CN116273092A - Metal organic framework-nickel phosphide composite material, preparation method and application thereof in ethane synthesis - Google Patents
Metal organic framework-nickel phosphide composite material, preparation method and application thereof in ethane synthesis Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
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- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 76
- 239000000463 material Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 46
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000004729 solvothermal method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
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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
- 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
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- 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
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Abstract
The invention provides a metal organic framework-nickel phosphide composite material, a preparation method and application thereof in ethane synthesis, belonging to the field of photo-thermal catalytic material preparation, wherein the method comprises the following steps: s1, calcining MIL-100 (Fe) in a protective gas atmosphere at 350-450 ℃ to obtain carbonized MIL-100 (Fe); s2, dispersing carbonized MIL-100 (Fe) and nickel phosphide into absolute ethyl alcohol according to the mass ratio of (0.5-2), and then carrying out heat treatment to obtain a reaction solution; s3, cooling the reaction liquid, separating a product, and washing and drying the product in sequenceObtaining the metal organic frame-nickel phosphide composite material. The invention combines porous nanospheres MIL-100/C with Ni 2 P is compounded well, and the formed structure has excellent photo-thermal catalysis effect.
Description
Technical Field
The invention belongs to the field of preparation of photo-thermal catalytic materials, and particularly relates to a metal organic framework-nickel phosphide composite material, a preparation method and application thereof in ethane synthesis.
Background
With the rapid development of modern society, a great deal of fossil fuels such as coal, petroleum and the like are consumed, and discharged CO 2 The threat of global warming, glacier melting, sea level rising, natural ecological balance and a series of environmental problems seriously affect the survival and development of human beings. Thus, solar energy is utilized to photo-catalyze CO 2 Conversion is the most promising CO recognized 2 A transformation pathway. However, CO is catalyzed only by light 2 Efficient conversion to fuel is quite difficult. In order to solve the defects of photocatalysis, photocatalysis and thermocatalysis are combined, and photocatalysis which cooperatively drives catalytic reaction becomes a promising solar fuel production strategy, and is a potential economical and environment-friendly method.
Photo-thermal CO-production 2 Catalytic conversion strategies are one of the most promising directions for practical industrial applications, with the advantage that: (1) the solar spectrum is fully utilized; (2) the light energy utilization rate is high; (3) the conversion efficiency is high; (4) the reaction rate is fast.
Compared with the traditional photocatalyst material, the metal organic frameworks (Metal Organic Frameworks, MOFs) have the advantages of ultrahigh specific surface area, adjustable porosity and structure, and the like, so that the excellent physicochemical properties of the MOFs material enable the MOFs material to have extremely high value in the field of photocatalysis. As a member of MOFs materials, MIL-100 (Fe) not only has the advantages of large specific surface area, high porosity, coordinated structure and the like, but also has the advantages of strong redox activity and good visible light response, and besides, MIL-100 (Fe) also has the advantages of high thermal stability, abundant Lewis acid sites and the like. And compared with other metal ions, the toxicity of the iron ions is relatively low, and the trace leaching of the iron ions in the iron-based MOFs material does not cause harm to the environment. Therefore, MIL-100 (Fe) has received much attention in the field of photocatalysis. MIL-100 (Fe) based composite material in CO compared to single MIL-100 (Fe) material 2 The capture field has polesAnd has wide application prospect. Ni (Ni) 2 The d hole is increased due to the incorporation of P atoms in the P structure, the state density near the Fermi level is increased, and Ni is caused 2 P may exhibit properties similar to those of noble metals, ni in all metal phosphides 2 P shows the highest catalytic activity and stability. But up to now how to use p-CO 2 MIL-100 (Fe) with strong adsorptivity and Ni with high catalytic activity 2 P, CO-conversion of CO in photo-thermal 2 The field exerts excellent potential and has not been reported yet.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a metal organic frame-nickel phosphide composite material, a preparation method and application thereof in ethane synthesis, and the metal organic frame-nickel phosphide composite material has good photo-thermal catalytic performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a metal organic framework-nickel phosphide composite material comprises the following steps:
s1, calcining MIL-100 (Fe) in a protective gas atmosphere at 350-450 ℃ to obtain carbonized MIL-100 (Fe);
s2, dispersing carbonized MIL-100 (Fe) and nickel phosphide into absolute ethyl alcohol according to the mass ratio of (0.5-2), and then carrying out heat treatment to obtain a reaction solution;
and S3, cooling the reaction liquid, separating a product, and washing and drying the product in sequence to obtain the metal organic framework-nickel phosphide composite material.
