CN116139868B - Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst - Google Patents

Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst Download PDF

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CN116139868B
CN116139868B CN202310135329.8A CN202310135329A CN116139868B CN 116139868 B CN116139868 B CN 116139868B CN 202310135329 A CN202310135329 A CN 202310135329A CN 116139868 B CN116139868 B CN 116139868B
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CN116139868A (en
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梁倩
闫晓童
李忠玉
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Changzhou University
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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
    • B01J23/76—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
    • B01J23/825—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 gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/802—Visible light

Abstract

The invention relates to a carbon point loaded NiAlLDH/In 2 O 3 Preparation method and application of composite photocatalyst, and NiAlLDH is coated In hollow In 2 O 3 The surface of the nanotube forms a unique heterostructure, and then carries Carbon Dots (CDs), and the prepared CDs-NiAlLDH/In 2 O 3 The composite photocatalyst has the advantages of stable chemical property, high catalytic efficiency and the like. The composite photocatalyst has the advantages of easily available preparation raw materials, low preparation cost, simple process and easily controlled conditions, and has certain research and application values.

Description

Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst
Technical Field
The invention belongs to the technical field of nano material preparation and application, in particular to a Carbon Dot (CD) S ) Loaded NiAl LDH/In 2 O 3 A preparation method and application of a composite photocatalyst.
Background
Currently, world energy consumption is mainly based on fossil fuels. The consumption of large amounts of fossil fuels increases carbon dioxide emissions, leading to increasingly serious energy and environmental problems. Therefore, there is a need to explore an efficient, low cost carbon dioxide abatement process. Many methods of reducing carbon dioxide have been developed including thermochemical, electrochemical, bioelectrochemical and photocatalytic methods, and the like. The photocatalytic reduction of carbon dioxide can store renewable solar energy in fuel, is more energy-saving and environment-friendly, and is a very promising method. Much research has been devoted to constructing efficient photocatalysts to reduce carbon dioxide to high value carbon-based fuels.
Layered Double Hydroxides (LDH) are two-dimensional metal compounds having a unique structure consisting of a metal compound containing M (OH) 6 The octahedral positive charged host layer, interlayer anions and water molecules. Some LDHs show photocatalytic activity, can degrade organic matters, decompose water and reduce CO in the presence of water or hydrogen 2 . LDH is alkaline as a whole, and surface hydroxyl groups are combined with CO 2 Molecular binding favors CO 2 Is a photocatalytic reduction of (a). Meanwhile, the synthesis method of the LDH material is relatively simple. LDH catalysts with different morphologies can be synthesized by adopting various methods and strategies, and the composition, particle size, surface defects and electronic properties of the LDH catalysts can be adjusted to enhance the catalytic effect of the LDH catalysts. Although LDH can be used as a 2D layered material for enhancing photocatalytic activity, it is still affected by factors such as low charge mobility, easy aggregation of nanoplatelets, and high charge recombination rate, which results in low photocatalytic activity itself. Thus, efficient LDH-based composite materials are prepared for solar driven CO 2 Reduction remains a significant challenge.
In general, metal oxides are one of the effective decorative materials for constructing heterojunction catalysts. Wherein In 2 O 3 As a typical metal oxide photocatalyst, the catalyst has proper band gap (-2.8 eV) and excellent visible light absorption capacity, and can be used for photocatalytic hydrogen evolution and CO evolution 2 The method has important significance in reducing and degrading pollutants and the like. More importantly, in 2 O 3 Has unique electron conductivity and corrosion resistance, is favorable for the rapid transfer of photo-generated charges in a heterojunction structure and is suitable for carriersSeparation and transfer play a positive role. Therefore, it is an ideal strategy to select materials with high stability and strong visible light absorption capacity to couple with LDH and construct heterojunction to improve the photocatalytic conversion rate of LDH. In (In) 2 O 3 The photocatalytic performance is improved correspondingly with the formation of the LDH heterostructure, but the stability of the catalyst is poor, nano sheets are still easy to accumulate or agglomerate in the preparation process, the specific surface area and active sites of the catalyst are reduced, and the charge of the catalyst is quickly combined, so that the photocatalytic activity is lower than that of most other LDH-based photocatalytic materials.
Disclosure of Invention
Based on the above problems, it is an object of the present invention to provide a Carbon Dot (CDs) -supported NiAl LDH/In 2 O 3 Preparation method of composite photocatalyst, CDs-NiAl LDH/In prepared by method 2 O 3 Has higher photocatalytic carbon dioxide reduction activity.
