CN113145119B - CuNi-Cu with two-dimensional layered structure 2 O/NiAlO x Preparation method and application of nano composite material - Google Patents
CuNi-Cu with two-dimensional layered structure 2 O/NiAlO x Preparation method and application of nano composite material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 18
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 aromatic nitro compound Chemical class 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 35
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- 238000000034 method Methods 0.000 claims abstract description 31
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 13
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- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
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- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 4
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- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
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- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
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- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
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- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J35/39—
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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
- C02F2101/38—Organic compounds containing nitrogen
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
CuNi-Cu with two-dimensional layered structure 2 O/NiAlO x The nano composite material comprises CuNi and Cu 2 O and NiAlO x . The preparation method comprises the following steps: (1) fully dissolving copper salt, nickel salt and aluminum salt in deionized water, and synthesizing CuNiAl-LDH with a two-dimensional nanosheet structure by a hydrothermal synthesis method; (2) calcining the prepared CuNiAl-LDH to form uniformly dispersed multi-metal oxide; (3) the multi-metal oxide prepared in the above is reacted in H 2 High-temperature reduction in atmosphere to prepare CuNi-Cu 2 O/NiAlO x A nanocomposite material. The application of the nano composite material in photocatalysis is particularly applicable to conversion of aromatic nitro compound pollutants into aromatic amino compounds. The photoreaction catalyst has excellent photocatalytic performance and is relatively stable. The method has the advantages of simple process, universal preparation conditions, stable product appearance, high purity and convenient and simple product treatment, and is suitable for medium-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, relates to a technology for converting aromatic nitro compounds, and particularly relates to a catalyst for converting aromatic nitro compounds.
Background
Aromatic nitro compounds have attracted considerable attention as important industrial intermediates in the production of fine chemicals and pharmaceuticals. So far, the direct catalytic reduction of aromatic nitro compounds has become an important way for the efficient and environment-friendly process. However, due to the limitation of the reduction and conversion efficiency of the aromatic nitro compound, the residual solution in the industrial production process contains a large amount of unconverted aromatic nitro compound, and the unconverted aromatic nitro compound enters a subsequent sewage treatment device, which not only causes economic loss, but also increases the burden of sewage treatment. The aromatic nitro compound has high solubility and stability, and once discharged, the teratogenicity, carcinogenicity and mutagenicity of the aromatic nitro compound threatens the water environment. Therefore, it is very desirable to improve the conversion efficiency of aromatic nitro compounds to aromatic amino compounds, depending on the efficiency of the catalyst, whether the waste liquid is recycled or treated during the production of aromatic amino compounds. However, in the wastewater treatment, it is still a challenge how to construct an efficient, stable and low-cost catalyst to convert the highly toxic aromatic nitro compound into a valuable aromatic amino compound with low toxicity and easy degradation.
The performance of a catalyst is mainly influenced by its composition, which affects the intrinsic activity of the catalyst, and by its structure, which affects the arrangement and stability of the active sites. So far, some cheap zero-valent nano metals such as Fe, Co, Ni and Cu are widely used to catalyze the reduction of aromatic nitro compounds to aromatic amino compounds. However, the rapid decay of activity due to severe agglomeration limits the usefulness of its use. In order to fully utilize the activity of the uniformly dispersed nano-metal and avoid generating byproducts on a non-selective phase, reasonable structure and morphology of the alloy carrier nano-catalyst need to be constructed to improve the catalytic performance of the alloy carrier nano-catalyst. In fact, metal oxides, carbon materials and SiO 2 Have been developed as supports for catalysts. Wherein the semiconducting metal oxide is, for example, alpha-Fe 2 O 3 /Cu 2 O,CuO/Bi 2 MoO 6 ,TiO 2 /Cu 2 O and the like, which can be used as an active carrier of a catalyst to reduce the aromatic nitro compound by utilizing photogenerated electrons under the condition of illumination. Based on the above analysis, the preparation of the alloy-metal oxide support nano-catalyst not only needs to effectively disperse the active nano-alloy, but also adjusts the electron cloud density of the active metal through the synergistic effect between the metal and the metal oxide support, thereby finally improving the activity and stability of the catalyst. Structurally, two-dimensional (2D) nanostructures can provide high specific surface area, which is advantageous for exposing as many active sites as possible to obtain high catalytic performance. Therefore, the organic combination of the active nano alloy and the two-dimensional semiconductor metal oxide is an effective way to obtain cheap, efficient and stable nano catalyst.
Disclosure of Invention
The invention mainly aims to provide a nano composite material, a preparation method and application thereof, in particular to a catalyst for converting aromatic nitro compounds, wherein the nano composite material has stronger natural light absorption capacity, enhanced photocatalytic performance and relatively stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
nano compositeThe material is a material containing CuNi and Cu 2 O and NiAlO x Two-dimensional layered structure CuNi-Cu of 2 O/NiAlO x . Further, the nanoparticles CuNi and Cu 2 O is uniformly dispersed in NiAlO x The above.
The preparation method of the nano composite material comprises the following steps:
(1) preparing a CuNiAl-LDH composite material by a hydrothermal synthesis method;
(2) preparing a CuNiAl multi-metal oxide composite material by a high-temperature calcination method;
(3) by high temperature H 2 Reduction method for preparing CuNi-Cu 2 O/NiAlO x A composite material.
