CN116550387A - Ce-UiO-66 composite Ni NPs catalyst and preparation method and application thereof - Google Patents
Ce-UiO-66 composite Ni NPs catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000013207 UiO-66 Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 99
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 150000000703 Cerium Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- -1 cerium ions Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000006228 supernatant Substances 0.000 description 15
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst, which comprises the following steps: (1) Mixing cerium salt solution with DMF solution of terephthalic acid, stirring, heating for reaction, centrifuging, washing and drying the reaction product to obtain Ce-UiO-66; (2) Dipping Ce-UiO-66 in a methanol solution of nickel salt, and stirring for reaction; (3) Adding sodium borohydride methanol solution, stirring for reaction, centrifuging, taking precipitate, washing and drying to obtain the Ce-UiO-66 composite Ni NPs catalyst product. The preparation method of the Ce-UiO-66 composite Ni NPs catalyst provided by the invention has the advantages that the process is simple and mild, and the particle size of the catalyst product can be adjusted by adjusting the concentration of the reducing agent; meanwhile, the catalyst prepared by the method provided by the invention has extremely high catalytic conversion rate and tetrahydrodicyclopentadiene selectivity in dicyclopentadiene hydrogenation reaction.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a Ce-UiO-66 composite Ni NPs catalyst, a preparation method and application thereof.
The background technology is as follows:
MOFs materials have wide application in various fields such as catalysis, energy storage, adsorption and separation due to the advantages of high porosity, large specific surface area, ordered and controllable pore canal structure and the like. Cerium is the most abundant element in rare earth, and Ce in Ce-MOF generally exists in a mixed valence state of 3 and 4, and electron transfer between the two has a remarkable effect in the catalytic process. In addition, the use of Ce-MOF as a support to immobilize other metals may exhibit unique electronic interactions and synergistic effects, which may catalyze some high value added reactions such as dicyclopentadiene hydrogenation.
Dicyclopentadiene is a byproduct of petroleum cracking, and the product tetrahydrodicyclopentadiene produced by hydrogenation can be used to produce aviation fuel. The catalyst for dicyclopentadiene hydrogenation reaction used in industry at present is Raney nickel, a porous nickel material, but the catalyst has a certain danger and cannot be recycled, and many researches at present propose to use porous oxide or carbon material, molecular sieve and the like as carriers to fix noble metal and some transition metal as catalysts, so that the catalyst can be recycled more conveniently under the condition of ensuring the catalytic activity. However, the rare earth MOFs material supported metal is not directly used as a catalyst for dicyclopentadiene hydrogenation, and more MOFs material derivatives are used.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a Ce-UiO-66 composite Ni NPs catalyst with simple process and excellent product performance, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst, which comprises the following steps in sequence:
(1) Mixing cerium salt solution with DMF solution of terephthalic acid, stirring, heating for reaction, centrifuging, washing and drying the reaction product to obtain Ce-UiO-66;
(2) Dipping Ce-UiO-66 in a methanol solution of nickel salt, and stirring for reaction;
(3) Adding sodium borohydride methanol solution, stirring for reaction, centrifuging, taking precipitate, washing and drying to obtain the Ce-UiO-66 composite Ni NPs catalyst product.
Preferably or alternatively, the cerium salt in the cerium salt solution is ceric ammonium nitrate.
Preferably or alternatively, in step (1), the mass ratio of cerium ions to terephthalic acid in the cerium salt is 1:2 to 2:1, preferably the mass ratio is 1:1.
Preferably or alternatively, in step (1), the temperature of the heating reaction is 90-110 ℃, the reaction time is 15-20min, preferably, the temperature of the heating reaction is 100 ℃, and the reaction time is 20min.
Preferably or alternatively, in step (1), the washing step is washing with DMF and anhydrous methanol in sequence.
Preferably or alternatively, in step (2), the nickel salt is nickel chloride.
Preferably or alternatively, in step (2), the nickel salt is added in an amount of 5% by mass of Ce-UiO-66.
