CN113019381B - Three-dimensional porous self-supporting NiO/ZnO heterojunction material and preparation method thereof - Google Patents
Three-dimensional porous self-supporting NiO/ZnO heterojunction material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000007710 freezing Methods 0.000 claims abstract description 18
- 230000008014 freezing Effects 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 13
- 229940078494 nickel acetate Drugs 0.000 claims description 13
- 239000004246 zinc acetate Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 2
- 239000002149 hierarchical pore Substances 0.000 claims 4
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 247
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- 239000011787 zinc oxide Substances 0.000 description 123
- 239000000243 solution Substances 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
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- 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 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
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- B01J35/657—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
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Abstract
The invention relates to the technical field of porous materials, and provides a three-dimensional porous self-supporting NiO/ZnO heterojunction material and a preparation method thereof. The method comprises the steps of freezing a precursor solution containing a high molecular polymer, a nickel source, a zinc source and water to freeze the water in the solution into ice crystals, removing the ice crystals by ice-removing treatment to form macroporous channels, removing the high molecular polymer by calcining to form micropores and mesopores, decomposing the nickel source into NiO and the zinc source into ZnO by calcining, and forming macropores by stacking NiO particles and ZnO particles to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material. The embodiment shows that the preparation method provided by the invention is simple to operate, does not need to remove a template, and does not need to strictly control experimental conditions.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a three-dimensional porous self-supporting NiO/ZnO heterojunction material and a preparation method thereof.
Background
Untreated urban domestic water, agricultural sewage, industrial sewage and the like are discharged into rivers, so that water eutrophication or heavy metal exceeding can be caused, further, a large amount of bacteria in water are propagated, aquatic organisms are killed, and the ecological system is seriously influenced. The semiconductor photocatalysis technology is used as a safe, efficient and low-cost water pollution treatment method, and has wide application prospect in solving the problem of water pollution. The principle of semiconductor photocatalysis technology for treating water pollution is that reduction and oxidation capability of photon-generated carriers are mainly utilized, and the photo-generated carriers react with oxygen or water molecules at the interface of a catalyst and a water phase to generate active groups with strong oxidizing property and reducing property, so that pollutants or heavy metal ions in water are degraded or reduced. Among many semiconductor catalyst materials, nickel oxide (NiO) and zinc oxide (ZnO) are widely used as photocatalysts because of their low cost and high chemical stability. However, as ZnO and NiO are direct band gap semiconductors with wide forbidden bands, the recombination efficiency of electrons and holes is high, the light absorption range is narrow, and the photocatalytic efficiency is seriously influenced.
Semiconductor theory states that when two different types of semiconductors come into contact with each other, a heterojunction is formed at the interface, and the diffusion and drift motion of carriers causes the material to establish a stable built-in electric field at the interface. When a heterojunction is excited by light with energy higher than its band gap energy, the non-equilibrium carriers will be rapidly transferred under the modulation of the built-in electric field. The NiO/ZnO heterojunction has a typical II-type heterojunction energy band structure, so that the NiO/ZnO heterojunction can effectively prevent the ineffective recombination of photogenerated electrons and holes, and the high photocatalytic efficiency is obtained. In addition, the microstructure of the semiconductor catalyst also greatly influences the photocatalytic activity. The semiconductor photocatalyst with the porous structure has higher specific surface area and permeability, so that the semiconductor photocatalyst has more reaction active sites and rapid mass transfer channels, and the performance of the semiconductor photocatalyst is improved. At present, the method for preparing the porous semiconductor photocatalyst mainly comprises a template method and a self-assembly method. However, the template method usually requires a complex template removing process, and the self-assembly method requires strict control of experimental conditions, which is not suitable for large-scale popularization and application. Therefore, it is necessary to develop a method for preparing the porous NiO/ZnO heterojunction material with simple operation.
Disclosure of Invention
The preparation method provided by the invention is simple to operate, a template is not required to be removed, experimental conditions are not required to be strictly controlled, and the prepared three-dimensional porous self-supporting NiO/ZnO heterojunction material has excellent photocatalytic performance.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a three-dimensional porous self-supporting NiO/ZnO heterojunction material, which comprises the following steps:
(1) mixing a high molecular polymer, a nickel source, a zinc source and water to obtain a precursor solution;
(2) sequentially freezing and deicing the precursor solution obtained in the step (1) to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor;
(3) and (3) calcining the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor obtained in the step (2) to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material.
