CN115193438B - Indium oxide composite material with nickel nano particles modified on surface and preparation method and application thereof - Google Patents

Indium oxide composite material with nickel nano particles modified on surface and preparation method and application thereof Download PDF

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CN115193438B
CN115193438B CN202210590674.6A CN202210590674A CN115193438B CN 115193438 B CN115193438 B CN 115193438B CN 202210590674 A CN202210590674 A CN 202210590674A CN 115193438 B CN115193438 B CN 115193438B
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indium oxide
composite material
nickel
nano particles
preparation
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CN115193438A (en
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曲家福
李松琦
胡俊蝶
杨晓刚
李长明
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Suzhou University of Science and Technology
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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
    • B01J23/825—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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide

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Abstract

The invention belongs to the technical field of nano composite materials, and particularly relates to an indium oxide composite material with nickel nano particles modified on the surface, a preparation method and application thereof. Dissolving indium salt and 1, 4-phthalic acid, stirring uniformly, heating for reaction, centrifugally drying, calcining for two sections, dispersing in a solvent, adding a nickel-containing precursor, mixing, heating and drying, and calcining the obtained product in different gas atmospheres to obtain the indium oxide composite material with the surface modified nickel nano particles. The composite material of the black hexagonal hollow tubular structure indium oxide surface modified nickel nano particles is a novel composite material with controllable structure, high light absorption efficiency, excellent performance and good stability, and has excellent performance for photo-thermal catalytic carbon dioxide hydrogenation reaction; the preparation method has the advantages of low cost of raw materials, easy acquisition, simple experimental operation, no expensive equipment in the whole process and contribution to industrial production.

Description

Indium oxide composite material with nickel nano particles modified on surface and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to an indium oxide composite material with nickel nano particles modified on the surface, a preparation method and application thereof.
Background
Energy is an important guarantee for promoting social development and scientific and technical progress, along with economic development and rapid industrialization, fossil fuels are consumed in a large amount, the greenhouse effect is caused by serious exceeding of the carbon dioxide content in the atmosphere, and solar-driven photo-thermal catalysis of reduction of carbon dioxide into fuel or commodity chemicals is a promising strategy for meeting global energy demands and simultaneously relieving the greenhouse effect. The reduction of carbon dioxide comprises two parts, namely carbon dioxide activation and catalytic reduction, wherein an active site is required for adsorbing and activating carbon dioxide, and photo-generated electrons are required for catalytic reduction of carbon dioxide. Therefore, the design of high active sites and high surface area catalytic materials to promote carbon dioxide reduction is a focus of attention.
Photo-thermal catalysis has been widely studied in academia as a clean and pollution-free technique since the realization of photo-catalytic water decomposition in 1970. The research field of semiconductor photocatalysis mainly relates to various fields of energy sources, environment and the like, however, thermodynamic analysis shows that the Gibbs free energy of a part of complex chemical reaction is higher and can only be excited by ultraviolet light, so that the utilization of solar spectrum is greatly limited.
The photo-thermal catalysis has three modes, namely a photo-catalysis mode and a thermal catalysis series mode; the second is a photo-driven thermocatalytic reaction in which light only acts as a source of heat, the nature of the reaction being, in terms of reaction mechanism, a thermocatalytic process. The third is a thermally assisted photocatalytic reaction. Light plays a decisive role in the reaction process, and heating can promote the improvement of the reaction rate.
The photocatalysis is mainly that the semiconductor photocatalyst is excited to generate electron holes under the action of illumination, and then the electron holes are respectively migrated to the surface of the catalyst to participate in oxidation-reduction reaction, and the reaction path is different from that of thermocatalysis. The main mode of determining photo-thermal catalysis is as follows: 1. performance versus temperature curves under photoreaction and dark reaction conditions. The catalyst surface temperature was tested by thermocouple or the like to see if the photocatalytic and thermocatalytic product selectivities and yields were consistent under the same temperature conditions, and if there was no difference, the portion of the light in which the light might only act as heating ultraviolet light might not even be utilized. If the differences are large, it is stated that the light effect and the heat effect are significantly different. 2. Activation energy+photon utilization calculation. Whether the surface temperature measurement of the catalyst is accurate. Macroscopic thermocouples and other measurement methods cannot reflect the local temperature of the nanoparticles, and the change of the local temperature may lead to performance improvement.