Further, the preparation method of the CuNiAl-LDH composite material comprises the following steps:
(1) weighing copper salt and dissolving in a solvent;
(2) weighing nickel salt and dissolving in a solvent;
(3) weighing aluminum salt and dissolving in a solvent;
(4) weighing urea and dissolving in a solvent;
(5) adding the solution into a reaction kettle, and uniformly mixing and stirring;
(6) heating and preserving the temperature of the reaction kettle;
(7) and cooling the reaction system to room temperature, centrifugally separating the product in the reaction kettle, alternately washing the product with absolute ethyl alcohol and deionized water for 3 times in sequence, and drying the product in vacuum to obtain the CuNiAl-LDH composite material.
According to the preparation method of the CuNiAl-LDH composite material, deionized water is used as a solvent in the steps (1), (2), (3) and (4).
According to the preparation method of the CuNiAl-LDH composite material, the purities of copper salt, nickel salt, aluminum salt and urea in the steps (1), (2), (3) and (4) are not lower than chemical purity.
According to the preparation method of the CuNiAl-LDH composite material, the mass ratio of copper salt in the step (1) to nickel salt in the step (2) is (1-5): 1.
The preparation method of the CuNiAl-LDH composite material comprises the step of (0.1-1) and (3-50) mixing the aluminum salt in the step (3) and the copper salt in the step (1) by mass.
According to the preparation method of the CuNiAl-LDH composite material, the mass ratio of the aluminum salt in the step (3) to the nickel salt in the step (2) is (0.1-1) to (1-80).
According to the preparation method of the CuNiAl-LDH composite material, the mass concentration of the urea solution in the step (4) is 10-50%.
The preparation method of the CuNiAl-LDH composite material comprises the following steps of (5) dissolving the metal salt in deionized water to obtain the concentration of 0.1-1 mg/mL;
the preparation method of the CuNiAl-LDH composite material comprises the step (6) of heating at a rate of 2-5 ℃/min.
The preparation method of the CuNiAl-LDH composite material comprises the step (6) of keeping the temperature at 110-180 ℃.
The preparation method of the CuNiAl-LDH composite material has the advantage that the heat preservation time in the step (6) is 8-15 h.
The preparation method of the CuNiAl-LDH composite material comprises the step (7) of vacuum drying for 2-10 h.
The preparation method of the CuNiAl-LDH composite material comprises the step (7) of vacuum drying at the temperature of 40-80 ℃.
In addition, the preparation of the CuNiAl multi-metal oxide composite material comprises the following steps:
(1) weighing CuNiAl-LDH, uniformly spreading the CuNiAl-LDH in a corundum porcelain boat, and placing the corundum porcelain boat in the center of a quartz tube in a CVD tube furnace;
(2) introduction of N 2 The airflow is used as protective airflow;
(3) at N 2 Under the protection of atmosphere, heating and preserving heat;
(4) and cooling the reaction system to room temperature, and performing vacuum drying to collect a product to obtain the CuNiAl multi-metal oxide composite material.
According to the preparation method of the CuNiAl multi-metal oxide composite material, the mass of CuNiAl-LDH in the step (1) is 0.1-1 g; h 2 The flow rate of the carrier gas protective gas flow is 0.5-2L/min.
The preparation method of the CuNiAl multi-metal oxide composite material comprises the following steps that in the step (3), the temperature rising rate is divided into two stages; the first stage is 5-10 ℃/min; the second stage is 2-5 ℃/min.
The preparation method of the CuNiAl multi-metal oxide composite material comprises the step (3) of keeping the temperature at 300-500 ℃.
The preparation method of the CuNiAl multi-metal oxide composite material comprises the step (3) of keeping the temperature for 1-6 h.
The CuNi-Cu 2 O/NiAlO x The preparation of the composite material comprises the following steps:
(1) weighing CuNiAl multi-metal oxide, uniformly spreading the CuNiAl multi-metal oxide in a corundum porcelain boat, and placing the corundum porcelain boat in the center of a quartz tube in a CVD tube furnace;
(2) introduction of H 2 The gas flow is used as a reducing gas flow;
(3) at H 2 Heating and preserving heat under the atmosphere;
(4) cooling the reaction system to room temperature, and vacuum drying and collecting the product to obtain CuNi-Cu 2 O/NiAlO x A composite material.
The CuNi-Cu 2 O/NiAlO x The preparation method of the composite material comprises the following steps of (1) enabling the mass of CuNiAl-LDH to be 0.1-1 g; h 2 The flow rate of the carrier gas protective gas flow is 0.5-2L/min.
The CuNi-Cu 2 O/NiAlO x The preparation method of the composite material, the heating rate in the step (3) is divided into two stages; the first stage is 5-10 ℃/min; the second stage is 2-5 ℃/min.
The CuNi-Cu 2 O/NiAlO x The preparation method of the composite material comprises the step (3) of keeping the temperature at 300-500 ℃.
The CuNi-Cu 2 O/NiAlO x The preparation method of the composite material comprises the step (3) of keeping the temperature for 1-6 h.
