magnetic core layer @ first photocatalytic shell layer @ second catalytic shell layer coaxial nanoribbon by a hydrothermal method includes:
s21, preparing a second catalytic shell stock solution;
s22, carrying out hydrothermal reaction on the second catalytic shell stock solution and the magnetic core layer @ first photocatalytic shell coaxial nanobelt to obtain the magnetic core layer @ first photocatalytic shell @ second catalytic shell coaxial nanobelt.
Preferably, step S21 is:
adding Ce (NO)3)3Dissolving the solution in deionized water, and reacting with NaOH to obtain a second catalytic shell stock solution;
alternatively, the step S21 is:
mixing Na2WO4And Bi (NO)3)3Dissolving the two components in deionized water to obtain a second catalytic shell stock solution;
alternatively, the step S21 is:
mixing Na2MoO4And Bi (NO)3)3And dissolving the two components in deionized water to obtain a second catalytic shell stock solution.
Preferably, in the step S3, the roasting temperature is 500 ℃ and the roasting time is 3 hours during the roasting process.
Preferably, in step S22, the reaction temperature during the hydrothermal reaction is 180 ℃ and the reaction time is 8-12 h.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the magnetically separable photocatalytic nanomaterial comprises a magnetic core layer, a first photocatalytic shell layer coated on the surface of the magnetic core layer, and a second photocatalytic shell layer coated on the surface of the first photocatalytic shell layer, wherein the magnetic core layer is CoFe2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is CeO2、Bi2MoO6、Bi2WO6At least one of (1). The nano material takes a magnetic substance as a core layer, the surface of the core layer is coated with a first photocatalytic shell layer and a second photocatalytic shell layer, the material has photocatalytic performance, can be separated and recovered through an external magnetic field, is convenient to recycle through magnetic recovery, and reduces environmental pollution. Through the selection of the raw materials of the nuclear layer material, the first photocatalytic layer and the second photocatalytic layer, the nuclear layer has high resistivity, good magnetic spectrum characteristics and high magnetic response intensity, is easier to recover, has good photocatalytic performance, and can effectively reduce organic pollutants in sewage.
(2) The magnetic core layer of the magnetically separable photocatalytic nanomaterial is CoFe2O4The first catalytic shell layer is made of CoFe2O4TiO with coaxial nanoribbons2The second catalytic shell layer is made of CoFe2O4Nanobelt, TiO2The nano-belt is coaxial with the photocatalysis nano-belt. Compared with the conventional nanoparticles, the one-dimensional nano material not only has almost all typical characteristics of the nanoparticles, but also has a large width-thickness ratio, is beneficial to the transfer of photoproduction electrons, reduces the extinction rate of the electrons, can effectively improve the catalytic efficiency of photochemical reaction, and is not easy to agglomerate, so that the photocatalytic nano material prepared from the nanobelts has excellent photocatalytic performance and high recycling rate.
(3) The method for preparing the magnetically separable photocatalytic nanomaterial comprises the steps of preparing the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt by an electrostatic spinning method, preparing a second photocatalytic shell layer on the surface of the first photocatalytic shell layer by a hydrothermal method, and finally roasting to obtain the magnetically separable photocatalytic nanomaterial. The method has the advantages of simple process and mild conditions, and the prepared nano material has high magnetic response intensity and photocatalytic efficiency.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is CoFe described in example 1 of the present invention2O4@TiO2@CeO2XRD spectrum of coaxial nanobelt;
FIG. 2 is CoFe described in example 2 of the present invention2O4@TiO2@Bi2WO6XRD spectrum of coaxial nanobelt;
FIG. 3 is CoFe described in example 1 of the present invention2O4@TiO2@CeO2Degradation curve of the coaxial nanobelts to rhodamine B;
FIG. 4 is CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@CeO2Comparing the photocatalytic degradation effect of the coaxial nanobelts with a test chart;
FIG. 5 is CoFe2O4@TiO2@CeO2Coaxial nanoribbon circulationThe ring uses a curve of 3 degradation rates as a function of illumination time;