Preferably, MIL-100 (Fe) described in S1 is obtained as follows:
FeCl is added 3 ·6H 2 O and trimesic acid are dispersed in a solution formed by glycol and N, N-dimethylformamide, feCl 3 ·6H 2 The ratio of O, trimesic acid, ethylene glycol and N, N-dimethylformamide was 0.8194g:0.6370g:81mL:81mL, then preserving heat for 1.5-2.5 h at 70-90 ℃, then washing with deionized water and N, N-dimethylformamide in sequence, and finally drying at 60-80 ℃ to obtain nanosphere MIL-100 (Fe).
Preferably, the MIL-100 (Fe) in S1 is heated from room temperature to 350-450 ℃ at a heating rate of 3-5 ℃/min.
Preferably, the MIL-100 (Fe) in S1 is calcined at 350-450 ℃ for 50-70 min to obtain carbonized MIL-100 (Fe).
Preferably, the nickel phosphide described in S2 is obtained as follows:
according to 0.5657:0.2, nickel chloride and hexadecyl trimethyl ammonium bromide are dispersed in an N, N-dimethylformamide water solution, and then red phosphorus is added and mixed uniformly, wherein the mass ratio of the red phosphorus to the nickel chloride is 0.62:0.5657, the mixed system is obtained, the mixed system is kept at 150-180 ℃ for 8-12 h, and finally, the product is separated, washed, dried and ground in sequence, thus obtaining the nickel phosphide.
Further, the volume fraction of the N, N-dimethylformamide aqueous solution is 20-25%, and the mixed system is obtained after adding red phosphorus and stirring for 30-45 min at 1200-2000 rpm.
Preferably, the ratio of MIL-100 (Fe) and absolute ethanol after carbonization in S2 is 2mg:1mL.
Preferably, the heat treatment described in S2 is carried out at 150-180℃for 8-12 h.
A metal-organic framework-nickel phosphide composite material obtained by the method for preparing a metal-organic framework-nickel phosphide composite material as described in any one of the above.
Metal organic frame-nickel phosphide composite material in CO 2 The application of photo-thermal hydrogenation to ethane synthesis.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a metal organic frame-nickel phosphide composite material, which uses MIL-100 (Fe) with a nanosphere structure as a precursor, and obtains MIL-100 (Fe) after carbonization by calcining, wherein the MIL-100 (Fe) is of a porous nanosphere structure and can be recorded as MIL-100/C, then nickel phosphide is combined, and the metal organic frame-nickel phosphide composite material can be obtained by synthesizing through a solvothermal method and can be recorded as MIL-100/C-Ni 2 P composite material. The material has the advantage of high visible light catalytic performance. And a single MIL-100(Fe)、MIL-100/C、Ni 2 P can greatly improve the CO ratio 2 Is used for the photo-thermal conversion efficiency of the light-emitting diode. The invention combines porous nanospheres MIL-100/C with Ni 2 P is compounded well, and the formed structure has excellent photo-thermal catalysis effect. The invention has simple process, low price and easy obtainment of the used raw materials, does not need complex and expensive equipment, meets the environment-friendly requirement, and has reference function for the development of environment materials. The invention provides an important reference for the structural regulation of MOFs composite catalytic material, and improves the photo-thermal catalytic performance of the material, thereby better improving the photo-thermal conversion of CO 2 Performance of the catalyst is improved, ethane (C) 2 H 6 ) Is a yield of (2).