CuNi-Cu prepared according to the above preparation method 2 O/NiAlO x The composite material is prepared from the following components: CuNi, Cu 2 O and carrier NiAlO x 。
CuNi-Cu prepared according to the above preparation method 2 O/NiAlO x The composite material is applied to the conversion of aromatic nitro compound pollutants into aromatic amino compounds and photocatalysis.
Due to the adoption of the scheme, the invention has the beneficial effects that:
1. the invention utilizes a hydrothermal method and calcination and H 2 The reduction combined method has certain universality on preparation of multi-element metal alloy and multi-element metal oxide;
2. simple inorganic salt is respectively adopted as reactants, so that the raw material reserves are abundant, and the industrial cost is low;
3. the product prepared by the method has good conversion and photocatalytic performance of the aromatic nitro compound, can be used as a conversion and photocatalytic material of high-performance aromatic nitro compound pollutants, and has a wide development prospect and an application space;
4. the method has the advantages of simple process, mild preparation conditions, stable product appearance, high purity and convenient and simple product treatment, and is suitable for medium-scale industrial production;
5. the method is different from the synthesis method of other materials in that the binary metal alloy and the metal oxide nano particles are uniformly and densely dispersed in the two-dimensional layered multi-metal oxide NiAlO by utilizing one step of in-situ synthesis x The in-situ synthesis is more beneficial to the transfer of electron and hole pairs of the material in the catalytic process, the material can generate photocatalytic performance under natural light, and meanwhile, in the field of the conversion of aromatic nitro compounds, the excellent reaction rate of the nano composite material, particularly the conversion of p-nitrophenol, can be completely converted within about 30 seconds, so that the nano composite material has important application prospect in the field. The large specific surface area can provide the most active sites to effectively adsorb catalytic substrates for catalytic processes. Under natural light, Cu 2 Photo-generated electrons on the surface of O are quickly transferred to CuNi nano particles, and a catalytic substrate is reduced on the designed nano catalyst. The CuNi nano particles in the nano catalyst can not only effectively catalyze the formation of active hydrogen, but also promote electron transfer and conversion due to the structure effect, the composite effect and the size effect. NiAlO, on the other hand x NiO in the matrix can be mixed with Cu 2 O forms an ohmic back contact to enhance the photo-generated holes transfer to NiO, which is good for preventing Cu 2 Recombination of electrons and holes on O.
Drawings
FIG. 1 is a graph of CuNiAl-LDH, CuNiAl multi-metal oxide and CuNi-Cu in example 1 2 O/NiAlO x SEM photograph of the product obtained at a multiple of 1 μm, wherein:
panel A is an SEM photograph of a product of CuNiAl-LDH obtained in example 1 at a magnification of 1 μm;
panel B is an SEM photograph of a product of the CuNiAl multi-metal oxide of example 1 at a magnification of 1 μm;
diagram C shows CuNi-Cu in example 1 2 O/NiAlO x SEM photograph of the product obtained at a magnification of 1 μm.
FIG. 2 shows CuNi-Cu in example 1 2 O/NiAlO x A product XRD pattern and EDS pattern, wherein:
panel A shows CuNi-Cu in example 1 2 O/NiAlO x An XRD pattern of (a);
FIG. B shows CuNi-Cu in example 1 2 O/NiAlO x EDS spectrum of (a).
FIG. 3 shows CuNi-Cu in example 1 2 O/NiAlO x SEM photo, TEM photo atlas of the product of (a), wherein:
panel A shows CuNi-Cu in example 1 2 O/NiAlO x SEM photograph of the product obtained at a multiple of 100 nm;
panel B shows CuNi-Cu in example 1 2 O/NiAlO x TEM photograph of the product obtained at a multiple of 10 nm;
panel C is CuNi-Cu in example 1 2 O/NiAlO x TEM photograph of the product obtained at a multiple of 10 nm.
FIG. 4 shows CuNi-Cu in example 1 2 O/NiAlO x SEM photograph, TEM photograph of the product of (a), wherein:
panel A shows CuNi-Cu in example 1 2 O/NiAlO x HRTEM photograph of the product obtained at a multiple of 2 nm;
panel B shows CuNi-Cu in example 1 2 O/NiAlO x SAED photographs of the product obtained at multiples of 10 m.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are illustrated in the accompanying drawings.
Example 1
(1) Preparation of CuNiAl-LDH
In the first step, 426.2mg of copper chloride dihydrate are weighed out and dissolved in a 250mL volumetric flask. Transferring 7.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
in a second step, 594.2mg of nickel chloride hexahydrate were weighed out and dissolved in a 250mL volumetric flask. Transferring 3.3ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
third, 603.6mg of aluminum chloride hexahydrate were weighed and dissolved in a 250mL volumetric flask. Transferring 2.7ml of the solution to a polytetrafluoroethylene reaction kettle by using a liquid transfer gun;
in the fourth step, 1.501g of urea was weighed out and dissolved in a 250mL volumetric flask. Transferring 7.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
fifthly, placing the reaction kettle in an electric heating constant-temperature air blast drying oven, raising the temperature from room temperature to 140 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 10 hours;
and sixthly, when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 4 hours at the temperature of 60 ℃, taking out the product, and sealing and storing.
