CN110639567A - Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof - Google Patents
Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 60
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 91
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
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- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 36
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
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- 238000010438 heat treatment Methods 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 8
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
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- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
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- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
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- 208000030507 AIDS Diseases 0.000 description 1
- 108010020056 Hydrogenase Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000003907 antipyretic analgesic agent Substances 0.000 description 1
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- -1 quinoline compound Chemical class 0.000 description 1
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Images
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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
- 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
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst, a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: dispersing activated carbon powder and a Ru precursor in water, stirring to enable the Ru precursor to be fully adsorbed on the surface of the activated carbon, then evaporating to remove moisture, mixing and grinding the obtained solid powder and sodium hypophosphite, placing the mixture in a tubular furnace to carry out high-temperature calcination in an inert atmosphere, enabling the Ru precursor loaded on the activated carbon to react with the sodium hypophosphite at high temperature to be converted into a ruthenium phosphide active ingredient, washing the calcined product with water, and drying to obtain the carbon-loaded ruthenium phosphide nanocluster bifunctional catalyst. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst can be used for catalyzing the reaction of quinoline hydrogenation and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline, and is high in catalytic activity, good in stability, simple in preparation method and easy for industrial mass production.
Description
Technical Field
The invention discloses a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and a preparation method and application thereof.
Background
Quinoline and 1,2,3, 4-tetrahydroquinoline and derivatives thereof are important intermediates for synthesizing medicaments, pesticides, dye alkaloids and many other bioactive molecules, and have very important application value. Secondly, quinoline and derivatives thereof are important raw materials for synthesizing and preparing some medical medicines. The quinoline compound is mainly used for synthesizing antimalarial drugs, antipyretic analgesic drugs, local anesthetic drugs and the like, and besides being used for synthesizing drugs, quinoline and derivatives thereof are also used for researching and treating AIDS. Therefore, the development of the bifunctional catalyst for quinoline hydrogenation and dehydrogenation of 1,2,3, 4-tetrahydroquinoline and derivatives thereof is important in the industrial production of the hydrogenation and dehydrogenation reactions and has important industrial value. At present, the main focus is on developing a bifunctional catalyst which has high selectivity, high activity, high stability and can effectively complete the hydrogenation and dehydrogenation reactions in the aspects of the hydrogenation of quinoline and the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline. Although Pd, Pt, Rh and Co based catalysts (Danhua Ge, Lei Hu, Jiaqing Wang, Xininging Li, Fenqiang Qi, Jianmei Lu, Xueqin Cao, Hongwei Gu; Reversible Hydrogenation-Oxidative Dehydrogenation of quench oil, high Active Pt Nanowire Catalyst under mixtures Conditions; chemical Chem; 2013,5, 2183; Christophe Catalyst, Rong Ye, Walter T. Raton, F. Dean Catalyst, Gabor A. Somorjai; Dendri-Stabilized organic catalysts as catalysts for reaction, 53-62.) have been reported to be useful as bifunctional catalysts for the hydrogenation of quinoline and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline. However, the noble metal-based catalysts Pd, Pt and Rh have limited their catalytic applications due to their rarity and high cost, and the Co catalysts are too complicated in preparation process and expensive in support, and thus are not suitable for industrial catalytic applications. Therefore, the development of the supported bifunctional catalyst which is efficient, recyclable and simple to prepare is very important in the aspects of quinoline hydrogenation and tetrahydroquinoline dehydrogenation. The transition metal is expected to replace noble metal to become a novel catalyst because the transition metal contains unfilled d orbitals and unpaired d orbital electrons. To date, researchers have conducted some research into the catalytic activity of transition metals and their compounds (sulfides, nitrides, carbides, phosphides, etc.) in hydrogenation. Among them, transition metal phosphides are particularly spotlighted because of their high catalytic activity as a mechanism of catalysis like hydrogenase.