Drawings
FIG. 1 is a sample of MIL-100 (Fe), MIL-100/C, MIL-100/C-Ni prepared in example 2 of the present invention 2 P1:0.5，MIL-100/C-Ni 2 P 1:1，MIL-100/C-Ni 2 XRD pattern of P1:2.
FIG. 2 is a sample of MIL-100 (Fe), MIL-100/C, MIL-100/C-Ni prepared in example 2 of the present invention 2 P1:0.5，MIL-100/C-Ni 2 P 1:1，MIL-100/C-Ni 2 FT-IR diagram at P1:2.
FIG. 3 is Ni prepared in example 2 of the present invention 2 P，MIL-100/C，MIL-100/C-Ni 2 P1:1 Electrochemical Impedance (EIS) plot.
FIG. 4 is MIL-100/C-Ni prepared in example 2 of the present invention 2 TEM image of P1:1 composite.
FIG. 5 is MIL-100/C, MIL-100/C-Ni prepared in example 2 of the present invention 2 P 1:0.5，MIL-100/C-Ni 2 P 1:1，MIL-100/C-Ni 2 P1:2 photothermal conversion of CO 2 Yield map of hydro-synthesized alkanes.
FIG. 6 is an XPS survey of MIL-100 (Fe) and MIL-100/C prepared in example 2 of the present invention.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to examples. It should be understood that the specific embodiments described herein are only for the purpose of illustrating the present invention, but the present invention is not limited to the following examples.
The invention relates to a solvothermal methodMIL-100/C-Ni with prepared porous super-cage structure 2 The preparation method of the P composite material comprises the following steps:
(1) MIL-100 (Fe) was prepared by an oil bath method. The operation steps are as follows: 0.8194g of ferric trichloride (FeCl) 3 ·6H 2 O) and 0.6370g trimesic acid are respectively dispersed into a solution formed by 81mL of ethylene glycol and 81mL of N, N-Dimethylformamide (DMF) and stirred for 30-45 min, then the solution is subjected to heat treatment for 1.5-2.5 h in an oil bath at 70-90 ℃, then the solution is washed by deionized water and DMF in sequence, and finally the solution is dried at 60-80 ℃ to obtain dark red powder, namely nanosphere MIL-100 (Fe);
(2) Uniformly placing MIL-100 (Fe) in a quartz boat, heating up at 3-5 ℃/min under the protection of nitrogen, heating up to 350-450 ℃ from room temperature, calcining at high temperature, and keeping for 50-70 min to obtain black powder. XRD and TEM prove that the black substance keeps the integral form of the original MIL-100 (Fe), but a plurality of holes with different sizes appear on the surface of the black substance, which is caused by the fact that the organic ligand is decomposed to release a large amount of gas at high temperature; the content of C of the substance is slightly higher than MIL-100 (Fe), so that the substance is named as porous nanosphere MIL-100 (Fe)/C, and is abbreviated as MIL-100/C;
(3) 0.5657g of nickel chloride and 0.2g of Cetyl Trimethyl Ammonium Bromide (CTAB) are dispersed into 100-150 mL of 20-25% DMF water solution by volume fraction and stirred for 30-45 min under the condition of 1200-2000 rpm to obtain mixed solution, so that the interface of the two-phase reaction is enlarged, and the reaction is accelerated; then adding 0.62g of red phosphorus into the mixed solution, mixing uniformly, loading into a reaction kettle, reacting for 8-12 h at 150-180 ℃, cooling, centrifuging, washing with deionized water and absolute ethyl alcohol in sequence, drying at 60-80 ℃ and grinding to obtain black powder, namely nickel phosphide (Ni 2 P)；
(4) Porous nanospheres MIL-100/C and Ni 2 P is uniformly dispersed in absolute ethyl alcohol, MIL-100/C and Ni 2 The mass ratio of P is 1 (0.5-2), and the ratio of MIL-100/C to absolute ethyl alcohol is 2mg:1mL, putting the mixture into a reaction kettle and reacting for 8-12 h at 150-180 ℃;
(5) Cooling, centrifuging, washing with absolute ethanol and stripping at 60-80 DEG CDrying under the piece to obtain the porous super-cage structure MIL-100/C-Ni 2 P composite material.