(2) Preparation of CuNiAl multi-metal oxide
The first step is as follows: weighing 20mg of the prepared CuNiAl-LDH, and uniformly spreading the CuNiAl-LDH in a corundum porcelain boat with the density of 1cmx4 cm;
the second step is that: placing the porcelain boat in the center of a quartz tube in a CVD tube furnace, and introducing a certain amount of N before the reaction starts 2 Maintaining the flow rate at 0.5L/min;
the third step: in N 2 Rapidly raising the temperature from room temperature to 300 ℃ at a heating rate of 10 ℃/min under the protection of atmosphere, then slowly raising the temperature to 400 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 4 h;
the fourth step: waiting until the reaction system is naturally cooled to room temperature.
(3)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 20mg of the prepared CuNiAl multi-metal oxide, and uniformly spreading the CuNiAl multi-metal oxide in a corundum porcelain boat with the diameter of 1cmx4 cm;
the second step is that: placing the porcelain boat in the center of a quartz tube in a CVD tube furnace, and introducing a certain amount of H before the reaction starts 2 Maintaining the flow rate at 1L/min;
the third step: at H 2 Rapidly raising the temperature from room temperature to 300 ℃ at a heating rate of 10 ℃/min under the protection of atmosphere, then slowly raising the temperature to 400 ℃ at a heating rate of 2 ℃/min, and preserving the temperature for 3 h;
the fourth step: after the reaction system had cooled naturally to room temperature, the product in the porcelain boat was collected by transferring into a test tube for further characterization.
As shown in the figure:
FIG. 1(A-C) shows CuNiAl-LDH (A), CuNiAl multimetal oxide (B) and CuNi-Cu obtained under the same magnification in example 1 2 O/NiAlO x (C) SEM photograph of emission scanning electron microscope.
FIG. 2(A, B) is a graph of CuNiAl-LDH (a), CuNiAl multimetal oxide (b), and CuNi-Cu prepared 2 O/ NiAlO x (c) XRD (A) and EDS (B) patterns of (A). With Cu-Cu 2 O/Al 2 O 3 And X/NiAlO x Diffraction peak ratio of CuNi-Cu 2 O/NiAlO x Peaks at 43.5 ℃, 50.6 ℃ and 74.4 ℃ were between Cu (JCPDS pattern No.: 04-0836) and X (JCPDS pattern No.: 65-0380), confirming that Cu is excluded 2 Forming CuNi nano alloy particles besides O (JCPDS map number: 65-3288) and XO (JCPDS map number: 65-6920). Wherein Cu 2 O (JCPDS map No. 65-3288) and XO (JCPDS map No. 65-6920) in Cu-Cu 2 O/Al 2 O 3 Or X/NiAlO x, Can also be observed separately. Due to Al 2 O 3 Is amorphous and therefore there is no corresponding diffraction peak in the synthesized sample. EDS analysis shows that Cu, Ni, Al and O elements, CuNi-Cu exist 2 O/NiAlO x Has a Cu/Ni/Al/O molar ratio of about 40:17:14:29, which corresponds toThe original target ratio. Cu-Cu 2 O/Al 2 O 3 Has a Cu/Al/O molar ratio of about 53.82:23.56:23.12, Ni/NiAlO x Has a molar ratio of Ni/Al/O of about 41.85:18.94: 40.21. In addition, the element distribution of the obtained composite material is analyzed by measuring the element mapping, and the obtained CuNi-Cu of each component is shown 2 O/NiAlO x The nano catalyst is uniformly distributed in the nano catalyst.
FIG. 3(A-C) shows CuNi-Cu prepared 2 O/NiAlO x SEM (A) and HRTEM (B, C) images. As can be seen, the prepared CuNi-Cu 2 O particles are tightly adhered to NiAlO x Filling the whole laminated structure with Cu, and Ni 2 O/ NiAlO x The HRTEM analysis of (A) shows that CuNi-Cu is present 2 O particles of about 4nm diameter, NiAlO x The thickness of the layered structure is about 2 nm.
FIG. 4(A, B) shows HRTEM (A) and SAED (B) plots of CuNiAl multimetal oxide. HRTEM image display except amorphous Al 2 O 3 In addition, the lattice spacing of the CuNi NAs (111) plane was 0.207nm, and Cu 2 The lattice spacing of the O (111) plane was 0.246nm, and the lattice spacing of the NiO (111) plane was 0.242 nm. It shows Cu 2 O nano phase and CuNi nano particle in NiAlO x The nanoplatelets are adjacent on the surface. SAED map shows, Cu 2 The results of HRTEM were identical for the O (111) plane, the NiO (111) plane, and the CuNi NAs (111), (200), and (220) plane.
CuNi-Cu with large specific surface area 2 O/NiAlO x The most active sites can be provided to efficiently adsorb catalytic substrates for catalytic processes. Under illumination, Cu 2 Photo-generated electrons on the surface of O are quickly transferred to CuNi nano particles, and the CuNi nano particles in the nano catalyst can effectively catalyze the formation of active hydrogen and promote the electron transfer and conversion. NiAlO x NiO in the matrix can be mixed with Cu 2 And O forms ohmic reverse contact, so that photoproduction holes transferred to NiO are enhanced, and combination of photoproduction electrons and holes is prevented.