When the photon energy is smaller than the silicon bandgap, light participates in the reaction mainly by providing a form of thermal energy; when the photon energy is greater than the silicon bandgap, a portion of the photon-excited catalyst generates electron-hole pairs that participate in the reaction, but most of them re-provide heat to the reaction by thermal relaxation.
Indium oxide is a highly efficient thermochemical catalyst with high selectivity to carbon monoxide, but its broad bandgap characteristics (3.2 eV) lead to its adverse effects on light absorption and photothermal conversion, limiting its application to photothermal catalysis.
CN113398944B discloses a bismuth vanadate surface-modified nickel cobaltate spinel composite material, and preparation and application thereof, wherein the preparation method of the bismuth vanadate surface-modified nickel cobaltate spinel composite material comprises the steps of adding bismuth nitrate and ammonium metavanadate into an acidic solution, adjusting the pH value to 0.25-2, and heating and reacting to obtain decahedral bismuth vanadate; dispersing the obtained decahedral bismuth vanadate in a solvent, adding a nickel cobaltate precursor, heating for reaction, centrifuging, drying and calcining the obtained product. The bismuth vanadate surface-modified nickel cobaltate spinel composite material is a novel composite material with controllable structure, high visible light absorption efficiency, excellent performance and good stability, and has excellent performance on photocatalytic water oxidation.
CN2021114345252 discloses a metal organic framework derived (MOF) carbon cloth surface modified nickel cobaltate nano-sheet array composite material, preparation and application thereof, specifically, the carbon cloth is put into a mixed solution of nitric acid and hydrochloric acid, soaked, put into a buffer solution, added with dopamine hydrochloride, and reacted to obtain cc@pda; immersing the CC@PDA into a soluble cobalt salt solution, adding a dimethyl imidazole solution, and reacting to obtain CC@Co-MOF; adding a soluble nickel salt solution, and calcining after the reaction; placing the calcined product into NaBH 4 And in the solution, reacting to obtain the carbon cloth surface modified nickel cobaltate nano-sheet array composite material. The composite material of the invention is a novel composite material with controllable structure, large specific surface area, excellent performance and good stability, and can catalyze CO by light 2 The reduction has excellent properties.
CN114225947a discloses a photocatalytic CO 2 Graphite alkyne composite material for preparing fuel by reductionThe graphite alkyne composite material is formed by compounding a precursor solution of NiIn2S4 and graphite alkyne, wherein the precursor solution of NiIn2S4 comprises a solvent, nickel salt, indium salt and a sulfur source; the NiIn2S 4/graphite alkyne composite material has the characteristics of excellent thermal stability, ultrahigh carrier mobility, high specific surface area, natural intrinsic band gap and the like of graphite alkyne, integrates the high catalytic activity of NiIn2S4, widens the visible light absorption range of a heterojunction formed by the NiIn2S4 and the graphite alkyne, and combines the NiIn2S4 and the graphite alkyne to improve photocatalytic CO 2 Reducing.
CN113740390a discloses a nickel doped indium oxide nanoparticle, a preparation method and application thereof. The nickel doped indium oxide nanoparticles consist of indium oxide with nickel doped in the lattice of the indium oxide. The preparation method comprises the steps of carrying out solvothermal reaction on an indium source, a nickel source and an organic ligand to obtain an In/Ni bimetallic MOF precursor, and carrying out annealing treatment on the In/Ni bimetallic MOF precursor to obtain nickel-doped indium oxide nano particles; wherein the molar amount of the indium source is larger than the molar amount of the nickel source. The provided nickel doped indium oxide nano particles are used for preparing gas sensitive element pair NO 2 The gas has sensitivity.