Disclosure of Invention
The invention aims to provide a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and a preparation method and application thereof. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst can be used for catalyzing the reaction of quinoline hydrogenation and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline, and is high in catalytic activity, good in stability, simple in preparation method and easy for industrial mass production.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized by comprising the following steps of:
1) uniformly dispersing activated carbon powder in water at room temperature, adding a Ru precursor into the obtained suspension, and stirring to ensure that the Ru precursor is fully adsorbed on the surface of the activated carbon to obtain suspension A;
2) evaporating the suspension A obtained in the step 1) to remove water to obtain solid powder;
3) mixing the solid powder obtained in the step 2) with sodium hypophosphite, fully grinding, transferring the obtained mixed powder into a tubular furnace, carrying out high-temperature calcination in an inert atmosphere, reacting a Ru precursor loaded on active carbon with the sodium hypophosphite at high temperature to convert the Ru precursor into a ruthenium phosphide active component, washing the calcined solid product with deionized water, and drying to obtain the carbon-loaded ruthenium phosphide nanocluster bifunctional catalyst.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that in the step 1), a Ru precursor is ruthenium trichloride, ruthenium (III) tris (acetylacetonate) or ruthenium (III) acetate, preferably ruthenium trichloride, and the mass ratio of the activated carbon powder to the Ru precursor is 20 ~ 60: 1.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that in the step 2), the temperature for evaporating the suspension A is 75-90 ℃.
The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized in that in the step 3), the gas in the inert atmosphere is nitrogen; the high-temperature calcination temperature is 400-700 ℃, and the high-temperature calcination time is 3-7 h.
The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst prepared by the method.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing quinoline hydrogenation reaction is characterized in that the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is added into a high-pressure reactor, quinoline and a solvent are added into the high-pressure reactor, and H is used2After the air in the high-pressure reactor is replaced and exhausted, the high-pressure reactor is filled with H with a certain pressure2Heating and stirring for reaction for several hours, filtering the reaction solution after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the quinoline hydrogenation reaction product.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing quinoline hydrogenation reaction is characterized in that the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to quinoline is 1:4 ~ 7, preferably 1:5, the solvent is ethanol or water, and the using amount of the solvent is 5-8 times of the mass of quinoline.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in the catalytic quinoline hydrogenation reaction is characterized in that H filled in a high-pressure reactor is subjected to thermal stirring reaction2The pressure is 0.3-1Mpa, the heating reaction temperature is 50-80 ℃, the heating reaction time is 3-10h, and the stirring speed is 800-1200 rpm.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing tetrahydroquinoline dehydrogenation reaction is characterized in that the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is added into a high-pressure reactor and reacts at high pressurePutting tetrahydroquinoline and solvent into a reactor, and adding N2Displacing and exhausting air in the high-pressure reactor and leading N to be2And (3) after the internal space of the high-pressure reactor is filled, heating and stirring for reaction, filtering the reaction liquid after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the tetrahydroquinoline dehydrogenation reaction product.
The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing dehydrogenation reaction of tetrahydroquinoline is characterized in that the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to the tetrahydroquinoline is 1 (1.5-2); the solvent is benzene solvent, and the benzene solvent is p-xylene, o-xylene, m-xylene, xylene or mesitylene; the dosage of the solvent is 10-12 times of the mass of the tetrahydroquinoline; the reaction temperature is 135-145 ℃, and the reaction time is 20-24 h; the stirring speed was 250-450 rpm.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the preparation method of the carbon-supported ruthenium phosphide nanocluster catalyst, the impregnation method is utilized, Ru (III) in the Ru precursor solution is successfully supported on the surface of the active carbon, then the active carbon and sodium hypophosphite are fully ground and then the active carbon is calcined at high temperature in the inert atmosphere, so that the Ru precursor supported on the surface of the active carbon is decomposed and subjected to phosphorization, the prepared catalyst is good in stability, and the active component of the ruthenium phosphide nanoparticles, which has good dispersity and is in the shape of a nanocluster, is supported on the surface of the active carbon. Compared with the catalyst in the prior art, the catalyst has the advantages that the surface of the active carbon carrier is rich in active species of high-valence Ru (I) and Ru (II) (under the action of phosphorus, a ruthenium component in the phosphorized ruthenium dioxide can show a high valence state relative to zero), so that the reaction for catalyzing the hydrogenation of quinoline and the application of the bifunctional catalyst for the dehydrogenation of 1,2,3, 4-tetrahydroquinoline are realized, and the catalyst shows excellent activity and stability for the hydrogenation reaction and the dehydrogenation reaction.