In the following examples, MIL-100/C-Ni 2 P is respectively marked as MIL-100/C-Ni 2 P1:X, 1:X is MIL-100/C and Ni 2 P, wherein x=0.5, 1 or 2.
Example 1
The invention relates to MIL-100/C-Ni with a porous super-cage structure prepared by a solvothermal method 2 A method of preparing a P composite, wherein:
porous nano spherical MIL-100/C is synthesized at high temperature by an oil bath method. The method comprises the following steps:
(1) 0.8194g of ferric trichloride and 0.6370g of trimesic acid were respectively dispersed in a solution of ethylene glycol (81 mL) and DMF (81 mL), and stirred for 45min;
(2) Transferring the mixture into a round bottom flask, carrying out oil bath at 70 ℃ for 2.5 hours, then washing with deionized water and DMF for 3 times respectively, and drying at 80 ℃ to obtain dark red powder, namely MIL-100 (Fe) with a nanosphere structure.
(3) Uniformly placing MIL-100 (Fe) in a quartz boat, heating to 450 ℃ at a speed of 4 ℃/min under the protection of nitrogen, calcining at a high temperature, and maintaining for 70min to obtain black powder, namely obtaining the porous nanosphere MIL-100/C.
Ni 2 P is synthesized by solvothermal method. The method comprises the following steps:
(1) 0.5657g of nickel chloride and 0.2g of Cetyl Trimethyl Ammonium Bromide (CTAB) are dispersed into 120mL of DMF water solution with volume fraction of 20%, stirred for 40min at the rotating speed of 1500rpm, then 0.62g of red phosphorus is added, and after uniform mixing, the mixture is transferred into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining;
(2) The reaction vessel was then placed in a forced air drying oven and reacted at 170℃for 12h. After the reaction kettle is cooled to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, drying at 60 ℃, grinding to obtain Ni 2 P nanoparticles.
MIL-100/C-Ni with porous super-cage structure 2 P composite materialSolvothermal method to synthesize MIL-100/C and Ni 2 P is combined to prepare successfully, which comprises the following steps:
(1) 40mg MIL-100/C and 20mg Ni 2 Dispersing P into 20mL of absolute ethyl alcohol, uniformly stirring, and transferring to a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining;
(2) The reaction vessel was then placed in a forced air drying oven and reacted at 170℃for 12h. After the reaction kettle is cooled to room temperature, centrifuging, washing 3 times by using absolute ethyl alcohol, and drying at 60 ℃ to obtain the MIL-100/C-Ni with the porous super-cage structure 2 P 1:0.5。
Example 2
The invention relates to MIL-100/C-Ni with a porous super-cage structure prepared by a solvothermal method 2 A method of preparing a P composite, wherein:
porous nano spherical MIL-100/C is synthesized at high temperature by an oil bath method. The method comprises the following steps:
(1) 0.8194g of ferric trichloride and 0.6370g of trimesic acid were respectively dispersed in a solution of ethylene glycol (81 mL) and DMF (81 mL), and stirred for 30min;
(2) Transferring the mixture into a round bottom flask, carrying out oil bath at 80 ℃ for 2 hours, then washing with deionized water and DMF for 3 times respectively, and drying at 60 ℃ to obtain dark red powder, namely MIL-100 (Fe) with a nanosphere structure.
(3) Uniformly placing MIL-100 (Fe) in a quartz boat, heating to 400 ℃ at a speed of 3 ℃/min under the protection of nitrogen, calcining at a high temperature, and maintaining for 60min to obtain black powder, namely obtaining the porous nanosphere MIL-100/C.
Ni 2 P is synthesized by solvothermal method. The method comprises the following steps:
(1) 0.5657g of nickel chloride and 0.2g of Cetyl Trimethyl Ammonium Bromide (CTAB) are dispersed into 100mL of 25% volume fraction DMF water solution, stirred for 30min at a rotating speed of 1200rpm, then 0.62g of red phosphorus is added, and after uniform mixing, the mixture is transferred into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining;
(2) Then the reaction kettle is placed in a blast drying box to be reversely rotated at 160 DEG C10h should be taken. After the reaction kettle is cooled to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, drying at 80 ℃, grinding to obtain Ni 2 P nanoparticles.