Considering that the diffusion length from the body to the surface can be reduced by constructing the hollow structure, accelerating electron-hole separation, multiple light scattering/reflection in the internal voids can increase light absorption, while increasing the surface area can promote carbon dioxide adsorption and surface catalysis. The nickel-loaded nano particles can provide more active sites, more oxygen vacancy active sites can be formed in the material by further utilizing hydrogen reduction, the material is changed into black, the light absorption range can be enlarged, and the photo-thermal catalytic performance is improved.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of an indium oxide composite material with surface modified nickel nano particles, which comprises the following steps:
s11: adding indium salt and 1, 4-phthalic acid into an organic solvent, and heating for reaction to obtain a hexagonal prism indium oxide metal organic framework material;
s12: performing two-stage calcination on the hexagonal prism indium oxide metal organic framework material to obtain hexagonal hollow tubular structure indium oxide;
s13: placing the hexagonal hollow tubular structure indium oxide in a mixed gas atmosphere for reduction reaction to obtain black hexagonal hollow tubular indium oxide; the mixed gas consists of hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is 4-6:96-94;
s14: and mixing the black hexagonal hollow tubular indium oxide and the nickel-containing precursor in water, drying and calcining to obtain the indium oxide composite material with the surface modified nickel nano particles.
Preferably, the indium salt is indium nitrate or indium chloride.
Preferably, the mass ratio of the indium salt to the 1, 4-phthalic acid is 11-13: 11 to 13.
Further, the mass ratio of the indium salt to the 1, 4-phthalic acid is 1:1.
preferably, in the step S11, the addition amount of the solute is 22-26 mg/7-9 ml of the organic solvent to the mixed solution obtained by adding the indium salt and the 1, 4-phthalic acid to the organic solvent.
Further, in the mixed solution obtained by adding the indium salt and 1, 4-phthalic acid to the organic solvent, when the addition amount of the indium salt is 60mg and the addition amount of the 1, 4-phthalic acid is 60mg, the volume addition amount of the organic solvent is 35 to 45ml.
Specifically, in the mixed solution obtained by adding the indium salt and 1, 4-phthalic acid to the organic solvent, when the addition amount of the indium salt was 60mg and the addition amount of the 1, 4-phthalic acid was 60mg, the volume addition amount of the organic solvent was 40ml.
Preferably, the organic solvent is N, N-dimethylformamide.
Preferably, in the step S11, the heating reaction is performed at 115 to 125 ℃ for 20 to 60 minutes.
Further, the temperature of the heating reaction is 120 ℃ and the time is 30min.
Further, in the step S11, the product obtained after the heating reaction is washed with ethanol, and then is put into an oven for drying; the drying temperature is 60-90 ℃.
Specifically, the drying temperature is 80 ℃.
Preferably, in the step S12, the temperature rising rate of the first stage calcination of the two stages of calcination is 1-5 ℃/min, the temperature is 110-130 ℃, and the heat preservation time is 1-3 h; the temperature rising rate of the second stage calcination is 1-5 ℃/min, the temperature is 450-550 ℃, and the heat preservation time is 1-3 h; the gas atmosphere of the two-stage calcination is air.
Further, in the step S12, the temperature rising rate of the first stage calcination of the two-stage calcination is 2 ℃/min, the temperature is 120 ℃, and the heat preservation time is 2h; the temperature rising rate of the second stage calcination is 2 ℃/min, the temperature is 500 ℃, and the heat preservation time is 2h.
Preferably, in the step S13, the temperature of the reduction reaction is 200 to 400 ℃ and the time is 1 to 3 hours.
Further, in the step S13, the temperature of the reduction reaction is 300 ℃ and the time is 2 hours.
Preferably, in the step S13, the concentration of the hydrogen gas is 5vt%.
Preferably, in the step S14, the mass of nickel in the nickel-containing precursor is 2 to 20% of the mass of the black hexagonal hollow tubular indium oxide.
Further, the nickel-containing precursor is nickel acetylacetonate or nickel nitrate.
Preferably, in the step S14, the drying temperature is 60 to 90 ℃.