FIG. 6 is CoFe described in example 2 of the present invention2O4@TiO2@Bi2WO6Degradation curve of the coaxial nanobelts to rhodamine B;
FIG. 7 is CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2WO6Comparing the photocatalytic degradation effect of the coaxial nanobelts with a test chart;
FIG. 8 is CoFe2O4@TiO2@Bi2WO6The degradation rate of the coaxial nanobelts is changed along with the illumination time after being recycled;
FIG. 9 is CoFe described in example 3 of the present invention2O4@TiO2@Bi2MoO6A degradation curve of the coaxial nanobelts to methyl orange;
FIG. 10 is CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2MoO6Comparing the photocatalytic degradation effect of the coaxial nanobelts with a test chart;
FIG. 11 is CoFe2O4@TiO2@Bi2MoO6The degradation rate of the coaxial nanobelts is changed along with the illumination time after being recycled;
FIG. 12 is CoFe2O4@TiO2@CeO2A hysteresis loop of the coaxial nanoribbon at room temperature;
FIG. 13 is CoFe2O4@TiO2@Bi2WO6A hysteresis loop of the coaxial nanoribbon at room temperature;
FIG. 14 is CoFe2O4@TiO2@Bi2MoO6Hysteresis loop of coaxial nanoribbon at room temperature.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a magnetically separable photocatalytic nanomaterial, which comprises a magnetic core layer, a first photocatalytic shell layer coated on the surface of the magnetic core layer, and a second photocatalytic shell layer coated on the surface of the first photocatalytic shell layer, wherein the magnetic core layer is CoFe2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is CeO2。
Specifically, the magnetic core layer is CoFe2O4The first photocatalytic shell layer is made of CoFe2O4TiO with coaxial nanoribbons2The second photocatalytic shell layer is made of CoFe2O4Nanobelt, TiO2Nano-belt coaxial CeO2A nanoribbon. The photocatalytic nanomaterial finally formed is a 3-layer nanoribbon structure with the thickness of 100nm and the width of 2 μm. The CoFe2O4Nanobelt and the TiO2The mass ratio of the nano-belts is 1:1, and the CeO2Nanobelt and the TiO2The mass ratio of the nanobelts was also 1: 1.
The embodiment also provides a method for preparing the magnetically separable photocatalytic nanomaterial, which comprises the following steps:
s1 preparation of CoFe by electrospinning method2O4Magnetic core layer @ TiO2The first photocatalytic shell layer is coaxial with the nanobelt.
S2 hydrothermal method on CoFe2O4Magnetic core layer @ TiO2CeO grows on the coaxial nanobelt of the first photocatalytic shell2Second oneCatalytic shell to obtain i.e. CoFe2O4Magnetic core layer @ TiO2First photocatalytic shell @ CeO2The second catalytic shell layer is coaxial with the nanobelt.
S3, roasting the coaxial nanobelts obtained in the step S2 to obtain the magnetically separable photocatalytic nanomaterial.
Specifically, the step S1 includes:
s11, mixing Co (NO)3)2And Fe (NO)3)3Preparing the core layer spinning solution according to the proportion.
In this example, Co (NO) was added in a molar ratio of 1:23)2And Fe (NO)3)3Uniformly mixing the solution to obtain a core layer spinning solution with certain viscosity, and adding a template agent polyvinylpyrrolidone (PVP) into the core layer spinning solution, wherein Co (NO) is contained in the core layer spinning solution3)2And Fe (NO)3)3The mass percent of the template agent is 10 percent, and the mass percent of the template agent in the nuclear layer spinning solution is 16-20 percent.
S12, taking tetrabutyl titanate (TBOT) as a raw material, adding the tetrabutyl titanate (TBOT) into a mixed solution of ethanol and DMF to prepare a first shell spinning solution, and adding a template agent PVP with the mass percent of 18-22% into the first shell spinning solution.
S13, carrying out electrostatic spinning on the core layer spinning solution and the first shell layer spinning solution to obtain the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt.
Specifically, a nuclear layer spinning solution and a first shell layer spinning solution are placed in a coaxial electrostatic spinning device, the voltage is adjusted to be 12KV, the solidification distance is 16cm, and { PVP/[ Fe (NO) is obtained on a receiving device3)3+Co(NO3)2]}@[PVP/TBOT]Coaxial nanoribbons. Then keeping the temperature at 500 ℃ for 3h to obtain CoFe2O4@TiO2Coaxial nanoribbons.
The step S2 specifically includes the following steps:
s21, preparing a second catalytic shell stock solution: taking proper amount of Ce (NO)3)3Dissolving in deionized water, adding appropriate amount of NaOH, and precipitating to obtain second catalystAnd (4) shell layer stock solution.