MIL-100/C-Ni with porous super-cage structure 2 The P composite material is prepared by synthesizing MIL-100/C and Ni by a solvothermal method 2 P is combined to prepare successfully, which comprises the following steps:
(1) 40mg MIL-100/C and 40mg Ni 2 Dispersing P into 20mL of absolute ethyl alcohol, uniformly stirring, and transferring to a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining;
(2) The reaction vessel was then placed in a forced air drying oven and reacted for 10 hours at 160 ℃. After the reaction kettle is cooled to room temperature, centrifuging, washing 3 times by using absolute ethyl alcohol, and drying at 80 ℃ to obtain the MIL-100/C-Ni with the porous super-cage structure 2 P 1:1。
Example 3
The invention relates to a MIL-100/C-Ni with a porous super-cage structure prepared by a solvothermal method 2 A method of preparing a P composite, wherein:
porous nano spherical MIL-100/C is synthesized at high temperature by an oil bath method. The method comprises the following steps:
(1) 0.8194g of ferric trichloride and 0.6370g of trimesic acid were respectively dispersed in a solution of ethylene glycol (81 mL) and DMF (81 mL), and stirred for 40min;
(2) Transferring the mixture into a round bottom flask, carrying out oil bath at 90 ℃ for 1.5 hours, then washing with deionized water and DMF for 3 times respectively, and drying at 80 ℃ to obtain dark red powder, namely MIL-100 (Fe) with a nanosphere structure.
(3) Uniformly placing MIL-100 (Fe) in a quartz boat, heating to 450 ℃ at a speed of 5 ℃/min under the protection of nitrogen, calcining at a high temperature, and keeping for 50min to obtain black powder, namely obtaining the porous nanosphere MIL-100/C.
Ni 2 P is synthesized by solvothermal method. The method comprises the following steps:
(1) 0.5657g of nickel chloride and 0.2g of Cetyl Trimethyl Ammonium Bromide (CTAB) are dispersed into 150mL of DMF water solution with 23 percent volume fraction, stirred for 30min at the rotating speed of 2000rpm, then 0.62g of red phosphorus is added, and the mixture is transferred into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining after uniform mixing;
(2) The reaction vessel was then placed in a forced air drying oven and reacted at 150℃for 12h. After the reaction kettle is cooled to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, drying at 70 ℃, grinding to obtain Ni 2 P nanoparticles.
MIL-100/C-Ni with porous super-cage structure 2 The P composite material is prepared by synthesizing MIL-100/C and Ni by a solvothermal method 2 P is combined to prepare successfully, which comprises the following steps:
(1) 40mg MIL-100/C and 80mg Ni 2 Dispersing P into 20mL of absolute ethyl alcohol, uniformly stirring, and transferring to a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining;
(2) The reaction vessel was then placed in a forced air drying oven and reacted at 150℃for 12h. After the reaction kettle is cooled to room temperature, centrifuging, washing 3 times by using absolute ethyl alcohol, and drying at 70 ℃ to obtain the MIL-100/C-Ni with the porous super-cage structure 2 P 1:2。
MIL-100/C-Ni with porous super cage structure prepared in example 2 2 The P1:1 composite material was confirmed by X-ray diffraction (XRD), fourier infrared spectroscopy (FT-IR), electrochemical Impedance (EIS) and Transmission Electron Microscopy (TEM).
FIG. 1 is MIL-100 (Fe), MIL-100/C, MIL-100/C-Ni 2 P 1:0.5，MIL-100/C-Ni 2 P1:1，MIL-100/C-Ni 2 The XRD patterns of P1:2 show that the characteristic peaks of MIL-100 (Fe) and MIL-100/C are different from each other, and the fact that MIL-100 (Fe) is carbonized to obtain a new substance is shown. In MIL-100/C-Ni 2 MIL-100/C and Ni are all present on P 2 P crystal plane, indicating MIL-100/C and Ni 2 P is successfully compounded.