The technical scheme of the invention is as follows: CDs-NiAl LDH/In 2 O 3 The preparation method of the composite photocatalyst comprises the following steps:
(1)NiAl LDH/In 2 O 3 preparation of a composite photocatalyst: in is to 2 O 3 Dissolving nanotube In water to obtain In 2 O 3 Adding nickel nitrate and aluminum nitrate into the aqueous solution, stirring to uniformly mix, sequentially adding urea and ammonia fluoride, uniformly stirring, reacting the mixed solution at 120 ℃, centrifuging to obtain precipitate, washing, and drying to obtain NiAl LDH/In 2 O 3 ；
(2) Carbon dot supported NiAl LDH/In 2 O 3 Preparation of a composite photocatalyst: the NiAl LDH/In prepared In the step (1) is mixed with 2 O 3 Dispersing In ethanol, stirring, adding carbon dot ethanol solution into the mixed solution, stirring, washing precipitate with ethanol for several times, and drying to obtain CDs-NiAl LDH/In product 2 O 3 。
In used In the present invention 2 O 3 The preparation method of the nanotube comprises the following steps: weighing indium nitrate hydrate, dissolving in N, N-dimethylformamide solution, stirring to dissolve, addingTerephthalic acid is stirred uniformly at room temperature, the mixed solution is heated In an oil bath at 120 ℃ for reaction for 2 hours, white precipitate is collected by centrifugation after cooling, and is washed with ethanol for multiple times, and is dried at 60-65 ℃ for 10-12 hours to obtain MIL-68 (In); MIL-68 (In) was heated In a muffle furnace at 5℃for min -1 Calcining at 550 ℃ for 2h to obtain hollow In 2 O 3 A nanotube sample; wherein the mass ratio of the indium nitrate hydrate to the terephthalic acid is 1:1.
Further, the mass ratio of nickel nitrate, aluminum nitrate, urea and ammonia fluoride in the step (1) is 0.6-0.8:0.1-0.3:4-5:1-2, preferably 0.7:0.2:4.8:1.9.
Further, in step (1) 2 O 3 The mass ratio of the catalyst to the NiAl LDH is 1:1-3, more preferably 1:1-1.5, and still more preferably 1:1.5; wherein In is 2 O 3 The concentration of the aqueous solution is 0.4-1.25 mg/ml.
Further, the ethanol solution of carbon dots in the step (2) is a solution in which carbon dot powder is uniformly dispersed in ethanol at a concentration of 1mg/ml.
Further, the carbon point and NiAl LDH/In the step (2) 2 O 3 The mass ratio of (2) is 1-5:100; further preferably 3 to 5:100; still more preferably 3:100.
CDs-NiAl LDH/In prepared by the invention 2 O 3 The composite photocatalyst is used for photocatalytic carbon dioxide reduction, and further, is used for preparing carbon monoxide and methane by photocatalytic carbon dioxide reduction.
Compared with the prior art, the invention has the technical principle and beneficial effects that:
(1) The NiAl LDH nano-sheets are easy to accumulate or agglomerate In the preparation and application processes, and hollow In 2 O 3 A tubular structure with two open ends of the nanotube may provide an opportunity to complex with other semiconductors on both surfaces of the shell. The invention selectively wraps the NiAl LDH nano-sheet In the hollow In 2 O 3 Around the nanotubes, a unique core-shell heterostructure is formed, ensuring good contact between the materials. This unique structure retains the advantages of the individual components and enhances the synergistic effect between the componentsNot only reduce In 2 O 3 The specific surface area of the nanotubes is lost and also causes multiple reflections and refractions of the incident light in the nanoplatelets, thereby improving the light absorption of the photocatalyst. In addition, in 2 O 3 The hollow structure of the (2) not only can effectively shorten the diffusion distance of the photon-generated carriers from the material phase to the surface and accelerate the separation of electron and hole, but also provides large surface area and rich active sites and accelerates the reaction rate.