S22, adding the CoFe into the stock solution of the second catalytic shell2O4@TiO2Coaxial nano belt, ultrasonic dispersing for 10min, and placing in a hydrothermal reaction kettle. Putting into a baking oven, and keeping the temperature at 180 ℃ for 8 h.
The step S3 is to bake the sample at 500 ℃ for 3h to obtain magnetically separable CoFe2O4@TiO2@CeO2Coaxial nanoribbons.
Example 2
The embodiment provides a magnetically separable photocatalytic nanomaterial, which comprises a magnetic core layer, a first photocatalytic shell layer coated on the surface of the magnetic core layer, and a second photocatalytic shell layer coated on the surface of the first photocatalytic shell layer, wherein the magnetic core layer is CoFe2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is Bi2WO6。
Specifically, the magnetic core layer is CoFe2O4The first photocatalytic shell layer is made of CoFe2O4TiO with coaxial nanoribbons2The second photocatalytic shell layer is made of CoFe2O4Nanobelt, TiO2Bi with coaxial nanoribbons2WO6A nanoribbon. The photocatalytic nanomaterial finally formed is a 3-layer nanoribbon structure with the thickness of 200nm and the width of 6 μm. The CoFe2O4Nanobelt and the TiO2The mass ratio of the nano belt is 1:1, and the TiO is2Nanobelt and the Bi2WO6The mass ratio of the nanobelts is 1: 4.
The embodiment also provides a method for preparing the magnetically separable photocatalytic nanomaterial, which comprises the following steps:
s1 preparation of CoFe by electrospinning method2O4Magnetic core layer @ TiO2The first photocatalytic shell layer is coaxial with the nanobelt.
S2 preparation of CoFe by hydrothermal method2O4Magnetic core layer @ TiO2First photocatalytic shell @ Bi2WO6The second catalytic shell layer is coaxial with the nanobelt.
S3, roasting the coaxial nanobelts obtained in the step S2 to obtain the magnetically separable photocatalytic nanomaterial.
Specifically, the step S1 includes:
s11, mixing Co (NO)3)2And Fe (NO)3)3Preparing the core layer spinning solution according to the proportion.
In this example, Co (NO) was added in a molar ratio of 1:23)2And Fe (NO)3)3Uniformly mixing the solution to obtain a core layer spinning solution with certain viscosity, and adding a template agent polyvinylpyrrolidone (PVP) into the core layer spinning solution, wherein Co (NO) is contained in the core layer spinning solution3)2And Fe (NO)3)3The mass percent of the template agent is 10 percent, and the mass percent of the template agent in the nuclear layer spinning solution is 18 percent.
S12, taking tetrabutyl titanate (TBOT) as a raw material, adding the tetrabutyl titanate (TBOT) into a mixed solution of ethanol and DMF to prepare a spinning solution with a first shell layer, and adding a template agent PVP with the mass percent of 20% into the spinning solution.
S13, carrying out electrostatic spinning on the core layer spinning solution and the first shell layer spinning solution to obtain the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt.
Specifically, a nuclear layer spinning solution and a first shell layer spinning solution are placed in a coaxial electrostatic spinning device, the voltage is adjusted to be 12KV, the solidification distance is 16cm, and { PVP/[ Fe (NO) is obtained on a receiving device3)3+Co(NO3)2]}@[PVP/TBOT]Coaxial nanoribbons. Then keeping the temperature at 500 ℃ for 3h to obtain CoFe2O4@TiO2Coaxial nanoribbons.
The step S2 specifically includes the following steps:
s21, preparing a second catalytic shell stock solution: taking a proper amount of Na2WO4And Bi (NO)3)3Dissolving in deionized water to obtain a second catalytic shell stock solution.
S22, adding the CoFe into the stock solution of the second catalytic shell2O4@TiO2Coaxial nano belt, ultrasonic dispersing for 10min, and placing in a hydrothermal reaction kettle. Putting into an oven, and keeping the temperature at 180 ℃ for 10 h.
The step S3 is to bake the sample at 500 ℃ for 3h to obtain magnetically separable CoFe2O4@TiO2@Bi2WO6Coaxial nanoribbons.