Further, in the step S14, the drying temperature is 80 ℃.
Preferably, in the step S14, the calcining conditions are as follows: the gas atmosphere consists of hydrogen and inert gas, and the concentration of the hydrogen is 0-6 vt; the temperature rising rate is 1-5 ℃/min, the temperature is 200-400 ℃ and the time is 1-3 h.
Preferably, in the step S14, the calcining conditions are as follows: the gas atmosphere is composed of an inert gas, excluding hydrogen; the temperature rising rate is 2 ℃/min, the temperature is 300 ℃ and the time is 2h.
Preferably, in the step S14, the calcining conditions are as follows: the gas atmosphere consists of hydrogen and inert gas, wherein the concentration of the hydrogen is 5 vt; the temperature rising rate is 2 ℃/min, the temperature is 300 ℃ and the time is 2h.
The invention also provides an indium oxide composite material with the surface modified nickel nano particles prepared by the preparation method.
The invention also provides application of the indium oxide composite material with the surface modified nickel nano particles in photo-thermal catalysis of carbon dioxide reduction.
Preferably, the application of the photo-thermal catalytic carbon dioxide reduction comprises the following steps:
s21: dispersing the indium oxide composite material with the nickel nano particles on the surface into an aqueous solution of alcohol, coating the aqueous solution on conductive glass, and drying to obtain composite application conductive glass;
s22: placing the composite application conductive glass in a glass reactor, and filling CO 2 And H 2 Then using a 300W xenon lamp to carry out photo-thermal catalytic carbon dioxide reduction reaction;
s23: analysis of CO by on-line gas chromatography 2 Conversion, curve CO and CH are drawn 4 Standard curve to obtain CO and CH 4 Is a yield of (2).
Specifically, the application of the photo-thermal catalytic carbon dioxide reduction comprises the following steps:
dispersing 40-60 mg of material in 3-7 ml of mixed solvent of water and ethanol, uniformly dispersing the material by ultrasonic, dripping the material on circular conductive glass (radius of 1.9 cm), drying at 50 ℃, transferring the obtained conductive glass into a customized glass reactor, sealing, degassing the reactor to remove air in the system, and injecting CO into the reactor after the completion of the process 2 And H 2 (v: v=1:4) until the pressure reached 90kPa, performance test was performed using a 300W xenon lamp as simulated sunlight, light was collected using a convex lens and temperature was monitored using an infrared temperature sensing device, and CO was analyzed by an on-line gas chromatograph with Flame Ionization Detector (FID) and hot wire heat detector (TCD) 2 Transformation conditions (every 1 h). After the test is finished, CO and CH are prepared 4 Standard curve, and according to the standard curve, obtaining CO and CH of the material 4 Yield.
According to the invention, indium nitrate or indium chloride and 1, 4-phthalic acid are used as solutes, N-dimethylformamide is used as a solvent, a hexagonal prism indium oxide metal organic framework material is prepared by a simple oil bath method, and is converted into hexagonal hollow tubular structure indium oxide by two-stage calcination, and finally, the hexagonal hollow tubular structure indium oxide is obtained by high-temperature reduction under the hydrogen atmosphere, so that the hexagonal hollow tubular structure indium oxide has the advantages of controllable structure, good repeatability and easiness in preparation. Then taking the material as a carrier material, taking nickel acetylacetonate or nickel nitrate as a precursor, and preparing the composite material of the black hexagonal hollow tubular structure indium oxide surface modified nickel nano particles by high-temperature calcination under the protection of inert gas or high-temperature reduction under the hydrogen atmosphere. The hollow structure inhibits the recombination of photo-generated electrons and holes, and the modification and hydrogen reduction of the high-surface-area nickel nano particles provide a large number of active sites, so that the black characteristic enlarges the light absorption range and greatly improves the photo-thermal catalytic performance.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the raw materials used in the preparation method of the composite material with the black hexagonal hollow tubular structure indium oxide surface modified nickel nano particles disclosed by the invention are low in cost, easy to obtain, simple and convenient in experimental operation, and expensive equipment is not used in the whole process, so that the preparation method is beneficial to industrial production;
2. the composite material of the black hexagonal hollow tubular structure indium oxide surface modified nickel nano particles disclosed by the invention is a novel composite material with controllable structure, high light absorption efficiency, excellent performance and good stability, has excellent performance on photo-thermal catalytic carbon dioxide reduction, can be used for preparing fuel or commodity chemicals, and is very beneficial to industrial application.