(2) CDs show good electron transfer/reservoir characteristics, can effectively inhibit the recombination of photoexcitation electron-hole pairs, and the composite photocatalyst prepared by the method has good stability, has no secondary pollution, and can 3% CDs-NiAl LDH/In within 240min 2 O 3 The CO reduction rate of the photocatalytic carbon dioxide can reach 7.12 mu mol g -1 h -1 ,CH 4 The yield can reach 9.77 mu mol g -1 h -1 。
(3) The preparation method of the composite photocatalyst has the advantages of simplicity, easy control of preparation conditions, no secondary pollution and the like, and has certain research and application values.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 shows pure In prepared In example 1 of the present invention 2 O 3 Pure NiAl LDH, niAl LDH/In 2 O 3 ，CDs-NiAl LDH/In 2 O 3 An X-ray diffraction pattern of the composite photocatalyst;
FIG. 2 shows pure In prepared In example 1 of the present invention 2 O 3 Pure NiAl LDH, niAl LDH/In 2 O 3 ，CDs-NiAl LDH/In 2 O 3 Infrared spectrogram of the composite photocatalyst;
FIG. 3 shows pure In prepared In example 1 of the present invention 2 O 3 Pure NiAl LDH, CDs-NiAl LDH/In 2 O 3 Scanning electron microscope image of composite photocatalyst, wherein (a) is pure In 2 O 3 (b) is a pure NiAl LDH; (c) Is CDs-NiAl LDH/In 2 O 3 ；
FIG. 4 is a schematic illustration of the present inventionExample 1 pure In prepared 2 O 3 ，NiAl LDH/In 2 O 3 A photo-catalytic reduction carbon dioxide rate plot for a pure NiAl LDH;
FIG. 5 shows pure In prepared In example 1 of the present invention 2 O 3 ，NiAl LDH/In 2 O 3 ，CDs-NiAl LDH/In 2 O 3 Photocatalytic reduction carbon dioxide rate plot for pure NiAl LDHs.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are intended to illustrate the invention and not to limit it further.
The method for carrying out photocatalytic carbon dioxide reduction by using the composite photocatalyst in the following embodiment comprises the following steps: 5mg of the sample was weighed and dispersed in 2ml of ethanol, sonicated for 10min, and then the mixed solution was dropped onto a clean glass plate and dried at 65℃for 30min to prepare a uniformly dispersed catalyst sample. The prepared catalyst sample and 30ml deionized water were placed in a Pyrex glass reactor and bubbled with the carbon dioxide system for 30min to ensure anaerobic conditions for 30min. The photocatalysis experiment uses a 300W xenon lamp to simulate the full spectrum of sunlight, and the wavelength range is 200-2500nm. Samples were taken four hours after the reaction was run and detected by gas chromatography (GC-7860 plus, TCD detector).
Example 1
(1) Preparation of Carbon Dots (CDs): two graphite rods are used as carbon sources, and ultrasonic cleaning is carried out in deionized water for 30min to remove surface impurities. Two graphite rods are respectively connected with the anode and the cathode and then inserted into a beaker filled with ultrapure water to serve as an anode and a cathode. The two electrodes were spaced apart by about 7.5cm and protruded outwardly from the electrolyte surface by 3-5cm, and a voltage of 30V was applied between the two electrodes by a DC power supply. And (3) electrolyzing the graphite rod for about half a month, filtering with a chronic quantitative filter paper for three times when the aqueous solution in the beaker turns into brown black, or centrifuging at 22000rpm for about 20min to remove precipitated graphite oxide and larger graphite particles, and finally obtaining the aqueous solution of pure CDs. The CDs aqueous solution was freeze-dried to obtain CDs powder, and dispersed in ethanol for use at a concentration of 1mg/ml.
(2) Indium oxide [ ]In 2 O 3 ) Is prepared from the following steps:
preparation of MIL-68 (In): 500mg of indium nitrate hydrate was weighed out in 150ml of N, N-dimethylformamide solution, stirred for 10 minutes, then 500mg of terephthalic acid was added and stirred at room temperature for 30 minutes. The solution was then heated In an oil bath at 120℃for 2h, cooled and the white precipitate collected by centrifugation, washed with ethanol several times and dried In an oven at 60℃to give MIL-68 (In).
In 2 O 3 Is prepared from the following steps: placing the MIL-68 (In) precursor into a ceramic boat wrapped with tinfoil, and then placing In a muffle furnace at 5deg.C for min -1 Calcining at 550 ℃ for 2h to obtain hollow In 2 O 3 Nanotube samples.
