CN114797932A - Bimetal 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof - Google Patents
Bimetal 3D unique honeycomb-shaped carbon dioxide reduction catalyst and preparation method and application thereof Download PDFInfo
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- CN114797932A CN114797932A CN202210315844.XA CN202210315844A CN114797932A CN 114797932 A CN114797932 A CN 114797932A CN 202210315844 A CN202210315844 A CN 202210315844A CN 114797932 A CN114797932 A CN 114797932A
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- honeycomb
- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 230000009467 reduction Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
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- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
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- 235000020188 drinking water Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 20
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- 230000001699 photocatalysis Effects 0.000 abstract description 14
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- 239000010941 cobalt Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000012546 transfer Methods 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
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Abstract
The invention discloses a bimetal 3D unique honeycomb-shaped carbon dioxide reduction catalyst and a preparation method and application thereof. The invention obtains the 3D unique honeycomb composite material by carrying out simple polymer high-temperature heat treatment on a specific carbon source material, cobalt and iron compounds, namely the composite material has a structure consisting of CoFe alloy nanoparticles and a 3D honeycomb nitrogen-doped graphite carbon framework, and the composite material is irradiated by visible light with the wavelength of 200-800nmFor photocatalytic CO 2 In the reduction, CH 4 The maximum yields of CO and 58.53. mu. mol g, respectively ‑1 And 54.07. mu. mol. g ‑1 . The preparation method provided by the invention is simple to operate, low in cost and convenient to popularize.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a method for preparing a carbon dioxide catalyst by a simple high-temperature heat treatment method of a polymer.
Background
Industrial processCarbon dioxide (CO) produced by burning fossil fuel 2 ) Emissions are a major cause of global warming, and photocatalytic carbon dioxide emission reduction has received wide attention as a possible green technology in the production of fuels (CH) 4 ,CH 3 OH) and valuable commodity chemicals (CO, HCOOH) while reducing anthropogenic carbon dioxide emissions. Despite the great amount of work done to adjust the morphology and structure of catalysts to improve their catalytic activity, there are still serious challenges of large overpotential, poor selectivity, etc. There is a pressing need to design a catalyst with higher energy efficiency, selectivity and durability.
At present, three-dimensional transition non-noble metals, particularly Fe, Co, Ni and derivatives thereof, have high catalytic activity for energy conversion reaction, and are considered to be most promising substitutes for noble metals such as Pt. However, the activity and even the stability of a single three-dimensional transition metal material under certain conditions are not sufficient to catalyze the long-term operation of electrochemical reactions.
The existing preparation method of the carbon dioxide photocatalyst has the problems of complex process, harsh reaction conditions, over-high test temperature and the like, and the development of a preparation method of the carbon dioxide catalyst which is easy to obtain raw materials, mild in reaction conditions and environment-friendly is urgently needed.
Disclosure of Invention
It is an object of the present invention to provide a method for preparing carbon dioxide (CO) by a simple high-temperature heat treatment of a polymer 2 ) The method of the catalyst can reduce greenhouse gas CO in the atmosphere 2 And simultaneously can make CO under the condition of visible light 2 Conversion to CO and CH 4 The available energy source.
The invention also aims to provide a nitrogen-doped graphite carbon framework composite material with embedded CoFe alloy nanoparticles in a 3D honeycomb porous structure.
The invention also aims to provide application of the CoFe alloy nanoparticle embedded 3D honeycomb porous nitrogen-doped graphite carbon frame composite material in photocatalytic reduction of carbon dioxide.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a bimetallic 3D unique honeycomb-shaped reduced carbon dioxide catalyst, comprising the steps of:
(1) dissolving cobalt-iron alloy nanoparticles and a carbon material of a 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework in water, uniformly stirring at room temperature, heating, stirring and drying the mixture to form reddish brown powder, thereby obtaining a precursor of the composite material with the CoFe nanoparticles embedded in the 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework;
(2) and (2) calcining the dried sample obtained in the step (1) in a tubular furnace under the protection of inert gas to obtain the CoFe nano-particles embedded 3D honeycomb porous nitrogen-doped graphite carbon frame composite material.
Further, the cobalt-iron alloy nanoparticles are composed of cobalt salt and iron salt; the cobalt salt is selected from one or two of cobalt acetate and cobalt nitrate, and is preferably cobalt nitrate; the iron salt is selected from one or two of ferric chloride and ferric nitrate, and is preferably ferric nitrate.