Preferably or alternatively, in step (2), the stirring reaction time is from 4 to 12 hours, preferably, the stirring reaction time is 4 hours.
Preferably or alternatively, in step (3), the stirring reaction time is from 0.5 to 1.5 hours, preferably, the stirring reaction time is 1 hour.
Preferably or alternatively, the mass ratio of the sodium borohydride added in step (3) to the nickel ions in the nickel salt added in step (2) is 7-11:1, preferably 10:1; the concentration of the sodium borohydride solution is 0.2-0.4M, and the concentration of the sodium borohydride solution is preferably 0.4M. .
On the other hand, the invention also provides a Ce-UiO-66 composite Ni NPs catalyst prepared by the method and application thereof in catalyzing dicyclopentadiene hydrogenation reaction.
Advantageous effects
The preparation method of the Ce-UiO-66 composite Ni NPs catalyst provided by the invention has the advantages that the process is simple and mild, and the particle size of the catalyst product can be adjusted by adjusting the concentration of the reducing agent; meanwhile, the catalyst prepared by the method provided by the invention has extremely high catalytic conversion rate and tetrahydrodicyclopentadiene selectivity in dicyclopentadiene hydrogenation reaction.
Drawings
FIG. 1 is a scanning electron microscope image of the Ce-UiO-66 composite Ni NPs catalyst prepared in example 1;
FIG. 2 is a scanning electron microscope image of the Ce-UiO-66 composite Ni NPs catalyst prepared in example 2;
FIG. 3 is a scanning electron microscope image of the Ce-UiO-66 composite Ni NPs catalyst prepared in comparative example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
Example 1
The embodiment of the invention provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst.
12.5mmol of ammonium cerium nitrate was dissolved in 25mL of deionized water at normal temperature to prepare an aqueous ammonium cerium nitrate solution.
12.5mmol of terephthalic acid was dissolved in 60mL of DMF at 100deg.C in an oil bath, and an aqueous solution of ceric ammonium nitrate was added, and after stirring for 15min, the system was cooled to room temperature. And taking a precipitate after centrifugation, washing with DMF, centrifuging to remove the supernatant, washing with absolute methanol, and centrifuging to remove the supernatant. The remaining product was dried at 60℃for 12h to give a pale yellow Ce-UiO-66 powder.
100mg of the prepared Ce-UiO-66 powder was weighed and dispersed in 5mL of methanol, and 1mL of NiCl with a concentration of 20.25mg/mL was added 2 ·6H 2 O methanol solution is stirred for 12h at normal temperature, then 4.5mL sodium borohydride methanol solution with concentration of 0.2M is added into the system dropwise, and the mixture is stirred for 1h, so that Ni in the system is obtained 2+ Reducing the catalyst into Ni NPs, centrifuging, taking precipitate, washing with methanol, centrifuging, removing supernatant, and vacuum drying at 60deg.C to obtain Ce-UiO-66 composite Ni NPs catalyst product, wherein the scanning electron microscope diagram of the product is shown in figure 1.
Example 2
The embodiment of the invention provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst.
12.5mmol of ammonium cerium nitrate was dissolved in 25mL of deionized water at normal temperature to prepare an aqueous ammonium cerium nitrate solution.
12.5mmol of terephthalic acid was dissolved in 60mL of DMF at 100deg.C in an oil bath, and an aqueous solution of ceric ammonium nitrate was added, and after stirring for 18min, the system was cooled to room temperature. And taking a precipitate after centrifugation, washing with DMF, centrifuging to remove the supernatant, washing with absolute methanol, and centrifuging to remove the supernatant. The remaining product was dried at 60℃for 12h to give a pale yellow Ce-UiO-66 powder.
100mg of the prepared Ce-UiO-66 powder was weighed and dispersed in 4mL of methanol, and 1mL of NiCl with a concentration of 20.25mg/mL was added 2 ·6H 2 O methanol solution is stirred for 12h at normal temperature, then 2.25mL sodium borohydride methanol solution with concentration of 0.4M is added into the system dropwise, and the mixture is stirred for 1h, so that Ni in the system is obtained 2+ Reducing into Ni NPs, centrifuging, collecting precipitate, washing with methanol, centrifuging to remove supernatant, vacuum drying at 60deg.C to obtain Ce-UiO-66 composite Ni NPs catalyst product, and scanning electron microscope image of the productAs shown in fig. 2.