2) The active component of the catalyst is unique Ru2The catalyst has a P structure, can be applied to the hydrogenation reaction of quinoline, has good dehydrogenation effect on 1,2,3, 4-tetrahydroquinoline, and is a bifunctional catalyst (A)Since hydrogenation and dehydrogenation are a pair of reversible reactions, switching between reactants and products can be achieved by changing reaction conditions using one catalyst). In the active component of the catalyst of the present invention, the phosphorus atom bonded to the metallic ruthenium generates an electron-deficient metal by extracting electrons from the metallic ruthenium, and the change of the electron density of the 3d layer of the metallic ruthenium is also a main reason for having both the catalytic hydrogenation of quinoline and the dehydrogenation of 1,2,3, 4-tetrahydroquinoline as a bifunctional catalyst.
Drawings
FIG. 1 is a TEM image of a carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1;
FIG. 2 is a graph of the results of a statistical analysis of the particle size of the black dots of FIG. 1;
FIG. 3 is an XPS plot of a carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1;
FIG. 4 is a graph showing the reaction results of the continuous hydrogenation reaction of quinoline;
FIG. 5 is a comparison graph of reaction results of quinoline hydrogenation reaction for 5 hours under different application times of the catalyst;
FIG. 6 is a graph showing the results of the continuous dehydrogenation of 1,2,3, 4-tetrahydroquinoline;
FIG. 7 is a graph showing the comparison of the reaction results of 1,2,3, 4-tetrahydroquinoline dehydrogenation reaction for 23h under different application times of the catalyst.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
The starting reagents used in the following examples were all of analytical purity, purchased directly from the market, and did not require further processing.
Example 1
Adding 0.5 g of activated carbon powder (particle size of 170 ~ 220 mesh) into 50 mL of water at room temperature, performing ultrasonic treatment to uniformly disperse the activated carbon to obtain a first suspension, adding 1 mL of RuCl with the concentration of 10mg/mL3The aqueous solution was added dropwise to the first suspension, and stirred at room temperature for 3 hours to allow RuCl3Fully adsorbing the suspension on the surface of the activated carbon to obtain second suspension.
The second suspension was stirred continuously at a temperature of 80 ℃ until the water was totally evaporated, yielding a first solid powder. Fully grinding the first solid powder and 100 mg of sodium hypophosphite in a mortar, transferring the ground mixed powder into a porcelain boat, and calcining the porcelain boat in a tube furnace under the nitrogen atmosphere, wherein the calcining process comprises the following steps: heating from room temperature to 600 deg.C at a heating rate of 5 deg.C/min, maintaining at 600 deg.C for 5h, and naturally cooling to room temperature to obtain a second solid powder. And washing the second solid powder with deionized water for 3 times (the volume of the deionized water adopted in each washing is 30 mL), and then drying in a vacuum drying oven at 60 ℃ for 10h to obtain the carbon-supported ruthenium phosphide nanocluster catalyst.
A TEM image of the carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that: the active component of the ruthenium phosphide is uniformly dispersed on the active carbon carrier in the form of nanocluster, and the particle size distribution of the active component of the ruthenium phosphide is basically in the range of 1.2-4.0 nm (the particle size distribution of the active component of the ruthenium phosphide is concentrated and is uniformly distributed on the surface of the active carbon). According to the map result of fig. 1, the analysis was performed by using the particle size distribution statistical software (i.e., the analysis was performed on the size of the black dot portion in fig. 1), and the analysis result is shown in fig. 2, and it can be seen from fig. 2 that the average particle size of the ruthenium phosphide active ingredient was 2.6 nm.
The carbon-supported ruthenium phosphide nanocluster catalyst prepared in example 1 was subjected to X-ray analysis, and the XPS analysis result thereof is shown in fig. 3. As can be seen from fig. 3, the Ru component on the catalyst surface is a high-valence Ru component.
Example 2
Adding 1 g of activated carbon powder (170 mesh 170 ~ 220 mesh) into 120 mL of water at room temperature, performing ultrasonic treatment to uniformly disperse the activated carbon to obtain a first suspension, adding 2.2 mL of RuCl with the particle size of 10mg/mL3The aqueous solution was added dropwise to the first suspension, and stirred at room temperature for 4 hours to allow RuCl3Fully adsorbing the suspension on the surface of the activated carbon to obtain second suspension.