Example 3
The embodiment provides a magnetically separable photocatalytic nanomaterial, which comprises a magnetic core layer, a first photocatalytic shell layer coated on the surface of the magnetic core layer, and a second photocatalytic shell layer coated on the surface of the first photocatalytic shell layer, wherein the magnetic core layer is CoFe2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is Bi2MoO6。
Specifically, the magnetic core layer is CoFe2O4The first photocatalytic shell layer is made of CoFe2O4TiO with coaxial nanoribbons2The second photocatalytic shell layer is made of CoFe2O4Nanobelt, TiO2Bi with coaxial nanoribbons2MoO6A nanoribbon. The photocatalytic nanomaterial finally formed is a 3-layer nanoribbon structure with the thickness of 180nm and the width of 4 μm. The CoFe2O4Nanobelt and the TiO2The mass ratio of the nano belt is 1:1, and the TiO is2Nanobelt and the Bi2MoO6The mass ratio of the nanobelts is 1: 2.
The embodiment also provides a method for preparing the magnetically separable photocatalytic nanomaterial, which comprises the following steps:
s1 preparation of CoFe by electrospinning method2O4Magnetic core layer @ TiO2The first photocatalytic shell layer is coaxial with the nanobelt.
S2 preparation of CoFe by hydrothermal method2O4Magnetic core layer @ TiO2First photocatalytic shell @ Bi2MoO6The second catalytic shell layer is coaxial with the nanobelt.
S3, roasting the coaxial nanobelts obtained in the step S2 to obtain the magnetically separable photocatalytic nanomaterial.
Specifically, the step S1 includes:
s11, mixing Co (NO)3)2And Fe (NO)3)3Preparing the core layer spinning solution according to the proportion.
In this example, Co (NO) was added in a molar ratio of 1:23)2And Fe (NO)3)3Uniformly mixing the solution to obtain a core layer spinning solution with certain viscosity, and adding a template agent polyvinylpyrrolidone (PVP) into the core layer spinning solution, wherein Co (NO) is contained in the core layer spinning solution3)2And Fe (NO)3)3The mass percent of the template agent is 10 percent, and the mass percent of the template agent in the nuclear layer spinning solution is 18 percent.
S12, taking tetrabutyl titanate (TBOT) as a raw material, adding the tetrabutyl titanate (TBOT) into a mixed solution of ethanol and DMF to prepare a first shell spinning solution, and adding a template agent PVP with the mass percent of 20% into the first shell spinning solution.
S13, carrying out electrostatic spinning on the core layer spinning solution and the first shell layer spinning solution to obtain the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt.
Specifically, a nuclear layer spinning solution and a first shell layer spinning solution are placed in a coaxial electrostatic spinning device, the voltage is adjusted to be 12KV, the solidification distance is 16cm, and { PVP/[ Fe (NO) is obtained on a receiving device3)3+Co(NO3)2]}@[PVP/TBOT]Coaxial nanoribbons. Then keeping the temperature at 500 ℃ for 3h to obtain CoFe2O4@TiO2Coaxial nanoribbons.
The step S2 specifically includes the following steps:
s21, preparing a second catalytic shell stock solution: taking a proper amount of Na2MoO4And Bi (NO)3)3Dissolving in deionized water to obtain a second catalytic shell stock solution.
S22, adding the CoFe into the stock solution of the second catalytic shell2O4@TiO2Coaxial nano belt, ultrasonic dispersing for 10min, and placing in a hydrothermal reaction kettle. Put into an oven, 180Keeping the temperature for 12h at the temperature.
The step S3 is to bake the sample at 500 ℃ for 3h to obtain magnetically separable CoFe2O4@TiO2@Bi2MoO6Coaxial nanoribbons.
Examples of the experiments
1. X-ray diffraction (XRD) analysis
CoFe obtained in examples 1-2 was tested separately2O4@TiO2@CeO2Coaxial nanoribbon, CoFe2O4@TiO2@Bi2WO6The XRD spectrum of the coaxial nanobelt shows the test result as shown in the figure 1-2. The test results were specifically analyzed as follows:
FIG. 1 shows that the diffraction peak d values and relative intensities at 2 θ angles of 30.084 ° (220), 35.437 ° (311), 56.973 ° (511), 62.585 ° (440) and CoFe of the sample obtained in example 12O4The PDF standard cards (22-1086) of (A) are consistent, and have no diffraction peaks of other impurities. TiO 22Four main diffraction peaks (101), (004), (200) and (211) of (1), (004), and (211), and the d value and relative intensity and TiO2The PDF cards (21-1272) are matched with the value listed and belong to anatase type TiO2Is tetragonal system, space group is I41/amd, and CeO2The strongest peak (111) appeared at 2 q-28.588 °, the second strongest peak appeared at 47.555 ° (220), and distinct ceos also appeared at 33.129 ° (200), 56.429 ° (311), 59.181 ° (222), 76.829 ° (331), 79.210 ° (420), 88.586 ° (422)2Characteristic diffraction peak, with CeO2(PDF #34-0394, cubic, space group Fm-3m) substantially coincided. When analysis by XRD showed that magnetically separable CoFe was prepared in pure phase2O4@TiO2@CeO2Coaxial nanoribbons.