Preferably, the mass concentration of the high molecular polymer in the precursor solution in the step (1) is 2-8%, the mass concentration of the nickel source is 0.7-1.0%, and the mass concentration of the zinc source is 0.4-0.7%.
Preferably, the high molecular polymer in step (1) comprises polyvinylpyrrolidone or polyvinyl alcohol; the nickel source comprises nickel acetate or nickel nitrate; the zinc source comprises zinc acetate or zinc nitrate.
Preferably, the temperature of the freezing treatment in the step (2) is below-196 ℃, and the time of the freezing treatment is 10-15 min.
Preferably, the temperature of the deicing treatment in the step (2) is-70 to-50 ℃, and the time of the deicing treatment is 24 to 48 hours.
Preferably, the vacuum degree of the deicing treatment in the step (2) is 10-30 Pa.
Preferably, the calcining temperature in the step (3) is 500-550 ℃.
Preferably, the heating rate of heating to the calcining temperature is 1-2.5 ℃/min.
The invention also provides the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared by the preparation method in the technical scheme, wherein the three-dimensional porous NiO/ZnO heterojunction material has a multi-level pore structure, and the multi-level pores comprise macropores, mesopores and micropores.
Preferably, the aperture of the micropores is 0.5-2 nm, the aperture of the mesopores is 2-50 nm, and the aperture of the macropores is 50 nm-10 μm.
The invention provides a preparation method of a three-dimensional porous self-supporting NiO/ZnO heterojunction material, which comprises the following steps: mixing a high molecular polymer, a nickel source, a zinc source and water to obtain a precursor solution; sequentially freezing and deicing the precursor solution to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor; and calcining the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material. The method comprises the steps of freezing a precursor solution containing a high molecular polymer, a nickel source, a zinc source and water to freeze the water in the solution into ice crystals, removing the ice crystals by ice-removing treatment to form macroporous channels, removing the high molecular polymer by calcining to form micropores and mesopores, decomposing the nickel source into NiO and the zinc source into ZnO by calcining, and forming macropores by stacking NiO particles and ZnO particles to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material. The embodiment shows that the preparation method provided by the invention is simple to operate, does not need to remove a template, and does not need to strictly control experimental conditions.
In addition, the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared by the method has excellent photocatalytic performance.
Drawings
FIG. 1 is a process flow diagram for preparing a three-dimensional porous self-supporting NiO/ZnO heterojunction material according to example 1 of the invention;
FIG. 2 is an SEM image of a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor and a three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention, and the inset is an SEM image of the three-dimensional porous self-supporting NiO/ZnO heterojunction material;
FIG. 3 is an SEM image of the side of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2 of the invention, and the inset is an SEM image of a cross section of the three-dimensional porous self-supporting NiO/ZnO heterojunction material;
FIG. 4 is an SEM image of the side of a three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 3 of the invention, and the inset is an SEM image of a cross section of the three-dimensional porous self-supporting NiO/ZnO heterojunction material;
FIG. 5 is an X-ray diffraction analysis plot of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention, NiO prepared in comparative example 1, and ZnO prepared in comparative example 2;
FIG. 6 is an X-ray electron energy spectrum of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention, NiO prepared in comparative example 1 and ZnO prepared in comparative example 2;
FIG. 7 is an X-ray electron energy spectrum of Zn 2p of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention and the ZnO prepared in comparative example 2;
FIG. 8 is an X-ray electron energy spectrum of Ni 2p of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention and NiO prepared in comparative example 1;
FIG. 9 is a nitrogen adsorption and desorption curve of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention;
FIG. 10 is a BET pore size distribution diagram of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention;
FIG. 11 is a distribution diagram of the pore diameter obtained by mercury intrusion test on the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention;
FIG. 12 is a graph of the photocatalytic performance of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention, NiO prepared in comparative example 1, and ZnO prepared in comparative example 2;
FIG. 13 is a first order kinetic line fit plot of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 of the invention, NiO prepared in comparative example 1, and ZnO degraded methyl orange prepared in comparative example 2;
FIG. 14 is a graph showing the photocatalytic performance of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2 of the present invention and the powdered NiO/ZnO heterojunction material prepared in comparative example 3;
FIG. 15 is a first order kinetic linear fit graph of degradation of rhodamine B by the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2 of the invention and the powdered NiO/ZnO material prepared in comparative example 3.