The second suspension was stirred continuously at a temperature of 78 ℃ until the water was totally evaporated, yielding a first solid powder. Fully grinding the first solid powder and 500 mg of sodium hypophosphite in a mortar, transferring the ground mixed powder into a porcelain boat, and calcining the porcelain boat in a tube furnace under the nitrogen atmosphere, wherein the calcining process comprises the following steps: heating to 650 deg.C at a heating rate of 7 deg.C/min from room temperature, maintaining at 650 deg.C for 4.5 h, and naturally cooling to room temperature to obtain a second solid powder. And washing the second solid powder with deionized water for 3 times (the volume of the deionized water adopted in each washing is 80 mL), and then drying in a vacuum drying oven at 60 ℃ for 12 h to obtain the carbon-supported ruthenium phosphide nanocluster catalyst.
Example 3
Adding 0.3 g of activated carbon powder (with the particle size of 170 ~ 220 meshes) into 50 mL of water at room temperature, performing ultrasonic treatment to uniformly disperse the activated carbon to obtain a first suspension, dropwise adding 0.7 mL of 10mg/mL of aqueous solution of ruthenium (III) tris (acetylacetonate) into the first suspension, and stirring at room temperature for 3 hours to fully adsorb the ruthenium (III) tris (acetylacetonate) on the surface of the activated carbon to obtain a second suspension.
The second suspension was stirred continuously at a temperature of 90 ℃ until the water was totally evaporated, yielding a first solid powder. Fully grinding the first solid powder and 60 mg of sodium hypophosphite in a mortar, transferring the ground mixed powder into a porcelain boat, and calcining the porcelain boat in a tube furnace under the nitrogen atmosphere, wherein the calcining process comprises the following steps: heating from room temperature to 700 deg.C at a heating rate of 7 deg.C/min, maintaining at 700 deg.C for 6 h, and naturally cooling to room temperature to obtain a second solid powder. And (3) washing the second solid powder with deionized water for 3 times (the volume of the deionized water adopted in each washing is 20 mL), and then drying in a vacuum drying oven at 70 ℃ for 8 h to obtain the carbon-supported ruthenium phosphide nanocluster catalyst.
Example 4 the catalyst of example 1 was used to catalyze the quinoline hydrogenation reaction:
weighing 150 mg of prepared carbon-supported ruthenium phosphide nanocluster catalyst, 600 mu L of quinoline and 20 mL of ethanol, adding into a high-pressure reaction kettle, and adding H2Will high-pressure batch autoclaveAfter the air in the autoclave is replaced and exhausted, the autoclave is filled with H with the pressure of 0.5 Mpa2. The reaction solution in the autoclave was stirred at 60 ℃ for reaction, and the reaction results were sampled every 1 hour (gas chromatography was used for analysis to calculate the hydrogenation effect of quinoline), and the reaction results of the continuous hydrogenation of quinoline are shown in fig. 4. As can be seen from FIG. 4, the hydrogenation reaction of quinoline tends to be stable after 5 hours of continuous reaction, i.e. the reaction is substantially complete after 5 hours, and the yield of 1,2,3, 4-quinoline, which is the product of the hydrogenation reaction of quinoline, is as high as about 97%.
After the continuous hydrogenation reaction of the quinoline is finished for 5 hours, discharging the reaction liquid in the high-pressure reaction kettle, filtering, repeatedly applying the filtered solid catalyst for the continuous hydrogenation reaction of the quinoline, and applying the experimental conditions unchanged (and the catalyst is applied for each time and is subjected to catalytic reaction for 5 hours). The reaction result of the quinoline hydrogenation reaction for 5h under different application times of the catalyst is shown in fig. 5. As can be seen from FIG. 5, the yield of 1,2,3, 4-quinoline as the hydrogenation product was 91.5% after using the catalyst for 8 times. As can be seen from the reaction results, the catalytic activity of the catalyst is not obviously reduced under the condition of repeated application, thereby indicating that the catalyst has higher stability.
Example 5 the catalyst of example 1 was used to catalyze the dehydrogenation of 1,2,3, 4-tetrahydroquinoline:
weighing 300 mg of prepared carbon-supported ruthenium phosphide nanocluster catalyst, 400 mu L of 1,2,3, 4-tetrahydroquinoline and 20 mL of mesitylene, adding the mixture into a 100 mL round-bottom flask, and adding N into the flask2The air in the autoclave was replaced and exhausted (the autoclave was filled with a nitrogen atmosphere), the reaction was stirred at 135 ℃, sampling during the reaction was performed for analysis (gas chromatography was used for analysis to calculate the dehydrogenation effect of 1,2,3, 4-tetrahydroquinoline), and the reaction results of the continuous dehydrogenation of 1,2,3, 4-tetrahydroquinoline are shown in fig. 6. As can be seen from FIG. 6, the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline tends to be stable after 23 hours of continuous reaction, i.e. the reaction is substantially complete after 23 hours, and the yield of the dehydrogenation reaction product quinoline of 1,2,3, 4-tetrahydroquinoline is as high as about 98% or more.