Furthermore, the mass ratio of the cobalt salt to the iron salt is 3-1: 1-3. Preferably, the mass ratio of the cobalt salt to the iron salt is 1: 1.
Further, the carbon material of the 3D honeycomb-shaped porous nitrogen-doped graphitic carbon framework is selected from at least one of melamine, urea, and polyvinylpyrrolidone. Preferably, the carbon material is polyvinylpyrrolidone.
Further, the mass ratio of the cobalt-iron alloy nanoparticles to the carbon material is 4-1: 1-4. Preferably, the mass ratio of the cobalt-iron alloy nanoparticles to the carbon material is 3: 2.
Further, the water is selected from any one of distilled water, tap water, drinking water and deionized water, and preferably deionized water.
Further, the heating and stirring temperature in the step (1) is 95 ℃; in the step (2), the calcining temperature is 500-1100 ℃, the heating rate is 1-10 ℃/min, and the constant temperature time is 0.5-2 h. Preferably, the heating rate is 5 ℃/min, the calcining temperature is 800 ℃, and the constant temperature time is 1 h.
Further, the inert gas is carbon dioxide gas, nitrogen gas or argon gas. Preferably nitrogen.
In a second aspect, the present invention provides a bimetallic 3D unique honeycomb-shaped reduced carbon dioxide catalyst prepared using the method of the first aspect.
Further, the method for preparing the photocatalytic carbon dioxide reduction film by using the bimetallic 3D unique honeycomb carbon dioxide reduction catalyst comprises the following steps: placing the reduced carbon dioxide photocatalyst of the second aspect into a glass culture dish, adding deionized water, wherein the mass (mg)/volume (ml) ratio of the reduced carbon dioxide photocatalyst to the deionized water is 10:1, ultrasonically dispersing the catalyst, placing the culture dish into an oven, drying at 50-80 ℃, and finally uniformly distributing the deionized water on the surface of the dried catalyst to obtain the photocatalytic carbon dioxide reduction film.
In a third aspect, the invention provides the use of the bimetallic 3D unique honeycomb-shaped carbon dioxide reduction catalyst of the second aspect in reducing carbon dioxide.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the 3D unique honeycomb-shaped reduced carbon dioxide photocatalyst composite material provided by the invention comprises the following components in parts by weight: the 3D honeycomb structure of the CoFe/N-GC catalyst is helpful for absorbing light, and the charge transfer property is enhanced;
(2) 3D cellular structure and high specific surface area of CoFe/N-GC to CO 2 Reduction provides abundant adsorption, activation and reaction sites;
(3) photoelectrons in a 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework (N-GC) can be transferred to CoFe alloy nanoparticles after being compounded with the N-GC, so that more effective charge separation is realized;
(4) the 3D unique honeycomb-shaped reduced carbon dioxide photocatalyst composite material provided by the invention is used for photocatalytic CO 2 Reduction, no need of a heating system, detection at room temperature, low working temperature, mild operating conditions and simple operation;
(5) the 3D unique honeycomb-shaped reduced carbon dioxide photocatalyst composite material provided by the invention is used for photocatalytic CO 2 The reduction can be carried out at room temperature of 20-40 ℃, and the composite material is used for photocatalysis CO under the irradiation of visible light with the wavelength of 200-800nm 2 In the reduction, CH 4 The maximum yields of CO and 58.53. mu. mol g, respectively -1 And 54.07. mu. mol. g -1 And has high stability.
(6) The invention adopts cobalt and iron bimetallic nano-particles to prepare the catalyst, can utilize the synergistic effect between the metal content and the carrier, and is mainly represented as follows: the method has the advantages that firstly, the accelerated charge transfer behavior caused by the photoelectron secondary transfer on the surface of the FeCo alloy nanoparticle is realized; the other is a 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework which provides a carrier for fast electron transmission and has high specific surface area of CO 2 A large number of adsorption sites are provided. Therefore, the 3D unique honeycomb-shaped reduced carbon dioxide photocatalyst shows good reaction kinetics, higher activity and high photocatalytic CO 2 And (4) reducing efficiency.
(7) The preparation method of the composite material provided by the invention is simple to operate, low in cost and convenient to popularize.