Fig. 2 shows that the sample obtained in example 2 shows distinct diffraction peaks at 2q ═ 28.10 °, 32.66 °, 49.96 °, 55.68 ° and 58.42 °, which are the (111), (200), (220), (311) and (222) crystal planes of orthorhombic bismuth tungstate, respectively, and the test result is consistent with orthorhombic Bi2WO6The diffraction peaks of the standard card (PDF #73-1126) are completely consistent, and the d values and the relative intensities of other diffraction peaks are equal toCoFe2O4PDF standard card (22-1086) and TiO2Consistent with the PDF card (21-1272). When analysis by XRD showed that pure phase CoFe had been prepared2O4@TiO2@Bi2WO6Coaxial nanoribbons.
2. Photocatalytic degradation test results
a. CoFe obtained in example 12O4@TiO2@CeO2The coaxial nanobelts are subjected to a photocatalytic degradation rhodamine B test, the test result is shown in figure 3, the photocatalytic degradation reaction is carried out under the irradiation of a 400W metal halogen lamp, and CoFe is subjected to2O4@TiO2@CeO2Coaxial nanoribbons added to rhodamine B (1X 10) -containing-5mol/L)，1mL H2O2(3% by mass) and 0.05g of nanofibers in suspension, it can be seen from FIG. 3 that after 90min of UV irradiation, CoFe2O4@TiO2@CeO2The degradation rate of the coaxial nanobelts to RB reaches 95.7 percent. With the prolonging of the degradation time, the maximum absorption wavelength is blue-shifted from 553nm to 520nm, which indicates that RB is subjected to structural change in the photocatalysis process, and an intermediate product rhodamine which is more difficult to degrade is probably generated.
Further, for comparison, for CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@CeO2And comparing and testing the photocatalytic degradation effects of the coaxial nanobelts under the same test conditions. The test results are shown in FIG. 4, CoFe when the UV light is irradiated for 90min2O4@TiO2The degradation rate of the coaxial nanobelts is 80.6 percent, and the CoFe2O4@TiO2@CeO2The degradation rate of the coaxial nanobelts to RB reaches 95.7 percent, which is caused by CoFe2O4@TiO2@CeO2The coaxial nanobelts form a heterostructure to promote the transfer of photo-generated electron holes, effectively reduce the recombination probability of the photo-generated electrons and the holes, and be beneficial to improving the photocatalytic activity, thereby improving the CoFe2O4@TiO2@CeO2Catalytic activity of coaxial nanoribbons.
FIG. 5 is CoFe2O4@TiO2@CeO2The degradation rate of the coaxial nanobelt after being recycled for 3 times changes along with the change of illumination time, and as can be seen from the graph, the degradation rates of the sample after being recycled for three times are respectively 95.7%, 94.2% and 93.6%, and the result shows that CoFe2O4@TiO2@CeO2The coaxial nanoribbon has good repeated utilization rate.
b. For CoFe obtained in example 22O4@TiO2@Bi2WO6The coaxial nanobelts were subjected to a photocatalytic degradation rhodamine B test, and the test results are shown in fig. 6. The photocatalytic degradation reaction is carried out under the irradiation of a 400W metal halide lamp. The test suspension comprised 0.03g of coaxial nanoribbons and organic dye solution to which was added 1mL of 3% H2O2. The suspension was stirred in the dark for 30min, and the organic dye and the catalyst surface reached equilibrium of adsorption-desorption. FIG. 6 shows the application of rhodamine B solution in CoFe2O4@TiO2@Bi2WO6The absorption curve and degradation rate of the coaxial nanobelt under photocatalysis change with illumination time. As can be seen from FIG. 6, the maximum absorption peak of the rhodamine B solution is gradually reduced and the degradation rate is gradually increased along with the extension of the ultraviolet light irradiation time under the catalytic action. When the illumination time is 120min, CoFe2O4@TiO2@Bi2WO6The degradation rate of the coaxial nanobelts on rhodamine B is 97.5%.