3. Conventional In 2 O 3 The material is light yellow powder, and can increase CO by introducing oxygen defect 2 Can promote the adsorption of In at the same time 2 O 3 The light absorption capacity of the material, the color is changed from pale yellow to black.
Drawings
FIG. 1 is h-In example 1 2 O 3 Is transmitted through (a)Electron Microscopy (TEM);
FIG. 2 is a diagram of h-In example 1 2 O 3 Scanning Electron Microscope (SEM);
FIG. 3 is h-In example 2 2 O 3-Ov A Transmission Electron Microscope (TEM);
FIG. 4 is a diagram of h-In example 2 2 O 3-Ov Scanning Electron Microscope (SEM);
FIG. 5 is Ni/h-In example 3 2 O 3-Ov A Transmission Electron Microscope (TEM);
FIG. 6 is Ni/h-In example 3 2 O 3-Ov Scanning Electron Microscope (SEM);
FIG. 7 is a photo-thermal catalytic CO of the material prepared in example 9 2 And (3) an effect diagram of hydrogenation.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
Hexagonal hollow tubular structure indium oxide (h-In) 2 O 3 ) The preparation method comprises the following specific steps:
adding 60mg of indium nitrate and 60mg of 1, 4-phthalic acid into 40ml of N, N-dimethylformamide, stirring at room temperature, transferring into an oil bath pot, reacting for 30min at 120 ℃, washing a reaction product with ethanol, drying In an oven, further calcining the dried product In a tubular furnace at 120 ℃ for 2h at a heating rate of 2 ℃/min, then heating to 500 ℃ for 2h at a heating rate of 2 ℃/min, and obtaining In 2 O 3 . In obtained 2 O 3 The TEM image of (1) is shown In FIG. 1, the SEM image is shown In FIG. 2, and In can be seen from the figure 2 O 3 Is successfully prepared and has uniform size.
Example 2
Black hexagonal hollow tubular indium oxide (In 2 O 3-Ov ) The preparation method comprises the following specific steps:
conventional In 2 O 3 The material is light yellow powder, and can increase CO by introducing oxygen defect 2 Can promote the adsorption of In at the same time 2 O 3 The light absorption capacity of the material, the color is changed from pale yellow to black. First, taking In prepared as described above 2 O 3 100-300mg of the material is placed in a crucible, the crucible is placed in a 5% hydrogen atmosphere for calcination, the morphology of the material is precisely controlled by regulating and controlling the reduction temperature, so that the material maintains the original hexagonal hollow tubular structure, and experiments find that the optimal temperature is 300 ℃ and the heating rate is 2 ℃/min. The obtained material is like TEM and SEM of FIG. 3 and FIG. 4, and it can be seen that the morphology of the material is not changed after the oxygen defect is introduced.
Example 3
Composite material (Ni/h-In) of black hexagonal hollow tubular structure indium oxide surface modified nickel nano particle 2 O 3-Ov ) The preparation of the composite material comprises the following specific steps:
100mg of h-In prepared In example 2 above was taken 2 O 3-Ov And 24.65mg of nickel acetylacetonate hexahydrate are dispersed into 10ml of water, then stirred for 20 to 40 minutes under vacuum condition, after the completion, dried In water bath at 60 to 90 ℃, the dried sample is put into a tubular furnace, and calcined for 1 to 3 hours at 200 to 400 ℃ under the protection of inert gas, the heating rate is 1 to 5 ℃/min, and finally the Ni/h-In is obtained 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading amounts 2 O 3-Ov And (3) a composite material, namely an indium oxide composite material with the surface modified with nickel nano particles.