Example 2
(1) Preparation of CuNiAl-LDH
In the first step, 456.4mg of copper acetate monohydrate was weighed out and dissolved in a 250mL volumetric flask. Transferring 7.5ml of the solution to a three-neck round-bottom flask by using a pipette;
in a second step, 534.8mg of nickel nitrate hexahydrate were weighed and dissolved in a 250mL volumetric flask. Transferring 3ml of the solution to a three-neck round-bottom flask by using a pipette;
third, 593.2mg of aluminum nitrate nonahydrate were weighed and dissolved in a 250mL volumetric flask. Transferring 2.5ml of the solution to a three-neck round-bottom flask by using a pipette;
in the fourth step, 1.83g of urea was weighed out and dissolved in a 250mL volumetric flask. Transferring 7ml of the solution to a three-neck round-bottom flask by using a pipette;
fifthly, placing the three-neck round-bottom flask in an oil bath, raising the temperature from room temperature to 90 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 15 hours;
and sixthly, when the reaction system is naturally cooled to the room temperature, transferring and collecting the product in the three-neck round-bottom flask into a centrifuge tube, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at the temperature of 40 ℃, taking out the product, and sealing and storing.
(2)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 20mg of CuNiAl-LDH prepared above, placing in 40mL deionized water, adding 40mg of NaBH 4 ；
The second step: putting the system in an oil bath pot, raising the temperature from room temperature to 80 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 2 hours;
the third step: and (3) transferring and collecting the product in the three-neck round-bottom flask into a centrifuge tube after the reaction system is naturally cooled to room temperature, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 4 hours at the temperature of 60 ℃, taking out the product, sealing and storing so as to further characterize and test.
Example 3
(1) Preparation of CuNiAl-LDH
In the first step, 91.8mg of copper acetate monohydrate was weighed and dissolved in a 250mL volumetric flask. Transferring 6.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
in a second step, 544.2mg of nickel acetate tetrahydrate were weighed out and dissolved in a 250mL volumetric flask. Transferring 3ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
third, 589.5mg of aluminum nitrate nonahydrate were weighed and dissolved in a 250mL volumetric flask. Transferring 3ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
in the fourth step, 0.391g of urea is weighed out and dissolved in a 250mL volumetric flask. Transferring 7.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
fifthly, placing the reaction kettle in an electric heating constant-temperature air blast drying oven, raising the temperature from room temperature to 160 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 8 hours;
and sixthly, when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the reaction kettle into a centrifugal tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 3 hours at the temperature of 80 ℃, taking out the product, and sealing and storing.
(2)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 25mg of CuNiAl-LDH prepared above, placing the CuNiAl-LDH into a conical flask, adding 40mL of deionized water, carrying out ultrasonic treatment for 2h, and then adding 80mg of NaBH 4 ；
The second step is that: putting the system in a water bath kettle, heating to 80 ℃ from room temperature at the heating rate of 5 ℃/min, and keeping the temperature for 4 hours;
the third step: and (3) when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the conical flask into a centrifuge tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at 70 ℃, taking out the product, sealing and storing so as to further characterize and test.
Example 4
(1) Preparation of CuNiAl-LDH
In the first step, 206mg of copper acetate monohydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 8ml of the solution to a three-neck round-bottom flask by using a pipette;
second, 210mg of nickel chloride hexahydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 2ml of the solution to a three-neck round-bottom flask by using a pipette;
third, 205mg of aluminum nitrate nonahydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 2.5ml of the solution to a three-neck round-bottom flask by using a pipette;
in the fourth step, 0.3g of urea is weighed out and dissolved in a 100mL volumetric flask. Transferring 7.5ml of the solution to a three-neck round-bottom flask by using a pipette;
fifthly, placing the three-neck round-bottom flask in an oil bath, raising the temperature from room temperature to 90 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 15 hours;
and sixthly, when the reaction system is naturally cooled to the room temperature, transferring and collecting the product in the three-neck round-bottom flask into a centrifuge tube, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at the temperature of 40 ℃, taking out the product, and sealing and storing.
(2) Preparation of CuNiAl multi-metal oxide
The first step is as follows: weighing the prepared CuNiAl-LDH 2mg, and uniformly spreading the CuNiAl-LDH in a corundum porcelain boat with the diameter of 1cmx4 cm;
the second step: placing the porcelain boat in the center of a quartz tube in a CVD tube furnace, and introducing a certain amount of N before the reaction starts 2 Maintaining the gas flow rate at 2L/min;
the third step: in N 2 Rapidly raising the temperature from room temperature to 300 ℃ at a heating rate of 10 ℃/min under the protection of atmosphere, then slowly raising the temperature to 400 ℃ at a heating rate of 2 ℃/min, and preserving the temperature for 4 h;
the fourth step: waiting until the reaction system is naturally cooled to room temperature.
(3)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 1mg of the prepared CuNiAl-LDH, and uniformly spreading the CuNiAl-LDH in a corundum porcelain boat with the density of 1cmx4 cm;
the second step is that: placing the porcelain boat in the center of a quartz tube in a CVD tube furnace, and introducing a certain amount of H before the reaction starts 2 Maintaining the gas flow rate at 2L/min;
third stepThe method comprises the following steps: at H 2 Rapidly raising the temperature from room temperature to 300 ℃ at a heating rate of 10 ℃/min under the protection of atmosphere, then slowly raising the temperature to 400 ℃ at a heating rate of 2 ℃/min, and preserving the temperature for 3 h;
the fourth step: after the reaction system cooled naturally to room temperature, the product in the porcelain boat was transferred to a collection tube for further characterization of the test.