Further, for comparison, for CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2WO6And comparing and testing the photocatalytic degradation effects of the coaxial nanobelts under the same test conditions. FIG. 7 is CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2WO6Degradation contrast graph of coaxial nanobelts, illumination time of 120min, CoFe2O4@TiO2@Bi2WO6The degradation rate of the coaxial nanobelts on rhodamine B is 97.5 percent, which is superior to CoFe2O4@TiO2The degradation rate of the coaxial nanobelts on rhodamine is 86.4%. CoFe2O4@TiO2@Bi2WO6Coaxial nanoribbon ratio CoFe2O4@TiO2The coaxial nanobelts show higher photocatalytic activity to rhodamine. TiO 22And Bi2WO6Are all semiconductor oxides, due to TiO when irradiated by ultraviolet light2The forbidden band width is small, and electrons firstly pass through TiO2The valence band of (2) is transited to the conduction band due to TiO2And Bi2WO6Has different forbidden band widths and energy level distributions, and electrons are formed by TiO2Conduction band transfer to Bi2WO6Conduction band of from Bi2WO6Valence band transfer to TiO2In the valence band of (A) to make TiO2The surface hole concentration is increased and the photocatalytic activity is improved.
FIG. 8 is CoFe2O4@TiO2@Bi2WO6The degradation rates of the coaxial nanobelts after being recycled are respectively 97.5%, 94.4% and 91.4% along with the change of the illumination time, and the results show that the degradation rates of the samples after being recycled are 97.5%, 94.4% and 91.4%, respectively2O4@TiO2@Bi2WO6The coaxial nanoribbon has good repeated utilization rate.
c. CoFe obtained in example 32O4@TiO2@Bi2MoO6The coaxial nanobelts were subjected to the photocatalytic degradation methyl orange test, and the test results are shown in fig. 9. The photocatalytic degradation reaction is carried out under the irradiation of a 400W metal halide lamp. The test suspension comprised 0.03g of coaxial nanoribbons and organic dye solution to which was added 1mL of 3% H2O2. The suspension was stirred in the dark for 30min, and the organic dye and the catalyst surface reached equilibrium of adsorption-desorption. FIG. 9 is a solution of methyl orange in CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2MoO6The absorption curve and degradation rate of the coaxial nanobelt under photocatalysis change with illumination time. As can be seen from fig. 9, the maximum absorption peak of the methyl orange solution gradually decreases and the degradation rate gradually increases with the increase of the uv irradiation time under the catalytic action. Light (es)At illumination time of 80min, CoFe2O4@TiO2@Bi2MoO6The degradation rate of the coaxial nanobelts on methyl orange is 96.3%.
Further, for comparison, for CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2MoO6The photocatalytic degradation effect of the coaxial nanobelts is compared and tested, and CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2MoO6The coaxial nanobelt degradation methyl orange experiments were performed as described above. FIG. 10 is CoFe2O4@TiO2Coaxial nanoribbons and CoFe2O4@TiO2@Bi2MoO6Degradation contrast graph of coaxial nanobelts, illumination time of 80min, CoFe2O4@TiO2@Bi2MoO6The degradation rate of the coaxial nanobelts on methyl orange is 96.3 percent, which is superior to CoFe2O4@TiO2The degradation rate of the coaxial nanobelts on methyl orange is 85.3%. CoFe2O4@TiO2@Bi2MoO6Coaxial nanoribbon ratio CoFe2O4@TiO2The coaxial nanoribbon shows higher photocatalytic activity to methyl orange. Bi2MoO6And TiO2Are all semiconductor oxides, due to TiO when irradiated by ultraviolet light2The forbidden band width is small, and electrons firstly pass through TiO2The valence band of (B) is transited to the conduction band due to Bi2MoO6And TiO2Has different forbidden band widths and energy level distributions, and electrons are formed by TiO2Conduction band transfer to Bi2MoO6Conduction band of from Bi2MoO6Valence band transfer to TiO2In the valence band of (A) to make TiO2The surface hole concentration is increased and the photocatalytic activity is improved.