The Ni/h-In obtained 2 O 3-Ov The TEM image of the composite material is shown in fig. 5, and the SEM image is shown in fig. 6, from which it can be seen that the nickel nanoparticles are in the form of particles and successfully modified on the hexagonal hollow structure indium oxide.
Example 4
Composite material (Ni/h-In) of black hexagonal hollow tubular structure indium oxide surface modified nickel nano particle 2 O 3-Ov ) The preparation of the composite material comprises the following specific steps:
100mg of the above-mentioned preparation of example 2 was takenh-In 2 O 3-Ov And 21.78mg of nickel acetylacetonate is dispersed into 10ml of water, then stirred for 20 to 40 minutes under vacuum condition, dried In water bath at 60 to 90 ℃ after the completion, the dried sample is put into a tube furnace, calcined for 1 to 3 hours at 200 to 400 ℃ under the protection of inert gas, and the heating rate is 1 to 5 ℃/min, and finally the Ni/h-In is obtained 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading amounts 2 O 3-Ov A composite material. The Ni/h-In obtained 2 O 3-Ov The TEM image of the composite material is shown in fig. 5, and the SEM image is shown in fig. 6, from which it can be seen that the nickel nanoparticles are in the form of particles and successfully modified on the hexagonal hollow structure indium oxide.
Example 5
Composite material (Ni/h-In) of black hexagonal hollow tubular structure indium oxide surface modified nickel nano particle 2 O 3-Ov ) The preparation of the composite material comprises the following specific steps:
100mg of h-In prepared In example 2 above was taken 2 O 3-Ov And 24.65mg of nickel acetylacetonate hexahydrate is dispersed In 10ml of water, then stirred for 20min under vacuum condition, dried In water bath at 60 ℃ after the completion, the dried sample is put into a tube furnace, calcined for 1h at 200 ℃ under the protection of inert gas, and the heating rate is 1 ℃/min, and finally the Ni/h-In is obtained 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading amounts 2 O 3-Ov And (3) a composite material, namely an indium oxide composite material with the surface modified with nickel nano particles.
Example 6
Composite material (Ni/h-In) of black hexagonal hollow tubular structure indium oxide surface modified nickel nano particle 2 O 3-Ov ) The preparation of the composite material comprises the following specific steps:
100mg of h-In prepared In example 2 above was taken 2 O 3-Ov And 21.78mg of nickel acetylacetonate was dispersed in 10ml of water, followed by stirring under vacuum for 40min, after completion, drying in a water bath at 90℃and placing the dried sample in a tube furnaceCalcining for 3 hours at 400 ℃ under the protection of inert gas, wherein the heating rate is 5 ℃/min, and finally obtaining Ni/h-In 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading amounts 2 O 3-Ov A composite material.
Example 7
Composite material (Ni/h-In) of black hexagonal hollow tubular structure indium oxide surface modified nickel nano particle 2 O 3-Ov ) The preparation of the composite material comprises the following specific steps:
100mg of h-In prepared In example 2 above was taken 2 O 3-Ov And 24.65mg of nickel acetylacetonate hexahydrate is dispersed In 10ml of water, then stirred for 40min under vacuum condition, dried In water bath at 90 ℃, and the dried sample is put into a tube furnace to be calcined for 3h at 400 ℃ under the protection of inert gas, and the heating rate is 5 ℃/min, thus finally obtaining Ni/h-In 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading amounts 2 O 3-Ov And (3) a composite material, namely an indium oxide composite material with the surface modified with nickel nano particles.
Example 8
Composite material (Ni/h-In) of black hexagonal hollow tubular structure indium oxide surface modified nickel nano particle 2 O 3-Ov ) The preparation of the composite material comprises the following specific steps:
100mg of h-In prepared In example 2 above was taken 2 O 3-Ov And 21.78mg of nickel acetylacetonate is dispersed into 10ml of water, then stirring is carried out for 20min under vacuum condition, after the completion, water bath drying is carried out at 60 ℃, the dried sample is put into a tube furnace, and under the protection of inert gas, calcination is carried out at 200 ℃ for 1h, the heating rate is 1 ℃/min, and finally the Ni/h-In is obtained 2 O 3-Ov Composite material and by adjusting Ni 2+ The precursor dosage is used to obtain Ni/h-In with different loading amounts 2 O 3-Ov A composite material.