Drawings
FIG. 1X-ray diffraction pattern of a precursor of a CoFe alloy nanoparticle composite obtained in example 1, calcined at 800 ℃;
FIG. 2 is a scanning electron microscope image of a precursor of the CoFe alloy nanoparticle composite material obtained in example 1, which is baked at 600 ℃;
FIG. 3 is a scanning electron microscope image of the CoFe alloy nanoparticle composite material obtained in example 1, in which the precursor is calcined at 700 ℃;
FIG. 4 is a scanning electron microscope image of a CoFe alloy nanoparticle composite material precursor obtained in example 1 calcined at 800 ℃;
FIG. 5 is a scanning electron microscope image of the CoFe alloy nanoparticle composite material obtained in example 1, in which the precursor is calcined at 900 ℃;
FIG. 6 is a scanning electron microscope image of the CoFe alloy nanoparticle composite material obtained in example 1, in which the precursor is calcined at 1000 ℃;
FIG. 7 is a projection electron microscope image of the precursor of the CoFe alloy nanoparticle composite material obtained in example 1, which is baked at 800 ℃;
fig. 8 is a photocatalyst film of the porous nitrogen-doped graphitic carbon-frame composite with CoFe alloy nanoparticles embedded in 3D honeycombs obtained in example 6.
FIG. 9 shows CO and CH of CoFe alloy nanoparticles embedded in 3D honeycomb porous nitrogen-doped graphite carbon frame composite material obtained in examples 1-5 under visible light irradiation for 7 hours 4 And (5) comparing the yield. (wherein A:600 ℃, B:700 ℃, C:800 ℃, D:900 ℃, E:1000 ℃).
The photocatalytic CO calcined at 800 ℃ in the precursor of the CoFe alloy nanoparticle composite material is found by FIG. 9 2 The reducing properties are best.
Detailed Description
The present invention is further described in detail with reference to the following specific examples and the attached drawings, but those skilled in the art should understand that the specific examples of the present invention do not limit the present invention in any way, and any equivalent substitutions made on the basis of the present invention are within the protection scope of the present invention, and for the process parameters not particularly noted can be made with reference to the conventional techniques.
The material characterization instrument was as follows: field Emission Scanning Electron Microscope (Field Emission Scanning Electron Microscope, SEM, MIRA3),transmission electron microscope(Transmission Electron Microscopy,JEM-2100),X-Ray diffractometer (XPert Pro), Raman spectrometer Raman Spectrometer,RM1000),
The product was characterized as follows: the CO is analyzed by The Pofilly full glass automatic on-line trace gas analysis system (The reaction system is connected to an all-glass on-line detection system, Labsolar 6A (Beijing Perfectlight Technology Co., Ltd.) and gas chromatograph (gas chromatography with a film-ionization detector, GC-9790 II) 2 Reduction of the oxidation products CO and CH 4 Analysis was performed.
Example 1
The preparation method of the 3D unique honeycomb-shaped reduced carbon dioxide photocatalyst composite material comprises the following steps: 4.5g of cobalt nitrate, 4.5g of ferric nitrate and 6.0g of polyvinylpyrrolidone were dissolved in 180mL of deionized water in a chamberMagnetic stirring was carried out at room temperature. And keeping the mixture at 95 ℃, stirring and drying to form reddish brown powder, thereby obtaining a precursor of the cobalt-iron alloy nanoparticles embedded into the 3D honeycomb porous nitrogen-doped graphite carbon framework composite material. Placing the precursor powder in a ceramic crucible at N 2 Heating in a tube furnace at a heating rate of 5 ℃/min under the atmosphere, and keeping for 1h when roasting to 600 ℃.
By obtaining the topographical image of fig. 2 at 600 ℃, it can be observed that at this temperature there is a 3D honeycomb porous structure with smaller CoFe nanoparticles.
Example 2
This example was the same as example 1 except that the firing temperature was different, and in this example, firing was carried out to 700 ℃. The formation of the cellular structure obtained at this temperature is due to PVP-Co/Fe 2+ Decomposition during calcination.
FIG. 3 shows uniformly distributed CoFe nanoparticles embedded in a 3D honeycomb porous nitrogen-doped graphitic carbon-frame composite
Example 3
This example was the same as example 1 except that the firing temperature was different, and in this example, firing was carried out to 800 ℃.
The honeycomb structure obtained at this temperature as shown in fig. 4 shows that the uniformly distributed CoFe alloy nanoparticles are significantly larger than those of examples 1-2.