(3) Pure NiAl LDH, niAl LDH/In 2 O 3 Preparation of a composite photocatalyst:
preparation of pure NiAl LDH: 0.21g of Ni (NO) 3 ) 2 ·6H 2 O and 0.09gAl (NO) 3 ) 3 ·9H 2 O was dissolved in 60ml of water and stirred for 10min. 0.2883g of urea and 0.0711g of NH are then added 4 F is added to the suspension in sequence. After stirring at room temperature for 30min, the above mixed solution was reacted at 120℃in an oven for 24h. After the reaction, a precipitate was obtained by centrifugation and repeatedly washed with absolute ethanol and deionized water until the pH of the supernatant reached neutrality, and the precipitate was collected and dried overnight in an oven at 60 ℃. The resulting sample was pure NiAl LDH, which was weighed 75mg by mass.
NiAl LDH/In 2 O 3 -25 preparation of a composite photocatalyst: 25mg of In prepared In the step (2) 2 O 3 The nanotubes were dissolved in 60ml of water and 0.21g Ni (NO) 3 ) 2 ·6H 2 O and 0.09gAl (NO) 3 ) 3 ·9H 2 O, stir for 10min. 0.2883g of urea and 0.0711gNH 4 F is added to the suspension in sequence. After stirring at room temperature for 30min, the above mixed solution was reacted at 120℃in an oven for 24h. After the reaction is finished, obtaining a precipitate through centrifugation, repeatedly washing the precipitate with absolute ethyl alcohol and deionized water until the pH value of supernatant reaches neutrality, collecting the precipitate, and drying the precipitate In a 60 ℃ oven overnight to obtain a sample NiAl LDH/In 2 O 3 -25(25mg In 2 O 3 Calculated, the mass fraction supported in the catalyst was 25%).
NiAl LDH/In 2 O 3 -50 preparation of a composite photocatalyst: 50mg of In prepared In the step (2) 2 O 3 The nanotubes were dissolved in 60ml of water and 0.21g Ni (NO) 3 ) 2 ·6H 2 O and 0.09gAl (NO) 3 ) 3 ·9H 2 O, stir for 10min. 0.2883g of urea and 0.0711gNH 4 F is added to the suspension in sequence. After stirring at room temperature for 30min, the above mixed solution was reacted at 120℃in an oven for 24h. After the reaction is finished, obtaining a precipitate through centrifugation, repeatedly washing the precipitate with absolute ethyl alcohol and deionized water until the pH value of supernatant reaches neutrality, collecting the precipitate, and drying the precipitate In a 60 ℃ oven overnight to obtain a sample NiAl LDH/In 2 O 3 -50(50mg In 2 O 3 Calculated, the mass fraction of the catalyst supported was 40%).
NiAl LDH/In 2 O 3 -75 preparation of a composite photocatalyst: 75mg of In prepared In the step (2) 2 O 3 The nanotubes were dissolved in 60ml of water and 0.21g Ni (NO) 3 ) 2 ·6H 2 O and 0.09gAl (NO) 3 ) 3 ·9H 2 O, stir for 10min. 0.2883g of urea and 0.0711gNH 4 F is added to the suspension in sequence. After stirring at room temperature for 30min, the above mixed solution was reacted at 120℃in an oven for 24h. After the reaction is finished, obtaining a precipitate through centrifugation, repeatedly washing the precipitate with absolute ethyl alcohol and deionized water until the pH value of supernatant reaches neutrality, collecting the precipitate, and drying the precipitate In a 60 ℃ oven overnight to obtain a sample NiAl LDH/In 2 O 3 -75(75mg In 2 O 3 The mass fraction supported in the catalyst after calculation was 50%).
As can be seen from FIG. 4, niAl LDH/In within 240min 2 O 3 Up to a CO rate of 3.65. Mu. Mol g for the photocatalytic carbon dioxide reduction of-50 -1 h -1 ,CH 4 The highest yield can reach 5.08 mu mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Compared with pure In 2 O 3 (CO:3.27μmol g -1 h -1 ，CH 4 :2.16μmol g -1 h -1 ) The two times of the two times are respectively improved by 1.12 times and 2.35 times; compared with NiAl LDH (CO: 2.44. Mu. Mol g -1 h -1 ，CH 4 :0.55μmol g -1 h -1 ) The improvement is 1.50 times and 9.24 times respectively. Thus, it can be seen that the prepared NiAl LDH/In 2 O 3 The composite photocatalyst has higher photocatalytic activity than the pure sample.