Example 5
(1) Preparation of CuNiAl-LDH
In the first step, 506.5mg of copper nitrate trihydrate are weighed out and dissolved in a 250mL volumetric flask. Transferring 6.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
second, 104.2mg of nickel acetate tetrahydrate was weighed and dissolved in a 250mL volumetric flask. Transferring 3ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
in the third step, 173.6mg of aluminum chloride hexahydrate was weighed and dissolved in a 250mL volumetric flask. Transferring 3ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
in the fourth step, 1.13g of urea was weighed out and dissolved in a 250mL volumetric flask. Transferring 7.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
fifthly, placing the reaction kettle in an electric heating constant temperature air blast drying oven, raising the temperature from room temperature to 110 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 15 hours;
and sixthly, when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 3 hours at the temperature of 80 ℃, taking out the product, and sealing and storing.
(2) Preparation of CuNiAl multi-metal oxide
The first step is as follows: weighing 1mg of the prepared CuNiAl-LDH, and uniformly spreading the CuNiAl-LDH in a corundum porcelain boat with the density of 1cmx4 cm;
the second step is that: placing the porcelain boat in the center of a quartz tube in a CVD tube furnace, and introducing a certain amount of N before the reaction starts 2 Maintaining the flow rate at 1L/min;
the third step: in N 2 Rapidly raising the temperature from room temperature to 300 ℃ at the temperature raising rate of 8 ℃/min under the protection of atmosphere, then slowly raising the temperature to 500 ℃ at the temperature raising rate of 5 ℃/min, and preserving the temperature for 3 h;
the fourth step: waiting until the reaction system is naturally cooled to room temperature.
(3)CuNi-Cu 2 O/NiAlO x Preparation of (2)
The first step is as follows: weighing 30mg of the CuNiAl multi-metal oxide prepared above, placing the CuNiAl multi-metal oxide into a conical flask, adding 40mL of deionized water, performing ultrasonic treatment for 2h, and then adding 80mg of NaBH 4 ；
The second step is that: putting the system in a water bath kettle, raising the temperature from room temperature to 60 ℃ at the rate of 5 ℃/min, and preserving the temperature for 4 hours;
the third step: and (3) when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the conical flask into a centrifuge tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at the temperature of 40 ℃, taking out the product, and storing in a sealed manner so as to further characterize and test.
Example 6
(1) Preparation of CuNiAl-LDH
In the first step, 108.3mg of copper acetate monohydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 8ml of the solution to a three-neck round-bottom flask by using a pipette;
in the second step, 134.1mg of nickel nitrate hexahydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 2ml of the solution to a three-neck round-bottom flask by using a pipette;
third, 62.8mg of aluminum nitrate nonahydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 2.5ml of the solution to a three-neck round-bottom flask by using a pipette;
in the fourth step, 0.151g of urea was weighed and dissolved in a 100mL volumetric flask. Transferring 7.5ml of the solution to a three-neck round-bottom flask by using a pipette;
fifthly, placing the three-neck round-bottom flask in an oil bath, raising the temperature from room temperature to 90 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 15 hours;
and sixthly, when the reaction system is naturally cooled to the room temperature, transferring and collecting the product in the three-neck round-bottom flask into a centrifuge tube, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at the temperature of 40 ℃, taking out the product, and sealing and storing.
(2) Preparation of CuNiAl multi-metal oxide
The first step is as follows: weighing 0.5mg of the prepared CuNiAl-LDH, and uniformly spreading the CuNiAl-LDH in a corundum porcelain boat with the density of 1cmx4 cm;
the second step is that: placing the porcelain boat in the center of a quartz tube in a CVD tube furnace, and introducing a certain amount of N before the reaction starts 2 Maintaining the gas flow rate at 2L/min;
the third step: in N 2 Rapidly raising the temperature from room temperature to 300 ℃ at a heating rate of 10 ℃/min under the protection of atmosphere, then slowly raising the temperature to 300 ℃ at a heating rate of 2 ℃/min and preserving the temperature for 6 h;
the fourth step: waiting until the reaction system is naturally cooled to room temperature.
(3)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 15mg of the CuNiAl multi-metal oxide prepared above, placing the CuNiAl multi-metal oxide into a conical flask, adding 40mL of deionized water, performing ultrasonic treatment for 2h, and then adding 80mg of NaBH 4 ；
The second step is that: putting the system in a water bath kettle, raising the temperature from room temperature to 60 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 4 hours;
the third step: and (3) when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the conical flask into a centrifuge tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at the temperature of 40 ℃, taking out the product, and storing in a sealed manner so as to further characterize and test.
Example 7
(1) Preparation of NiAl-LDH
In the first step, 301.6mg of aluminum chloride hexahydrate is weighed and dissolved in a 250mL volumetric flask. Transferring 2.7ml of the solution to a polytetrafluoroethylene reaction kettle by using a liquid transfer gun;
in a second step, 594.2mg of nickel chloride hexahydrate were weighed out and dissolved in a 250mL volumetric flask. Transferring 3.3ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
third, 1.501g of urea was weighed and dissolved in a 250mL volumetric flask. Transferring 7.5ml of the solution by using a liquid transfer gun to a polytetrafluoroethylene reaction kettle;
fourthly, placing the reaction kettle in an electric heating constant temperature blast drying oven, raising the temperature from room temperature to 140 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 10 hours;
and fifthly, when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 4 hours at the temperature of 60 ℃, taking out the product, and sealing and storing.