Example 4
This example was the same as example 1 except that the firing temperature was different, and in this example, firing was carried out to 900 ℃.
The honeycomb structure obtained at this temperature as shown in fig. 5 shows that the uniformly distributed CoFe alloy nanoparticle particles are significantly larger than those of examples 1-3.
Example 5
This example was the same as example 1 except that the firing temperature was different, and in this example, firing was carried out to 1000 ℃.
The honeycomb structure obtained at this temperature as shown in fig. 6 shows that the uniformly distributed CoFe alloy nanoparticle particles are significantly larger than those of examples 1-4.
Example 6
Photocatalytic CO 2 Preparation of a reduction film: 50mg of 3D unique honeycomb reduced carbon dioxide photocatalyst composite was placed in a glass petri dish with a diameter of 6cm, and 5ml of deionized water was added. The catalyst was dispersed for 3min with ultrasound. Placing the culture dish in an oven, drying at 60 ℃, and finally uniformly distributing 500 mu L of deionized water on the surface of the dried catalyst to obtain the photocatalytic CO 2 And (4) reducing the film.
The photocatalyst of the composite material with the nitrogen-doped graphite carbon framework, which is embedded into the 3D honeycomb-shaped porous structure and has a uniform surface and no cracks, of the CoFe alloy nanoparticles obtained by the method is shown in figure 8.
FIG. 9 shows the yield of carbon dioxide reduction by the photocatalysts prepared in examples 1 to 5, which is as follows:
CO and CH of example 1 4 The yields of (b) were 49.65. mu. mol. g, respectively -1 And 32.78. mu. mol. g -1 。
CO and CH of example 2 4 The yields of (b) were 49.65. mu. mol. g, respectively -1 And 32.78. mu. mol. g -1 。
CO and CH of example 3 4 The yields were 58.53. mu. mol g, respectively -1 And 54.07. mu. mol. g -1 。
CO and CH of example 4 4 The yields of (a) are 56.65. mu. mol. g, respectively -1 And 41.19. mu. mol. g -1 。
CO and CH of example 5 4 The yields were 49.36. mu. mol g, respectively -1 And 31.87. mu. mol. g -1 。
The photocatalytic CO calcined at 800 ℃ in the precursor of the CoFe alloy nanoparticle composite material is found by FIG. 9 2 The reducing properties are best.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method for preparing a bimetal 3D unique honeycomb-shaped reduced carbon dioxide catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving cobalt-iron alloy nanoparticles and a carbon material of a 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework in water, uniformly stirring at room temperature, heating, stirring and drying the mixture to form reddish brown powder, thereby obtaining a precursor of the composite material with the CoFe nanoparticles embedded in the 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework;
(2) and (2) calcining the dried sample obtained in the step (1) in a tubular furnace under the protection of inert gas to obtain the CoFe nano-particles embedded 3D honeycomb porous nitrogen-doped graphite carbon frame composite material.
2. The method of claim 1, wherein: the cobalt-iron alloy nanoparticles consist of cobalt salt and iron salt; the cobalt salt is selected from one or two of cobalt acetate and cobalt nitrate; the iron salt is selected from one or two of ferric chloride and ferric nitrate.
3. The method of claim 2, wherein: the mass ratio of the cobalt salt to the iron salt is 3-1: 1-3.
4. The method of claim 1, wherein: the carbon material of the 3D honeycomb-shaped porous nitrogen-doped graphite carbon framework is selected from at least one of melamine, urea and polyvinylpyrrolidone.
5. The method of claim 1, wherein: the mass ratio of the cobalt-iron alloy nano particles to the carbon material is 4-1: 1-4.
6. The method of claim 1, wherein: the water is selected from any one of distilled water, tap water, drinking water and deionized water.
7. The method of claim 1, wherein: the heating and stirring temperature in the step (1) is 95 ℃; in the step (2), the calcining temperature is 500-1100 ℃, the heating rate is 1-10 ℃/min, and the constant temperature time is 0.5-2 h.
8. The method of claim 1, wherein: the inert gas is carbon dioxide gas, nitrogen gas or argon gas.
9. A bimetal 3D unique honeycomb-shaped carbon dioxide reduction catalyst is characterized in that: prepared by the process of any one of claims 1 to 8.
10. Use of the bimetallic 3D unique honeycomb reduced carbon dioxide catalyst of claim 9 to reduce carbon dioxide.
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