(4)CDs-NiAl LDH/In 2 O 3 Preparation of a composite photocatalyst:
1％CDs-NiAl LDH/In 2 O 3 preparation of a composite photocatalyst: 100mg of NiAl LDH/In prepared In the step (3) is added 2 O 3 50 was dispersed in 20ml of ethanol, and after stirring for 10min, 1ml of an ethanol solution (concentration: 1 mg/ml) of CDs was added to the mixed solution. After stirring for 12h, the precipitate was washed with ethanol several times and dried at 60℃to give a sample of 1% CDs-NiAl LDH/In 2 O 3 。
3％CDs-NiAl LDH/In 2 O 3 Preparation of a composite photocatalyst: 100mg of NiAl LDH/In prepared In the step (3) is added 2 O 3 50 was dispersed in 20ml of ethanol, and 3ml of an ethanol solution (concentration: 1 mg/ml) of CDs was added to the mixed solution after stirring for 10 minutes. After stirring for 12h, the precipitate was washed with ethanol several times and dried at 60℃to give 3% CDs-NiAl LDH/In sample 2 O 3 。
5％CDs-NiAl LDH/In 2 O 3 Preparation of a composite photocatalyst: 100mg of NiAl LDH/In prepared In the step (3) is added 2 O 3 50 was dispersed in 20ml of ethanol, and after stirring for 10min, 5ml of an ethanol solution (concentration: 1 mg/ml) of CDs was added to the mixed solution. After stirring for 12h, the precipitate was washed with ethanol several times and dried at 60℃to give a sample of 5% CDs-NiAl LDH/In 2 O 3 。
The composite photocatalyst prepared in example 1 catalyzes CO 2 The reduction performance is shown in FIG. 5. As can be seen from FIG. 5, CDs-NiAl LDH/In within 240min 2 O 3 The CO reduction rate of 3% photocatalytic carbon dioxide can reach 7.12 mu mol g -1 h -1 ,CH 4 The yield can reach 9.77 mu mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the NiAl LDH/In compared to non-carbon-loaded dots 2 O 3 (CO:3.65μmol g - 1 h -1 ，CH 4 :5.08μmol g -1 h -1 ) The improvement is 1.95 times and 1.92 times respectively. Thus, it can be seen that the prepared CDs-NiAl LDH/In 2 O 3 The composite photocatalyst has high photocatalytic activity.
NiAl LDH/In 2 O 3 And CDs-NiAl LDH/In 2 O 3 Component determination of the composite photocatalyst:
pure In prepared In example 1 2 O 3 Pure NiAl LDH, niAl LDH/In 2 O 3 -50 and CDs-NiAl LDH/In 2 O 3 The crystal phase structure of the composite photocatalyst was analyzed by an X-ray diffractometer of Japanese D/MAX2500, wherein the X-ray was Cu target K.alphaThe voltage is 40kV, the current is 100mA, the step size is 0.02 DEG, and the scanning range is5 DEG-80 deg. The X-ray diffraction pattern is shown In figure 1, and the figure shows that the prepared NiAl LDH/In 2 O 3 And CDs-NiAl LDH/In 2 O 3 The characteristic diffraction peaks of the composite photocatalyst, which appear at 11.58 °, 23.13 °, 34.94 °, 39.33 °, 46.82 °, 60.92 ° and 62.25 °, can be seen In the XRD diffractogram of the NiAl LDH to correspond to the (003), (006), (012), (015), (018), (110) and (113) crystal planes of the NiAl LDH, 21.49 °,30.58 °,35.47 °,37.69 °,41.85 °,45.69 °,51.04 °,55.99 ° and 60.68 ° respectively, are In 2 O 3 The characteristic diffraction peaks of (a) correspond to In respectively 2 O 3 (211), (222), (400), (411), (332), (431), (440), (611) and (622) planes. 23 DEG and 42 DEG are characteristic diffraction peaks of CDs corresponding to (002) and (100) crystal planes of CDs, respectively. But CDs-NiAl LDH/In X-ray diffraction pattern 2 O 3 The composite material has no obvious CDs peak, which is related to low CDs load, small volume and the like. Therefore, the composite photocatalyst contains only In 2 O 3 And NiAl LDHs, and does not change the chemical structure and crystal form of both during the recombination process.