FIG. 11 is CoFe2O4@TiO2@Bi2MoO6The curve of the degradation rate of the coaxial nanobelt photocatalyst after being recycled and changed along with the illumination time is shown in the figure, and the degradation rate of the sample after being recycled and used for three times is shown inIn contrast, 96.3%, 92.3%, 91.4%, the results showed CoFe2O4@TiO2@Bi2MoO6The coaxial nanoribbon has good repeated utilization rate.
3. Magnetic assay
FIG. 12 is CoFe2O4@TiO2@CeO2Magnetic hysteresis loop of coaxial nanoribbon at room temperature, the magnetism of the sample is derived from magnetic CoFe of the nuclear layer2O4CoFe in unit mass sample2O4The content of (b) determines the magnitude of its saturation magnetization. CoFe2O4@TiO2@CeO2The saturation magnetization of the coaxial nanoribbon is 25.6emu g-1. Based on the experimental results, the magnetically separable CoFe with good photocatalytic performance is obtained by combining the coaxial electrostatic spinning technology with a hydrothermal method2O4@TiO2@CeO2Coaxial nanoribbons.
FIG. 13 is CoFe2O4@TiO2@Bi2WO6The magnetic hysteresis loop of the coaxial nanoribbon at room temperature, the magnetism of the sample is derived from the magnetic CoFe of the core layer2O4CoFe in unit mass sample2O4The content of (b) determines the magnitude of its saturation magnetization. For CoFe2O4@TiO2@Bi2WO6The saturation magnetization of the coaxial nanoribbon is 23.6emu g-1. Based on the experimental results, the magnetically separable CoFe with good photocatalytic performance is obtained by combining the coaxial electrostatic spinning technology with a hydrothermal method2O4@TiO2@Bi2WO6Coaxial nanoribbons.
FIG. 14 is CoFe2O4@TiO2@Bi2MoO6The magnetic hysteresis loop of the coaxial nanoribbon at room temperature, the magnetism of the sample is derived from the magnetic CoFe of the core layer2O4CoFe in unit mass sample2O4The content of (b) determines the magnitude of its saturation magnetization. For CoFe2O4@TiO2@Bi2MoO6The saturation magnetization of the coaxial nanoribbons is 21.5emug-1Based on the experimental results, the magnetically separable CoFe with good photocatalytic performance is obtained by combining the coaxial electrostatic spinning technology and the hydrothermal method2O4@TiO2@Bi2MoO6Coaxial nanoribbons.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. The magnetically separable photocatalytic nanomaterial is characterized by comprising a magnetic core layer, a first photocatalytic shell layer coated on the surface of the magnetic core layer, and a second photocatalytic shell layer coated on the surface of the first photocatalytic shell layer, wherein the magnetic core layer is CoFe2O4The first photocatalytic shell layer is TiO2The second photocatalytic shell layer is CeO2、Bi2MoO6、Bi2WO6At least one of (1).
2. The magnetically separable photocatalytic nanomaterial of claim 1, wherein the magnetic core layer is CoFe2O4The first catalytic shell layer is made of CoFe2O4TiO with coaxial nanoribbons2The second catalytic shell layer is made of CoFe2O4Nanobelt, TiO2The nano-belt is coaxial with the photocatalysis nano-belt.
3. The magnetically separable photocatalytic nanomaterial as claimed in claim 2, wherein the nanomaterial has a thickness of 100-200nm and a width of 2-6 μm; the CoFe2O4Nanobelt and the TiO2The mass ratio of the nano belt is 1:1-5, and the TiO is2Nano beltThe mass ratio of the nano-belt to the photocatalytic nano-belt is 1: 1-4.
4. A method for preparing a magnetically separable photocatalytic nanomaterial as defined in any one of claims 1 to 3, comprising the steps of:
s1, preparing a magnetic core layer @ first photocatalytic shell layer coaxial nanobelt by an electrostatic spinning method;
s2, growing a second photocatalytic shell layer coaxial nanoribbon on the magnetic core layer @ first photocatalytic shell layer coaxial nanoribbon through a hydrothermal method to obtain the magnetic core layer @ first photocatalytic shell layer @ second photocatalytic shell layer coaxial nanoribbon;
s3, roasting the coaxial nanobelts obtained in the step S2 to obtain the magnetically separable photocatalytic nanomaterial.