Detailed Description
The invention provides a preparation method of a three-dimensional porous self-supporting NiO/ZnO heterojunction material, which comprises the following steps:
(1) mixing a high molecular polymer, a nickel source, a zinc source and water to obtain a precursor solution;
(2) sequentially freezing and deicing the precursor solution obtained in the step (1) to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor;
(3) and (3) calcining the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor obtained in the step (2) to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material.
The invention mixes high molecular polymer, nickel source, zinc source and water to obtain precursor solution. The operation of mixing the high molecular polymer, the nickel source, the zinc source and the water is not particularly limited, and the technical scheme of solid-liquid mixing, which is well known to those skilled in the art, can be adopted. In the present invention, the mixing of the high molecular polymer, the nickel source, the zinc source and the water is preferably performed under stirring. In the invention, the stirring speed is preferably 500-600 r/min, and more preferably 550-600 r/min; the stirring time is preferably 10-15 h, and more preferably 12-14 h; the stirring temperature is preferably room temperature; the stirring mode is preferably magnetic stirring.
In the present invention, the high molecular polymer preferably includes polyvinylpyrrolidone or polyvinyl alcohol, and more preferably polyvinylpyrrolidone. The source of the high molecular polymer is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the invention, the high molecular polymer can hinder the self-aggregation of the nickel source and the zinc source, promote the formation of heterojunction, and can also hinder the transverse growth of ice crystal, and the high molecular polymer can be used as a framework for forming a pore channel structure.
In the invention, the mass concentration of the high molecular polymer in the precursor solution is preferably 2-8%, and more preferably 4-8%. According to the invention, the mass concentration of the high molecular polymer in the precursor solution is preferably controlled within the above range, and the collapse of the pore channel can be caused due to the over-high mass concentration of the high molecular polymer, so that the porous morphology can not be maintained, and the pore channel structure can not be formed due to the over-low concentration, so that the prepared material has the morphology of particle accumulation.
In the present invention, the nickel source preferably comprises nickel acetate or nickel nitrate, more preferably nickel acetate. The source of the nickel source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the mass concentration of the nickel source in the precursor solution is preferably 0.7-1.0%, and more preferably 0.74-0.99%. The invention preferably controls the mass concentration of the nickel source in the precursor solution within the above range, the concentration of the nickel source influences the mechanical strength of the material, and the higher the concentration is, the higher the hardness is, but the higher the concentration is, the photocatalytic performance of the material is influenced.
In the present invention, the zinc source preferably includes zinc acetate or zinc nitrate, more preferably zinc acetate. The source of the zinc source is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the mass concentration of the zinc source in the precursor solution is preferably 0.4-0.7%, and more preferably 0.44-0.65%. In the invention, the mass concentration of the zinc source in the precursor solution is preferably controlled within the range, the concentration of the zinc source influences the mechanical strength of the material, and the higher the concentration is, the higher the hardness is, but the higher the concentration is, the photocatalytic performance of the material is influenced.
In the present invention, the water is preferably deionized water.
After the precursor solution is obtained, the precursor solution is sequentially subjected to freezing treatment and deicing treatment to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor. The invention carries out freezing treatment on a precursor solution containing a high molecular polymer, a nickel source, a zinc source and water to freeze the water in the solution into ice crystals, and then removes the ice crystals through the freezing treatment to form macropores.
In the present invention, the temperature of the freezing treatment is preferably-196 ℃ or lower. In the present invention, the freezing treatment is preferably performed in liquid nitrogen. In the present invention, the time for the freezing treatment is preferably 10 to 15min, and more preferably 10 to 12 min. In the invention, the precursor solution is preferably frozen at the temperature, so that water in the precursor solution can be instantly frozen into ice crystals, and the ice crystals are removed by deicing treatment to form macropores.