Example 9
Photo-thermal catalysis of CO under visible light conditions 2 The performance test comprises the following specific steps:
the materials obtained in examples 1 to 3 were evaluated on-line by LabSolar-6A (Porphy, beijing) system for photo-thermal catalysis of CO 2 And (5) testing hydrogenation performance. Dispersing 50mg of material in 5ml of mixed solvent of water and ethanol, uniformly dispersing by ultrasonic, dripping on round (radius of 1.9 cm) conductive glass, oven drying at 50deg.C, transferring the obtained conductive glass into a customized glass reactor, sealing, degassing to remove air in the system, and injecting CO into the reactor 2 And H 2 (v: v=1:4) until the pressure reached 90kPa, performance testing was performed using a 300W xenon lamp as simulated sunlight, condensing light with a convex lens and monitoring temperature with an infrared temperature sensing device, CO was analyzed by an on-line gas chromatograph (GC D7900P) with FID and TCD detectors 2 Transformation conditions (every 1 h). After the test is finished, CO and CH are prepared 4 Standard curve, and according to the standard curve, obtaining CO and CH of the material 4 Yield. FIG. 7 shows the photo-thermal catalysis of CO for the materials prepared in examples 1 to 3 2 And (3) an effect diagram of hydrogenation. As can be seen from FIG. 7, ni/h-In 2 O 3-Ov The composite material has excellent photo-thermal catalytic CO 2 Hydrogenation Activity, wherein the yield of the optimal catalyst CO is 180 mmol.g.h -1 The composite material has the advantages of excellent performance, good stability, simple preparation process, low raw material price and easy industrial production.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (5)

1. The preparation method of the indium oxide composite material with the surface modified with the nickel nano particles for photo-thermal catalytic carbon dioxide reduction is characterized by comprising the following steps of:
s11: adding indium salt and 1, 4-phthalic acid into an organic solvent, and heating for reaction to obtain a hexagonal prism indium oxide metal organic framework material;
s12: performing two-stage calcination on the hexagonal prism indium oxide metal organic framework material to obtain hexagonal hollow tubular structure indium oxide; the first stage calcination temperature of the two stages of calcination is 110-130 ℃ and the time is 1-3 h; the second-stage calcination temperature is 450-550 ℃ and the time is 1-3 h;
s13: placing the hexagonal hollow tubular structure indium oxide in a mixed gas atmosphere for reduction reaction to obtain black hexagonal hollow tubular indium oxide; the mixed gas consists of hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is 4-6:96-94; the temperature of the reduction reaction is 200-400 ℃ and the time is 1-3 hours;
s14: mixing the black hexagonal hollow tubular indium oxide and a nickel-containing precursor in water, drying and calcining to obtain an indium oxide composite material with the surface modified nickel nano particles;
in the step S14, the mass of nickel in the nickel-containing precursor is 2-20% of the mass of the black hexagonal hollow tubular indium oxide; the nickel-containing precursor is nickel acetylacetonate; the conditions of the calcination are as follows: the gas atmosphere is composed of inert gas; the temperature is 200-400 ℃ and the time is 1-3 h.
2. The preparation method of claim 1, wherein the mass ratio of the indium salt to the 1, 4-phthalic acid is 11-13: 11-13.
3. The method according to claim 1, wherein in the step S11, the heating reaction is performed at 115 to 125 ℃ for 20 to 60 minutes.
4. An indium oxide composite material of surface-modified nickel nanoparticles prepared by the preparation method of any one of claims 1 to 3.
5. The use of the indium oxide composite material with the surface modified with nickel nano particles as claimed in claim 4 in photo-thermal catalytic reduction of carbon dioxide.
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