(2)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 20mg of the prepared NiAl-LDH, placing the NiAl-LDH into a conical flask, adding 40mL of deionized water, carrying out ultrasonic treatment for 2h, and then adding 80mg of NaBH 4 20mg of copper chloride dihydrate, and 5mg of nickel chloride hexahydrate;
the second step: putting the system in a water bath kettle, raising the temperature from room temperature to 80 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 4 hours;
the third step: and (3) when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the conical flask into a centrifuge tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 2 hours at the temperature of 80 ℃, taking out the product, and storing in a sealed manner so as to further characterize and test.
Example 8
(1) Preparation of NiAl-LDH
In the first step, 134.1mg of nickel nitrate hexahydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 2ml of the solution to a three-neck round-bottom flask by using a pipette;
in a second step, 57.8mg of aluminum nitrate nonahydrate was weighed and dissolved in a 100mL volumetric flask. Transferring 2.5ml of the solution to a three-neck round-bottom flask by using a pipette;
third, 0.301g of urea was weighed out and dissolved in a 100mL volumetric flask. Transferring 7.5ml of the solution to a three-neck round-bottom flask by using a pipette;
fourthly, placing the three-neck round-bottom flask into an oil bath, raising the temperature from room temperature to 90 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 15 hours;
and fifthly, when the reaction system is naturally cooled to the room temperature, transferring and collecting the product in the three-neck round-bottom flask into a centrifuge tube, centrifugally separating, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 6 hours at the temperature of 40 ℃, taking out the product, and sealing and storing.
(2)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 10mg of NiAl-LDH prepared above, placing the NiAl-LDH into a conical flask, adding 15mL of deionized water, carrying out ultrasonic treatment for 2h, and then adding 30mg of NaBH 4 20mg of copper chloride dihydrate, and 5mg of nickel chloride hexahydrate;
the second step is that: putting the system in a water bath kettle, raising the temperature from room temperature to 80 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 4 hours;
the third step: and (3) when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the conical flask into a centrifuge tube, performing centrifugal separation, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying for 2 hours at the temperature of 80 ℃, taking out the product, and storing in a sealed manner so as to further characterize and test.
Example 9
(1) Preparation of CuNiAl-LDH
In the first step, 426.2mg of copper chloride dihydrate are weighed out and dissolved in a 250mL volumetric flask. Using a pipette to pipette 11.2ml of the solution into a beaker;
in a second step, 594.2mg of nickel chloride hexahydrate were weighed out and dissolved in a 250mL volumetric flask. Using a pipette to transfer 4.8ml of the solution into a beaker;
third, 60.6mg of aluminum chloride hexahydrate was weighed and dissolved in a 250mL volumetric flask. Using a pipette to pipette 4ml of the solution into a beaker;
fourthly, uniformly stirring the three solutions in a beaker by magnetic force, weighing 0.2g of anhydrous sodium carbonate, dissolving the anhydrous sodium carbonate in 100mL of deionized water, dropwise adding the anhydrous sodium carbonate into the beaker by a rubber head dropper while stirring, and gradually turning green;
and fifthly, transferring and collecting the product in the beaker into a centrifuge tube, centrifuging, alternately washing the product for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying the product for 4 hours at the temperature of 60 ℃, taking out the product, and sealing and storing the product.
(2)CuNi-Cu 2 O/NiAlO x Preparation of
The first step is as follows: weighing 10mg of CuNiAl-LDH prepared above, placing in 20mL deionized water, adding 30mg of NaBH 4 ；
The second step is that: putting the system in an oil bath pot, raising the temperature from room temperature to 60 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 4 hours;
the third step: and (3) when the reaction system is naturally cooled to room temperature, transferring and collecting the product in the beaker into a centrifuge tube, performing centrifugal separation, alternately washing the product for 3 times by using absolute ethyl alcohol and deionized water, then placing the product in a vacuum drying oven, drying the product for 6 hours at the temperature of 60 ℃, taking out the product, and sealing and storing the product so as to further characterize and test the product.
The method adopts copper salt, nickel salt and aluminum salt as a copper source, a nickel source and an aluminum source respectively, adopts urea as a reaction precipitator, and adopts a hydrothermal method or a constant-temperature heating method, calcination and H 2 Reduction or NaBH 4 The reduction method successfully prepares the CuNi-Cu with a two-dimensional layered structure 2 O/NiAlO x A composite material. The photocatalytic reaction catalyst has excellent conversion performance on aromatic nitro compound pollutants. The method has the advantages of simple process, universal preparation conditions, stable product appearance, high purity and convenient and simple product treatment, and is suitable for medium-scale industrial production.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments herein, and modifications made without departing from the scope of the present invention are within the scope of the present invention.
Claims (9)
1. CuNi-Cu with two-dimensional layered structure 2 O/NiAlO x A nanocomposite characterized by: is composed of CuNi and Cu 2 O and NiAlO x ；
The nano particles CuNi and Cu 2 O is uniformly dispersed in NiAlO x The above.