After the freezing treatment is finished, the invention carries out deicing treatment on the frozen product to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor. The operation of the de-icing treatment is not particularly limited, and the ice crystals in the product can be removed. In the present invention, the deicing treatment is preferably freeze-drying. In the present invention, the temperature of the freeze-drying is preferably-70 to-50 ℃, more preferably-70 ℃; the freeze drying time is preferably 24-48 h, and more preferably 48 h. The invention preferably controls the temperature of the freeze drying in the range, so that the ice crystals can be directly sublimated and can not be melted into water, and the porous structure of the material can be favorably maintained. In the present invention, the freeze-drying device is preferably a vacuum freeze-dryer.
In the invention, the vacuum degree of the deicing treatment is preferably 10-30 Pa, and more preferably 20-30 Pa. The invention preferably controls the vacuum degree of the deicing treatment in the above range, the vacuum degree is too low, the sublimation rate of ice crystals is slow, and at the moment, the material itself may melt due to heat absorption, which is not beneficial to maintaining the porous structure of the material; and too high vacuum degree affects heat transfer, and the sublimation rate of ice crystals is slowed down, so that the maintenance of the porous structure of the material is affected.
After the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor is obtained, the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor is calcined to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material. According to the invention, the high molecular polymer is removed through calcination, so that micropores and mesopores are formed, meanwhile, the nickel source is decomposed into NiO and the zinc source is decomposed into ZnO through calcination, and the accumulation of NiO particles and ZnO particles can also form macropores.
In the invention, the calcination temperature is preferably 500-550 ℃, and more preferably 550 ℃. In the invention, the heating rate of heating to the calcination temperature is preferably 1-2.5 ℃/min, and more preferably 2.5 ℃/min. The present invention preferably controls the calcination temperature within the above range to facilitate the complete removal of the high molecular polymer; and the excessive calcination temperature can enlarge the particles forming the pore wall, reduce the specific surface area of the material and finally influence the photocatalytic performance of the material. In the present invention, the calcination apparatus is preferably a muffle furnace.
After the temperature is raised to the calcining temperature, the invention preferably keeps the temperature at the calcining temperature to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material. In the invention, the heat preservation time is preferably 1-5 h, and more preferably 2-3 h. The present invention preferably maintains the temperature for a period of time to completely remove the high molecular weight polymer while improving the crystallinity of the material.
The invention freezes the precursor solution containing high molecular polymer, nickel source, zinc source and water to freeze the water in the solution into ice crystal, removes the ice crystal to form macropores through ice treatment, removes the high molecular polymer to form micropores and mesopores through calcination, decomposes the nickel source into NiO through calcination, decomposes the zinc source into ZnO, and also forms macropores through the accumulation of NiO particles and ZnO particles, thereby obtaining the three-dimensional porous self-supporting NiO/ZnO heterojunction material with macropores, mesopores and micropores.
The invention also provides the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared by the preparation method in the technical scheme, wherein the three-dimensional porous NiO/ZnO heterojunction material has a multi-level pore structure, and the multi-level pores comprise macropores, mesopores and micropores. In the invention, the micropores and the mesopores are left by removing the high molecular polymer by calcining, the specific surface area of the material can be greatly improved, a large number of reaction sites are provided for the photocatalytic reaction, and the macropores are pore channel structures left after deicing and pore structures formed by stacking particles, so that the mass transfer efficiency of reactants can be obviously improved, and the efficiency of the photocatalytic reaction is further improved.