Using Thermo FisherThe characteristic functional groups of the composite photocatalyst prepared In example 1 are observed by an rIS 50 infrared spectrometer, the infrared spectrum IS shown In figure 2, and the pure In can be seen from the figure 2 O 3 At 565 and 609cm -1 The peak at this point is due to the stretching vibration of the In-O bond. Pure NiAl-LDH and composite material at 3490 cm and 1630cm -1 The broad peak at this point indicates the presence of O-H bonds and vibration adsorbing water molecules. At 1365cm -1 Peak at site and interlayer NO in layered structure 3 - The bending vibration of the ions is uniform and 800cm -1 The following partial characteristic peaks are derived from lattice vibrations of metal-oxygen (Al-O and Ni-O) and metal-oxygen-metal (Ni-O-Al). Simultaneous observation of NiAl-LDH and In composite material 2 O 3 Indicating successful formation of heterostructures.
Pure In prepared In example 1 was observed by using Quanta 200F-type field emission scanning electron microscope 2 O 3 Pure NiAl LDH, CDs-NiAl LDH/In 2 O 3 The morphology of the composite photocatalyst is shown In FIG. 3, and it can be seen from the graph that In prepared by the embodiment 2 O 3 The morphology of NiAl LDH is a hollow tubular structure, the morphology of NiAl LDH is a flower sphere structure formed by a plurality of ultrathin nano-sheets, and CDs-NiAl LDH/In 2 O 3 The morphology of the composite photocatalyst is that NiAl LDH sheets are uniformly dispersed In hollow rod-shaped In 2 O 3 Surface, and because the size of CDs is too small to be observed.

Claims (6)

1. Carbon point loaded NiAl LDH/In 2 O 3 The preparation method of the composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps: (1) NiAl LDH/In 2 O 3 Preparation of a composite photocatalyst: in is to 2 O 3 Dissolving nanotube In water to obtain In 2 O 3 Adding nickel nitrate and aluminum nitrate into the aqueous solution, stirring to uniformly mix, sequentially adding urea and ammonium fluoride, stirring uniformly, reacting the mixed solution at 120 ℃, centrifuging to obtain precipitate, washing, and drying to obtain NiAl LDH/In 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein In 2 O 3 Mass with NiAl LDHThe ratio is 1:1-3;
(2) Carbon dot supported NiAl LDH/In 2 O 3 Preparation of a composite photocatalyst: the NiAl LDH/In prepared In the step (1) is mixed with 2 O 3 Dispersing In ethanol, stirring, adding carbon dot ethanol solution into the mixed solution, stirring, washing precipitate with ethanol for several times, and drying to obtain CDs-NiAlLDH/In product 2 O 3； Carbon dots and NiAl LDH/In 2 O 3 The mass ratio of (2) is 1-5:100.
2. The carbon dot supported NiAl LDH/In of claim 1 2 O 3 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in (In) 2 O 3 The preparation method of the nano tube comprises the following steps:
weighing indium nitrate hydrate, dissolving In N, N-dimethylformamide solution, stirring and dissolving, adding terephthalic acid, stirring uniformly at room temperature, heating the mixed solution In an oil bath at 120 ℃ for reaction of 2h, cooling, centrifuging and collecting white precipitate, washing with ethanol for multiple times, and drying at 60-65 ℃ for 10-12h to obtain MIL-68 (In); MIL-68 (In) was heated In a muffle furnace at 5℃for min -1 Calcining at 550 ℃ for 2h to obtain hollow In 2 O 3 A nanotube sample; wherein the mass ratio of the indium nitrate hydrate to the terephthalic acid is 1:1.
3. The carbon dot supported NiAl LDH/In of claim 1 2 O 3 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in the step (1), the mass ratio of the nickel nitrate, the aluminum nitrate, the urea and the ammonium fluoride is 0.6-0.8:0.1-0.3:4-5:1-2.
4. The carbon dot supported NiAl LDH/In of claim 1 2 O 3 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in the step (1) 2 O 3 The concentration of the aqueous solution is 0.4-1.25 mg/ml.
5. The carbon dot loading of claim 1NiAl LDH/In 2 O 3 The preparation method of the composite photocatalyst is characterized by comprising the following steps: the ethanol solution of the carbon dots in the step (2) is prepared by uniformly dispersing carbon dot powder in the ethanol solution, wherein the concentration of the carbon dot powder is 1mg/ml.
6. A carbon dot supported NiAl LDH/In prepared by the method of any one of claims 1 to 5 2 O 3 The application of the composite photocatalyst is characterized In that the carbon point loading NiAl LDH/In 2 O 3 The application of the composite photocatalyst in photocatalytic carbon dioxide reduction.
CN202310135329.8A 2023-02-20 2023-02-20 Carbon point loaded NiAl LDH/In 2 O 3 Preparation method and application of composite photocatalyst Active CN116139868B (en)

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