5. The method for preparing the magnetic core layer-first photocatalytic shell layer coaxial nanoribbon by the electrospinning method according to claim 4, wherein the step S1 comprises:
s11, mixing Co (NO)3)2And Fe (NO)3)3Preparing a nuclear layer spinning solution according to a proportion;
s12, preparing tetrabutyl titanate into a first shell spinning solution;
s13, carrying out electrostatic spinning on the core layer spinning solution and the first shell layer spinning solution to obtain the magnetic core layer @ first photocatalytic shell layer coaxial nanobelt.
6. The preparation method of claim 5, wherein the step S2 is to prepare the magnetic core layer @ first photocatalytic shell layer @ second catalytic shell layer coaxial nanoribbon by a hydrothermal method, and the preparation method comprises:
s21, preparing a second catalytic shell stock solution;
s22, carrying out hydrothermal reaction on the second catalytic shell stock solution and the magnetic core layer @ first photocatalytic shell coaxial nanobelt to obtain the magnetic core layer @ first photocatalytic shell @ second catalytic shell coaxial nanobelt.
7. The method according to claim 6, wherein the step S21 is:
adding Ce (NO)3)3Dissolving the solution in deionized water, and reacting with NaOH to obtain a second catalytic shell stock solution;
alternatively, the step S21 is:
mixing Na2WO4And Bi (NO)3)3Dissolving the two components in deionized water to obtain a second catalytic shell stock solution;
alternatively, the step S21 is:
mixing Na2MoO4And Bi (NO)3)3And dissolving the two components in deionized water to obtain a second catalytic shell stock solution.
8. The preparation method of claim 7, wherein in the step S3, the roasting temperature is 500 ℃ and the roasting time is 3 h.
9. The preparation method according to claim 8, wherein in the step S22, the reaction temperature in the hydrothermal reaction process is 180 ℃ and the reaction time is 8-12 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387395A (en) * | 2021-05-19 | 2021-09-14 | 中国科学院上海硅酸盐研究所 | Efficient magnetic response catalytic medical nano-particle and preparation method and application thereof |
| CN116532084A (en) * | 2023-04-28 | 2023-08-04 | 淮安兴淮消防设备有限公司 | Nd-doped Bi 2 WO 6 Preparation and application of nanoflower-biomass porous carbon material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016102997A1 (en) * | 2014-12-23 | 2016-06-30 | Essilor International (Compagnie Generale D'optique) | A continuous flow process for manufacturing surface modified metal oxide nanoparticles by supercritical solvothermal synthesis |
| CN109957857A (en) * | 2017-12-14 | 2019-07-02 | 吉林建筑大学 | One kind can Magneto separate photocatalysis coaxial nanoribbon and its preparation process |
| CN111215119A (en) * | 2020-03-05 | 2020-06-02 | 浙江大学 | Preparation method of surface dispersion type nano bismuth molybdate composite photocatalytic material |
-
2020
- 2020-11-13 CN CN202011267444.3A patent/CN112337471A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016102997A1 (en) * | 2014-12-23 | 2016-06-30 | Essilor International (Compagnie Generale D'optique) | A continuous flow process for manufacturing surface modified metal oxide nanoparticles by supercritical solvothermal synthesis |
| CN109957857A (en) * | 2017-12-14 | 2019-07-02 | 吉林建筑大学 | One kind can Magneto separate photocatalysis coaxial nanoribbon and its preparation process |
| CN111215119A (en) * | 2020-03-05 | 2020-06-02 | 浙江大学 | Preparation method of surface dispersion type nano bismuth molybdate composite photocatalytic material |
Non-Patent Citations (1)
| Title |
|---|
| TIEPING CAO: "Three-dimensional hierarchical CeO2 nanowalls/TiO2 nanofibers heterostructure and its high photocatalytic performance", 《J SOL-GEL SCI TECHNOL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387395A (en) * | 2021-05-19 | 2021-09-14 | 中国科学院上海硅酸盐研究所 | Efficient magnetic response catalytic medical nano-particle and preparation method and application thereof |
| CN113387395B (en) * | 2021-05-19 | 2022-07-12 | 中国科学院上海硅酸盐研究所 | Efficient magnetic response catalytic medical nano-particle and preparation method and application thereof |
| CN116532084A (en) * | 2023-04-28 | 2023-08-04 | 淮安兴淮消防设备有限公司 | Nd-doped Bi 2 WO 6 Preparation and application of nanoflower-biomass porous carbon material |
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