In the invention, the aperture of the micropore is preferably 0.5-2 nm, and more preferably 1-2 nm; the aperture of the mesopores is preferably 2-50 nm, and more preferably 5-50 nm; the pore diameter of the macropores is preferably 50nm to 10 μm, more preferably 100nm to 10 μm.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Dissolving 0.372g of nickel acetate, 0.328g of zinc acetate and 4g of polyvinylpyrrolidone in 50mL of deionized water, and magnetically stirring at 600r/min at room temperature for 12h to obtain a precursor solution (the mass concentration of polyvinylpyrrolidone, nickel acetate and zinc acetate in the precursor solution are respectively 8%, 0.74% and 0.65%);
injecting the precursor solution into a centrifuge tube, vertically immersing the centrifuge tube into liquid nitrogen at the temperature of-196 ℃ at the speed of 1cm/s, keeping the centrifuge tube for 10min, removing a sealing cover of the centrifuge tube, placing the centrifuge tube into a vacuum freeze dryer, and drying the centrifuge tube for 48h under the conditions that the vacuum degree is 20Pa and the temperature is-70 ℃ to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor;
and (3) placing the precursor of the three-dimensional porous self-supporting NiO/ZnO heterojunction material in a muffle furnace, then raising the calcination temperature from room temperature to 550 ℃ according to the heating rate of 2.5 ℃/min, then preserving the temperature for 2h, and then naturally cooling to room temperature to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material (marked as NiO/ZnO-1) with macropores, mesopores and micropores. Wherein the aperture of the macropores is 7 mu m, the aperture of the mesopores is 48nm, and the aperture of the micropores is 1 nm.
Application example 1
The three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 is used for photocatalytic degradation of methyl orange, and a 50W ultraviolet lamp is used as a light source. 30mg of NiO/ZnO-1 prepared in example 1 was added to 30mL of a 10ppm methyl orange solution, and adsorbed in the dark for 30min to reach an adsorption-desorption equilibrium, after which the mixed solution was placed under an ultraviolet lamp, 2mL of the solution was taken out every 15min, and the absorbance of the solution at 463nm was measured using a UH4150 spectrophotometer, and the results are shown in FIG. 12.
Example 2
Dissolving 0.496g of nickel acetate, 0.219g of zinc acetate and 4g of polyvinylpyrrolidone in 50mL of deionized water, and magnetically stirring at 600r/min at room temperature for 12h to obtain a precursor solution (the mass concentration of polyvinylpyrrolidone in the precursor solution is 8%, the mass concentration of nickel acetate is 0.99%, and the mass concentration of zinc acetate is 0.44%);
injecting the precursor solution into a centrifuge tube, vertically immersing the centrifuge tube into liquid nitrogen at the temperature of-196 ℃ at the speed of 1cm/s, keeping the temperature for 10min, removing a sealing cover of the centrifuge tube, placing the centrifuge tube into a vacuum freeze dryer, and drying the centrifuge tube for 48h under the conditions that the vacuum degree is 20Pa and the temperature is-70 ℃ to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor;
and (3) placing the precursor of the three-dimensional porous self-supporting NiO/ZnO heterojunction material in a muffle furnace, raising the calcination temperature from room temperature to 550 ℃ according to the heating rate of 2.5 ℃/min, then preserving the temperature for 2h, and then naturally cooling to room temperature to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material (marked as NiO/ZnO-2) with macropores, mesopores and micropores. Wherein the aperture of the macropores is 6 mu m, the aperture of the mesopores is 48nm, and the aperture of the micropores is 1 nm.
Application example 2
The three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in the example 2 is used for photocatalytic degradation of rhodamine B, and a 50W ultraviolet lamp is used as a light source. 30mg of NiO/ZnO-2 prepared in example 2 was added to 30mL of 10ppm rhodamine B solution, and adsorbed in the dark for 30min to attain adsorption-desorption equilibrium, after which the mixed solution was placed under an ultraviolet lamp, 2mL of the solution was taken out every 15min, and the absorbance of the solution at 553nm was measured with a UH4150 spectrophotometer, the results of which are shown in FIG. 14.