FIG. 2 is MIL-100 (Fe), MIL-100/C, MIL-100/C-Ni 2 P 1:0.5，MIL-100/C-Ni 2 P1:1，MIL-100/C-Ni 2 FT-IR diagram at P1:2, MIL-100 (Fe) at 1710, 1573, 1440, 1381, 759 and 710cm can be seen on the diagram -1 Obvious detection of the positionUntil characteristic absorption peaks exist, at 1440 and 1381cm -1 The characteristic peak at this point is due to the presence of asymmetric and symmetric vibrational band-O-C-O-groups and is at 759 and 710cm -1 The peak at the peak corresponds to C-H bending vibration of benzene, and is consistent with data reported in related literature, which shows that MIL-100 (Fe) with a nanosphere structure is successfully prepared. And the MIL-100/C obtained by high-temperature calcination of MIL-100 (Fe) is 1573cm in an infrared spectrum of MIL-100 (Fe) -1 Characteristic peak at 1550cm -1 Indicating that MIL-100 (Fe) is successfully prepared into a novel substance after high-temperature calcination. For MIL-100/C-Ni 2 P composite material, characteristic peak corresponding to MIL-100/C can be observed, and MIL-100/C is positioned at 1620cm -1 The characteristic peak at the position is red shifted to 1610cm -1 In addition to this, with Ni 2 The increase of the P doping amount gradually narrows the characteristic peak-to-peak, which shows that MIL-100/C and Ni 2 The interaction occurs in the P compounding process and keeps good stability, thus obtaining high-purity MIL-100/C-Ni 2 P composite material.
FIG. 3 is Ni 2 P，MIL-100/C，MIL-100/C-Ni 2 EIS diagram of P1:1, MIL-100/C-Ni compared with MIL-100/C 2 The smaller arc radius of the P1:1 composite material illustrates MIL-100/C-Ni 2 The P1:1 has lower impedance, better conductivity and better charge separation efficiency, thereby improving the catalytic performance.
FIG. 4 is a porous super cage MIL-100/C-Ni structure 2 TEM image of P1:1 composite, MIL-100/C-Ni can be seen 2 The P1:1 composite material is prepared from MIL-100/C porous nanosphere structure and Ni 2 P are mutually assembled to form a closely contacted porous super-cage structure, and meanwhile, MIL-100/C-Ni can be seen 2 Ni in the synthesis process of P1:1 composite material 2 The P nanoparticles undergo agglomeration and stacking. The invention also provides the application of the composite material in the field of photo-thermal catalysis, and the composite material is used for preparing CO 2 Research on the performance of hydrogenation synthesis of ethane.
The XPS full spectrum results of FIG. 6 show that MIL-100/C and MIL-100 (Fe) are both composed of C, H, O, fe elements, but the C content is slightly higher than that of MIL-100 (Fe).
Photothermal conversion of CO 2 Photo-thermal catalytic test of performance:
20mg of catalyst, 200. Mu. L H 2 O is sequentially added into a 350mL high-pressure visual reaction kettle, the high-pressure visual reaction kettle is sealed, high-purity argon is introduced for 10min to exhaust the air in the reaction kettle, and 30mL CO is introduced 2 The method comprises the steps of carrying out a first treatment on the surface of the Then, the reaction kettle is heated to 200 ℃ at a speed of 3 ℃/min, and after the temperature is raised to 200 ℃, an LED lamp (lambda=420 nm, the power is 350W) is turned on to perform photo-thermal catalytic reaction, and 5mL of gas is taken out of the reaction kettle at intervals of 1h and analyzed by Gas Chromatography (GC). The invention uses a gas chromatograph model 7860B manufactured by Agilent technologies Co., ltd, the column box temperature is 90 ℃, and the detector temperature is 250 ℃.