2. A process for the preparation of a nanocomposite material as claimed in claim 1, characterized in that it comprises the following steps:
(1) preparing a CuNiAl-LDH composite material by a hydrothermal synthesis method;
(2) preparing a CuNiAl multi-metal oxide composite material by a high-temperature calcination method;
(3) by high temperature H 2 Reduction method for preparing CuNi-Cu 2 O/NiAlO x A composite material;
the preparation method of the CuNiAl-LDH composite material comprises the following steps:
(1) weighing copper salt and dissolving in a solvent;
(2) weighing nickel salt and dissolving in a solvent;
(3) weighing aluminum salt and dissolving in a solvent;
(4) weighing urea and dissolving the urea in a solvent;
(5) adding the solution into a reaction kettle, and mixing and stirring uniformly;
(6) heating and preserving the temperature of the reaction kettle;
(7) cooling the reaction system to room temperature, centrifugally separating the product in the reaction kettle, alternately washing with absolute ethyl alcohol and deionized water in sequence, and drying in vacuum to obtain a CuNiAl-LDH composite material;
in the preparation method of the CuNiAl-LDH composite material, the concentration of the metal salt dissolved in the deionized water in the step (5) is 0.001-1 mg/mL; and/or the mass ratio of the copper salt in the step (1), the nickel salt in the step (2) and the aluminum salt in the step (3) is (4-10): 1-6): 1;
the preparation method of the CuNiAl multi-metal oxide composite material comprises the following steps:
(1) weighing CuNiAl-LDH, uniformly spreading the CuNiAl-LDH in a corundum porcelain boat, and placing the CuNiAl-LDH in the center of a quartz tube in a CVD tube furnace;
(2) introduction of N 2 The airflow is used as protective airflow;
(3) in N 2 Under the protection of atmosphere, heating and preserving heat;
(4) cooling the reaction system to room temperature, and vacuum drying and collecting the product to obtain the CuNiAl multi-metal oxide composite material;
according to the preparation method of the CuNiAl multi-metal oxide composite material, the mass of CuNiAl-LDH in the step (1) is 0.1-1 g; n in step (2) 2 The flow rate of the carrier gas protective gas flow is 0.5-1L/min; in the step (3), the temperature rise rate is divided into two stages: the first stage is 5-10 deg.c/min; the second stage is 2-5 ℃/min; the heat preservation temperature is 300-500 ℃; the heat preservation time is 1h-6 h;
the CuNi-Cu 2 O/NiAlO x The preparation of the composite material comprises the following steps:
(1) weighing CuNiAl multi-metal oxide, uniformly spreading the CuNiAl multi-metal oxide in a corundum porcelain boat, and placing the corundum porcelain boat in the center of a quartz tube in a CVD tube furnace;
(2) introduction of H 2 The gas flow is used as a reducing gas flow;
(3) at H 2 Heating and preserving heat under the atmosphere;
(4) cooling the reaction system to room temperature, and vacuum drying and collecting the product to obtain CuNi-Cu 2 O/NiAlO x A composite material;
the CuNi-Cu 2 O/NiAlO x The preparation method of the composite material comprises the following two stages of temperature rise rate in the step (3): the first stage is 5-10 deg.c/min; the second stage is 2 ℃/min-5 ℃/min; the heat preservation temperature in the step (4) is 300-500 ℃; the heat preservation time in the step (4) is 1-6 h.
3. The method for preparing a nanocomposite material as claimed in claim 2, wherein the solvent in the step (1) is deionized water; the purity of the copper salt in the step (1) is not lower than chemical purity; and/or the presence of a gas in the gas,
the solvent in the step (2) is deionized water; the purity of the nickel salt in the step (2) is not lower than the chemical purity; and/or the presence of a gas in the gas,
in the step (3), the solvent is deionized water; the purity of the aluminum salt in the step (3) is not lower than the chemical purity; and/or the presence of a gas in the gas,
the solvent in the step (4) is deionized water; the purity of the urea in the step (4) is not lower than chemical purity.
4. The method for preparing a nanocomposite as claimed in claim 2, wherein the concentration of urea dissolved in deionized water in step (5) is 0.01-1 mg/mL.
5. The method for preparing a nanocomposite material as claimed in claim 2, wherein the temperature increase rate in the step (5) is 2 ℃/min to 10 ℃/min; and/or, the temperature in the step (5) is kept between 110 and 180 ℃; and/or the temperature in the step (5) is kept for 8-15 h.
6. The method for preparing a nanocomposite material as claimed in claim 2, wherein the method for preparing a CuNiAl-LDH composite material comprises the steps of (6) drying for 2-10 h under vacuum; and/or, the vacuum drying temperature in the step (6) is 40-80 ℃.
7. The method for preparing a nanocomposite material according to claim 2, characterized in that: the CuNi-Cu 2 The preparation method of the O/NiAlOx composite material comprises the following steps of (1) enabling the mass of CuNiAl multi-metal oxide to be 0.05-1 g; step (2) H 2 The flow rate of the carrier gas protective gas flow is 0.5-0.8L/min.
8. Use of a nanocomposite material according to claim 1 or 2 for photocatalysis.
9. Use according to claim 8, characterized in that: for converting aromatic nitro compound contaminants to para-aromatic amino compounds.
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