Example 3
Dissolving 0.496g of nickel acetate, 0.219g of zinc acetate and 2g of polyvinylpyrrolidone in 50mL of deionized water, and magnetically stirring at 600r/min at room temperature for 12h to obtain a precursor solution (the mass concentration of polyvinylpyrrolidone in the precursor solution is 4%, the mass concentration of nickel acetate is 0.99%, and the mass concentration of zinc acetate is 0.44%);
injecting the precursor solution into a centrifuge tube, vertically immersing the centrifuge tube into liquid nitrogen at the temperature of-196 ℃ at the speed of 1cm/s, keeping the temperature for 10min, removing a sealing cover of the centrifuge tube, placing the centrifuge tube into a vacuum freeze dryer, and drying the centrifuge tube for 48h under the conditions that the vacuum degree is 30Pa and the temperature is-50 ℃ to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor;
and (3) placing the precursor of the three-dimensional porous self-supporting NiO/ZnO heterojunction material in a muffle furnace, raising the calcining temperature from room temperature to 500 ℃ according to the heating rate of 1 ℃/min, then preserving the temperature for 2h, and then naturally cooling to room temperature to obtain the three-dimensional porous self-supporting NiO/ZnO heterojunction material (marked as NiO/ZnO-3) with macropores, mesopores and micropores. Wherein the pore diameter of the macropore is 2 μm, the pore diameter of the mesopore is 32nm, and the pore diameter of the micropore is 1 nm.
Comparative example 1
Dissolving 0.744g of nickel acetate and 4g of polyvinylpyrrolidone in 50mL of deionized water, and magnetically stirring at the speed of 600r/min at room temperature for 12 hours to obtain a precursor solution;
injecting the precursor solution into a centrifuge tube, vertically immersing the centrifuge tube into liquid nitrogen at the temperature of-196 ℃ at the speed of 1cm/s, keeping the temperature for 10min, removing a sealing cover of the centrifuge tube, placing the centrifuge tube into a vacuum freeze dryer, and drying the centrifuge tube for 48h under the conditions that the vacuum degree is 20Pa and the temperature is-70 ℃ to obtain a three-dimensional porous self-supporting NiO material precursor;
and (3) placing the precursor material of the three-dimensional porous self-supporting NiO material in a muffle furnace, raising the calcining temperature from room temperature to 550 ℃ according to the heating rate of 2.5 ℃/min, then preserving the temperature for 2h, and then naturally cooling to room temperature to obtain the three-dimensional porous self-supporting NiO with macropores, mesopores and micropores.
Comparative application example 1
The three-dimensional porous self-supporting NiO prepared in the comparative example 1 is used for photocatalytic degradation of methyl orange, and a 50W ultraviolet lamp is used as a light source. 30mg of NiO prepared in comparative example 1 was added to 30mL of a 10ppm methyl orange solution, adsorbed in the dark for 30min to reach an adsorption-desorption equilibrium, after which the mixed solution was placed under an ultraviolet lamp, 2mL of the solution was taken out every 15min, and the absorbance of the solution at 463nm was measured with a UH4150 spectrophotometer, and the results are shown in FIG. 12.
Comparative example 2
Dissolving 0.656g of zinc acetate and 4g of polyvinylpyrrolidone in 50mL of deionized water, and magnetically stirring at the speed of 600r/min at room temperature for 12 hours to obtain a precursor solution;
injecting the precursor solution into a centrifuge tube, vertically immersing the centrifuge tube into liquid nitrogen at the temperature of-196 ℃ at the speed of 1cm/s, keeping the temperature for 10min, removing a sealing cover of the centrifuge tube, placing the centrifuge tube into a vacuum freeze dryer, and drying the centrifuge tube for 48h under the conditions that the vacuum degree is 20Pa and the temperature is-70 ℃ to obtain a three-dimensional porous self-supporting ZnO material precursor;
and (3) placing the three-dimensional porous self-supporting ZnO material precursor in a muffle furnace, raising the calcining temperature from room temperature to 550 ℃ according to the heating rate of 2.5 ℃/min, then preserving the temperature for 2h, and then naturally cooling to room temperature to obtain the three-dimensional porous self-supporting ZnO with macropores, mesopores and micropores.
Comparative application example 2
The three-dimensional porous self-supporting ZnO prepared in the comparative example 2 is used for photocatalytic degradation of methyl orange, and an ultraviolet lamp of 50W is used as a light source. 30mg of ZnO prepared in comparative example 2 was added to 30mL of a 10ppm methyl orange solution, adsorbed in the dark for 30min to reach an adsorption-desorption equilibrium, and after that, the mixed solution was placed under an ultraviolet light source, 2mL of the solution was taken out every 15min, and the absorbance of the solution at 463nm was measured with a UH4150 spectrophotometer, and the results are shown in FIG. 12.