After the 1,2,3, 4-tetrahydroquinoline is continuously dehydrogenated for 23 hours, the reaction is finished, the reaction liquid in the round-bottom flask is discharged and filtered, the solid catalyst obtained by filtering is repeatedly used for the continuous dehydrogenation of the 1,2,3, 4-tetrahydroquinoline, and the application experimental conditions are unchanged (and the catalyst is used for catalytic reaction for 23 hours each time). The reaction results of the 1,2,3, 4-tetrahydroquinoline continuous dehydrogenation reaction for 23h under different application times of the catalyst are shown in fig. 7. As can be seen from FIG. 7, the yield of the dehydrogenation product, quinoline, was 93.0% after using the catalyst for 8 times. As can be seen from the reaction results, the catalytic activity of the catalyst is not obviously reduced under the condition of repeated application, thereby indicating that the catalyst has higher stability.
Example 6:
the catalyst of example 2 is used for catalyzing quinoline hydrogenation reaction, the operation steps are repeated in example 4, the reaction time is 5h, sampling analysis is carried out, and the result is that: the yield of 1,2,3, 4-quinoline, which is the product of the quinoline hydrogenation reaction, was 99.0%.
The catalyst of example 2 is used for catalyzing dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline, the operation steps are repeated for example 5, a sample is taken for 23h for analysis, and the result is that: the yield of the product quinoline from the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline was 99.1%.
Example 7:
the catalyst of example 3 is used for catalyzing quinoline hydrogenation reaction, the operation steps are repeated in example 4, the reaction time is 5h, sampling analysis is carried out, and the result is that: the yield of 1,2,3, 4-quinoline, which is the product of the quinoline hydrogenation reaction, was 99.2%.
The catalyst of example 3 is used for catalyzing dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline, the operation steps are repeated for example 5, a sample is taken for 23h for analysis, and the result is that: the yield of the product quinoline from the dehydrogenation reaction of 1,2,3, 4-tetrahydroquinoline was 99.1%.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. A preparation method of a carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is characterized by comprising the following steps of:
1) uniformly dispersing activated carbon powder in water at room temperature, adding a Ru precursor into the obtained suspension, and stirring to ensure that the Ru precursor is fully adsorbed on the surface of the activated carbon to obtain suspension A;
2) evaporating the suspension A obtained in the step 1) to remove water to obtain solid powder;
3) mixing the solid powder obtained in the step 2) with sodium hypophosphite, fully grinding, transferring the obtained mixed powder into a tubular furnace, carrying out high-temperature calcination in an inert atmosphere, reacting a Ru precursor loaded on active carbon with the sodium hypophosphite at high temperature to convert the Ru precursor into a ruthenium phosphide active component, washing the calcined solid product with deionized water, and drying to obtain the carbon-loaded ruthenium phosphide nanocluster bifunctional catalyst.
2. The preparation method of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 1, wherein in step 1), the Ru precursor is ruthenium trichloride, ruthenium (III) tris (acetylacetonate) or ruthenium (III) acetate, preferably ruthenium trichloride, and the mass ratio of the activated carbon powder to the Ru precursor is 20 ~ 60: 1.
3. The method for preparing the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as claimed in claim 1, wherein the temperature for evaporating the suspension A in the step 2) is 75-90 ℃.
4. The method for preparing the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst as recited in claim 1, wherein in the step 3), the gas of the inert atmosphere is nitrogen; the high-temperature calcination temperature is 400-700 ℃, and the high-temperature calcination time is 3-7 h.
5. The carbon-supported ruthenium phosphide nanocluster bifunctional catalyst prepared by the process of any one of claims 1 ~ 4.
6. Carbon-supported phosphating as claimed in claim 5The application of the dual-functional catalyst of the ruthenium nanocluster in catalyzing the quinoline hydrogenation reaction is characterized in that the carbon-supported dual-functional catalyst of the ruthenium nanocluster phosphide is added into a high-pressure reactor, quinoline and a solvent are added into the high-pressure reactor, and H is used2After the air in the high-pressure reactor is replaced and exhausted, the high-pressure reactor is filled with H with a certain pressure2Heating and stirring for reaction for several hours, filtering the reaction solution after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the quinoline hydrogenation reaction product.