The catalyst is MIL-100/C, MIL-100/C-Ni in sequence 2 P 1:0.5，MIL-100/C-Ni 2 P1:1，MIL-100/C-Ni 2 P1:2, four determinations were performed, and the results of the determinations are shown in FIG. 5 for photo-thermal conversion of CO 2 The yield of the hydrogenated alkane is shown in the figure. As can be seen from the figure, MIL-100/C-Ni 2 P1:1 composite material photo-thermal conversion CO 2 The highest yield is obtained to obtain C 2 H 6 The yield can reach 5.8X10 -5 Mu mol/g/h, and CH 4 The yield can also reach 5.2X10 -6 μmol/g/h。
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations can be made by one skilled in the art without departing from the spirit of the present invention, and the present invention is within the scope of the present invention.
Claims (10)
1. The preparation method of the metal organic framework-nickel phosphide composite material is characterized by comprising the following steps of:
s1, calcining MIL-100 (Fe) in a protective gas atmosphere at 350-450 ℃ to obtain carbonized MIL-100 (Fe);
s2, dispersing carbonized MIL-100 (Fe) and nickel phosphide into absolute ethyl alcohol according to the mass ratio of (0.5-2), and then carrying out heat treatment to obtain a reaction solution;
and S3, cooling the reaction liquid, separating a product, and washing and drying the product in sequence to obtain the metal organic framework-nickel phosphide composite material.
2. The method for preparing a metal organic framework-nickel phosphide composite material according to claim 1, wherein MILs-100 (Fe) in S1 is obtained according to the following process:
FeCl is added 3 ·6H 2 O and trimesic acid are dispersed in a solution formed by glycol and N, N-dimethylformamide, feCl 3 ·6H 2 The ratio of O, trimesic acid, ethylene glycol and N, N-dimethylformamide was 0.8194g:0.6370g:81mL:81mL, then preserving heat for 1.5-2.5 h at 70-90 ℃, then washing with deionized water and N, N-dimethylformamide in sequence, and finally drying at 60-80 ℃ to obtain nanosphere MIL-100 (Fe).
3. The method for preparing a metal organic framework-nickel phosphide composite material according to claim 1, wherein the temperature of MILs-100 (Fe) in S1 is raised from room temperature to 350-450 ℃ at a rate of 3-5 ℃/min.
4. The method for preparing a metal organic framework-nickel phosphide composite material according to claim 1, wherein the MILs-100 (Fe) in S1 is calcined at 350-450 ℃ for 50-70 min to obtain carbonized MILs-100 (Fe).
5. The method for preparing a metal organic framework-nickel phosphide composite material according to claim 1, wherein the nickel phosphide in S2 is obtained by the following steps:
according to 0.5657:0.2, nickel chloride and hexadecyl trimethyl ammonium bromide are dispersed in an N, N-dimethylformamide water solution, and then red phosphorus is added and mixed uniformly, wherein the mass ratio of the red phosphorus to the nickel chloride is 0.62:0.5657, the mixed system is obtained, the mixed system is kept at 150-180 ℃ for 8-12 h, and finally, the product is separated, washed, dried and ground in sequence, thus obtaining the nickel phosphide.
6. The method for preparing a metal organic frame-nickel phosphide composite material according to claim 5, wherein the volume fraction of the N, N-dimethylformamide aqueous solution is 20% -25%, and the mixed system is obtained by adding red phosphorus and stirring at 1200-2000 rpm for 30-45 min.
7. The method for preparing a metal organic framework-nickel phosphide composite material according to claim 1, wherein the ratio of MILs-100 (Fe) and absolute ethanol after carbonization in S2 is 2mg:1mL.
8. The method for preparing a metal-organic framework-nickel phosphide composite material according to claim 1, wherein the heat treatment in S2 is carried out at 150-180 ℃ for 8-12 h.
9. A metal-organic framework-nickel phosphide composite material obtained by the method for producing a metal-organic framework-nickel phosphide composite material as set forth in any one of claims 1 to 8.
10. The metal organic framework-nickel phosphide composite material as set forth in claim 9 in CO 2 The application of photo-thermal hydrogenation to ethane synthesis.
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