Comparative example 3
Dissolving 0.496g of nickel acetate, 0.219g of zinc acetate and 4g of polyvinylpyrrolidone in 50mL of deionized water, and magnetically stirring at the speed of 600r/min at room temperature for 12 hours to obtain a precursor solution;
injecting the precursor solution into a centrifugal tube, removing a sealing cover of the centrifugal tube, putting the centrifugal tube into an oven, and drying for 48 hours at 60 ℃ to obtain a powdery NiO/ZnO material precursor;
and (3) placing the precursor of the powder NiO/ZnO material in a muffle furnace, raising the calcination temperature from room temperature to 550 ℃ according to the heating rate of 2.5 ℃/min, then preserving the temperature for 2h, and naturally cooling to room temperature to obtain the powder NiO/ZnO material (marked as NiO/ZnO-E).
Comparative application example 3
The powder NiO/ZnO heterojunction material prepared in the embodiment 3 is used for photocatalytic degradation of rhodamine B, and a 50W ultraviolet lamp is used as a light source. 30mg of NiO/ZnO-E prepared in comparative example 3 was added to 30mL of 10ppm rhodamine B solution and adsorbed in the dark for 30min to achieve adsorption-desorption equilibrium. Then, the mixed solution was placed under an ultraviolet lamp, 2mL of the solution was taken out every 15min, and the absorbance of the solution at 553nm was measured with a UH4150 spectrophotometer, and the results are shown in FIG. 14.
FIG. 1 is a process flow diagram for the preparation of a three-dimensional porous self-supporting NiO/ZnO heterojunction material of example 1. As shown in fig. 1, firstly, nickel acetate, zinc acetate, polyvinylpyrrolidone and water are mixed to obtain a precursor solution, then the precursor solution is placed in liquid nitrogen for freezing treatment, then placed in a freeze dryer for deicing treatment, and finally placed in a muffle furnace for calcining, so that the three-dimensional porous self-supporting NiO/ZnO heterojunction material is obtained.
FIG. 2 is an SEM image of the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor and the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1, wherein the inset is the SEM image of the three-dimensional porous self-supporting NiO/ZnO heterojunction material; as can be seen from fig. 2, the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor and the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 both have a pore channel structure, the pore walls are thin and smooth, and the pore channel structure left after ice sublimation can be observed on the side surface.
FIG. 3 is an SEM image of the side of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2, wherein an inset is an SEM image of a cross section of the three-dimensional porous self-supporting NiO/ZnO heterojunction material. As can be seen from FIG. 3, the microstructure of NiO/ZnO-2 prepared in example 2 is similar to that of NiO/ZnO-1 prepared in example 1, and has rich channel structure.
FIG. 4 is an SEM image of the side of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 3, wherein an inset is an SEM image of a cross section of the three-dimensional porous self-supporting NiO/ZnO heterojunction material. As can be seen from FIG. 4, the microstructure of NiO/ZnO-3 prepared in example 3 is similar to the microstructure of NiO/ZnO-1 prepared in example 1 and the microstructure of NiO/ZnO-2 prepared in example 2, and the structures have rich channel structures, but the sizes of the channels are different, which indicates that the preparation method provided by the invention can adjust and control the sizes of the channel structures.
FIG. 5 is an X-ray diffraction analysis plot of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 and NiO prepared in comparative example 1 and ZnO prepared in comparative example 2; FIG. 6 is an X-ray electron energy spectrum of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1, NiO prepared in comparative example 1 and ZnO prepared in comparative example 2; FIG. 7 is an X-ray electron energy spectrum of Zn 2p of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 and the ZnO prepared in comparative example 2; FIG. 8 is an X-ray electron energy spectrum of Ni 2p for the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 and NiO prepared in comparative example 1. As can be seen from FIGS. 5 to 8, the preparation method provided by the invention successfully prepares the three-dimensional porous self-supporting NiO/ZnO heterojunction material.