7. The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in the catalytic quinoline hydrogenation reaction is characterized in that the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to quinoline is 1:4 ~ 7, preferably 1:5, the solvent is ethanol or water, and the using amount of the solvent is 5-8 times of the mass of quinoline.
8. The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in the quinoline hydrogenation reaction catalysis as claimed in claim 6, wherein the H filled in the high-pressure reactor is used for thermal stirring reaction2The pressure is 0.3-1Mpa, the heating reaction temperature is 50-80 ℃, the heating reaction time is 3-10h, and the stirring speed is 800-1200 rpm.
9. The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing tetrahydroquinoline dehydrogenation reaction as claimed in claim 5, wherein the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst is added into a high-pressure reactor, tetrahydroquinoline and a solvent are added into the high-pressure reactor, and N is used2Displacing and exhausting air in the high-pressure reactor and leading N to be2And (3) after the internal space of the high-pressure reactor is filled, heating and stirring for reaction, filtering the reaction liquid after the reaction is finished, and concentrating the filtrate to remove the solvent to obtain the tetrahydroquinoline dehydrogenation reaction product.
10. The application of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst in catalyzing tetrahydroquinoline dehydrogenation reaction according to claim 9, wherein the mass ratio of the carbon-supported ruthenium phosphide nanocluster bifunctional catalyst to the tetrahydroquinoline is 1 (1.5-2); the solvent is benzene solvent, and the benzene solvent is p-xylene, o-xylene, m-xylene, xylene or mesitylene; the dosage of the solvent is 10-12 times of the mass of the tetrahydroquinoline; the reaction temperature is 135-145 ℃, and the reaction time is 20-24 h; the stirring speed was 250-450 rpm.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101862673A (en) * | 2010-06-28 | 2010-10-20 | 南开大学 | New method for preparing loaded Ru2P under mild condition |
CN101992109A (en) * | 2010-09-06 | 2011-03-30 | 常州介孔催化材料有限公司 | Transition metal phosphide hydrofined catalyst and preparation method thereof |
US9636664B1 (en) * | 2015-06-04 | 2017-05-02 | Alliance For Sustainable Energy, Llc | Metal phosphide catalysts and methods for making the same and uses thereof |
CN107162968A (en) * | 2017-05-25 | 2017-09-15 | 陕西师范大学 | A kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound |
CN107824209A (en) * | 2017-11-09 | 2018-03-23 | 中国科学院上海硅酸盐研究所 | Catalyst for quinolines selective hydrogenation and preparation method thereof |
-
2019
- 2019-10-10 CN CN201910960532.2A patent/CN110639567B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101862673A (en) * | 2010-06-28 | 2010-10-20 | 南开大学 | New method for preparing loaded Ru2P under mild condition |
CN101992109A (en) * | 2010-09-06 | 2011-03-30 | 常州介孔催化材料有限公司 | Transition metal phosphide hydrofined catalyst and preparation method thereof |
US9636664B1 (en) * | 2015-06-04 | 2017-05-02 | Alliance For Sustainable Energy, Llc | Metal phosphide catalysts and methods for making the same and uses thereof |
CN107162968A (en) * | 2017-05-25 | 2017-09-15 | 陕西师范大学 | A kind of method of visible light catalytic Tetrahydroquinolinesas oxidative dehydrogenation synthesis of quinoline class compound |
CN107824209A (en) * | 2017-11-09 | 2018-03-23 | 中国科学院上海硅酸盐研究所 | Catalyst for quinolines selective hydrogenation and preparation method thereof |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111617785A (en) * | 2020-07-09 | 2020-09-04 | 北京化工大学 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
CN111617785B (en) * | 2020-07-09 | 2021-10-15 | 北京化工大学 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
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CN113584502A (en) * | 2021-07-28 | 2021-11-02 | 青岛科技大学 | Preparation and application of molybdenum phosphide-ruthenium phosphide bimetal phosphide |
CN113584502B (en) * | 2021-07-28 | 2022-07-01 | 青岛科技大学 | Preparation and application of molybdenum phosphide-ruthenium phosphide bimetal phosphide |
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