FIG. 9 is a nitrogen adsorption and desorption curve of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1; FIG. 10 is a BET pore size distribution plot of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1. As can be seen from fig. 9 and 10, the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 has a microporous and mesoporous structure.
FIG. 11 is a plot of pore size distribution from mercury intrusion test conducted on the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1. As can be seen from FIG. 11, the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 has a macroporous structure.
FIG. 12 is a graph of the photocatalytic degradation of methyl orange under ultraviolet light (λ <420nm) for the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1 and the NiO prepared in comparative example 1 and the ZnO prepared in comparative example 2; fig. 13 is a first order kinetic line fit plot of the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 1, NiO prepared in comparative example 1, and ZnO degraded methyl orange prepared in comparative example 2. As can be seen from FIGS. 12 and 13, NiO/ZnO-1 prepared in example 1 has better photocatalytic efficiency than NiO and ZnO of the same structure.
FIG. 14 is a photocatalytic degradation curve of rhodamine B under ultraviolet light (λ <420nm) for the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2 and the powdered NiO/ZnO material prepared in comparative example 3; FIG. 15 is a first order kinetic linear fit graph of degradation of rhodamine B by the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2 and the powder NiO/ZnO material prepared in comparative example 3. As can be seen from FIGS. 14 and 15, the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared in example 2 has a higher photocatalytic rate than the powdered NiO/ZnO heterojunction material prepared in comparative example 3, and the degradation rate is about 3 times that of the powdered NiO/ZnO material. Therefore, the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared by the preparation method provided by the invention has more excellent photocatalytic performance due to the unique hierarchical porous structure.
The embodiment shows that the preparation method of the three-dimensional porous self-supporting NiO/ZnO heterojunction material provided by the invention is simple to operate, and does not need to remove a template or strictly control experimental conditions. In addition, the three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared by the method has excellent photocatalytic performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a three-dimensional porous self-supporting NiO/ZnO heterojunction material comprises the following steps:
(1) mixing a high molecular polymer, a nickel source, a zinc source and water to obtain a precursor solution; the mass concentration of the high molecular polymer in the precursor solution is 2-8%, the mass concentration of the nickel source is 0.74-0.99%, and the mass concentration of the zinc source is 0.4-0.7%;
(2) sequentially freezing and deicing the precursor solution obtained in the step (1) to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor;
(3) calcining the three-dimensional porous self-supporting NiO/ZnO heterojunction material precursor obtained in the step (2) to obtain a three-dimensional porous self-supporting NiO/ZnO heterojunction material;
the three-dimensional porous self-supporting NiO/ZnO heterojunction material has a hierarchical pore structure, and the hierarchical pore comprises macropores, mesopores and micropores.
2. The method according to claim 1, wherein the high molecular weight polymer in step (1) comprises polyvinylpyrrolidone or polyvinyl alcohol; the nickel source comprises nickel acetate or nickel nitrate; the zinc source includes zinc acetate or zinc nitrate.
3. The method according to claim 1, wherein the temperature of the freezing treatment in the step (2) is-196 ℃ or less, and the time of the freezing treatment is 10-15 min.
4. The preparation method according to claim 1, wherein the temperature of the deicing in the step (2) is-70 to-50 ℃, and the time of the deicing is 24 to 48 hours.
5. The method according to claim 1 or 4, wherein the vacuum degree of the de-icing treatment in the step (2) is 10 to 30 Pa.
6. The method according to claim 1, wherein the calcination temperature in the step (3) is 500 to 550 ℃.
7. The method according to claim 6, wherein the rate of temperature increase to the calcination temperature is 1 to 2.5 ℃/min.
8. The three-dimensional porous self-supporting NiO/ZnO heterojunction material prepared by the preparation method of any one of claims 1 to 7, wherein the three-dimensional porous self-supporting NiO/ZnO heterojunction material has a hierarchical pore structure, and the hierarchical pores comprise macropores, mesopores and micropores.
9. The three-dimensional porous self-supporting NiO/ZnO heterojunction material according to claim 8, wherein the pore diameter of the micropores is 0.5-2 nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the macropores is 50 nm-10 μm.
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