Comparative example 1
The comparative example provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst.
12.5mmol of ammonium cerium nitrate was dissolved in 25mL of deionized water at normal temperature to prepare an aqueous ammonium cerium nitrate solution.
12.5mmol of terephthalic acid was dissolved in 60mL of DMF at 100deg.C in an oil bath, and an aqueous solution of ceric ammonium nitrate was added, and after stirring for 20min, the system was cooled to room temperature. And taking a precipitate after centrifugation, washing with DMF, centrifuging to remove the supernatant, washing with absolute methanol, and centrifuging to remove the supernatant. The remaining product was dried at 60℃for 12h to give a pale yellow Ce-UiO-66 powder.
100mg of the prepared Ce-UiO-66 powder was weighed and dispersed in 4mL of methanol, and 1mL of NiCl with a concentration of 20.25mg/mL was added 2 ·6H 2 O methanol solution is stirred for 12h at normal temperature, then 1.5mL sodium borohydride methanol solution with concentration of 0.6M is added into the system dropwise, and the mixture is stirred for 1h, so that Ni in the system is obtained 2+ Reducing the catalyst into Ni NPs, centrifuging, taking precipitate, washing with methanol, centrifuging, removing supernatant, and vacuum drying at 60deg.C to obtain Ce-UiO-66 composite Ni NPs catalyst product, wherein the scanning electron microscope diagram of the product is shown in figure 3.
Comparative example 2
The invention provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst.
12.5mmol of ammonium cerium nitrate was dissolved in 25mL of deionized water at normal temperature to prepare an aqueous ammonium cerium nitrate solution.
12.5mmol of terephthalic acid was dissolved in 60mL of DMF at 100deg.C in an oil bath, and an aqueous solution of ceric ammonium nitrate was added, and after stirring for 18min, the system was cooled to room temperature. And taking a precipitate after centrifugation, washing with DMF, centrifuging to remove the supernatant, washing with absolute methanol, and centrifuging to remove the supernatant. The remaining product was dried at 60℃for 12h to give a pale yellow Ce-UiO-66 powder.
100mg of the prepared Ce-UiO-66 powder was weighed and dispersed in 4mL of methanol, and 1mL of Ni (NO) having a concentration of 24.80mg/mL was added 3 ) 2 ·6H 2 O-armorStirring the alcohol solution for 12h at normal temperature, then dropwise adding 2.25mL of 0.4M sodium borohydride methanol solution into the system, and stirring for 1h to enable Ni in the system to be obtained 2+ Reducing the catalyst into Ni NPs, centrifuging, taking precipitate, washing with methanol, centrifuging, removing supernatant, and vacuum drying at 60deg.C to obtain Ce-UiO-66 composite Ni NPs catalyst product, wherein the scanning electron microscope diagram of the product is shown in figure 2.
Comparative example 3
The invention provides a preparation method of a Ce-UiO-66 composite Ni NPs catalyst.
12.5mmol of ammonium cerium nitrate was dissolved in 25mL of deionized water at normal temperature to prepare an aqueous ammonium cerium nitrate solution.
12.5mmol of terephthalic acid was dissolved in 60mL of DMF at 100deg.C in an oil bath, and an aqueous solution of ceric ammonium nitrate was added, and after stirring for 18min, the system was cooled to room temperature. And taking a precipitate after centrifugation, washing with DMF, centrifuging to remove the supernatant, washing with absolute methanol, and centrifuging to remove the supernatant. The remaining product was dried at 60℃for 12h to give a pale yellow Ce-UiO-66 powder.
100mg of the prepared Ce-UiO-66 powder was weighed and dispersed in 4mL of methanol, and 1mL of Ni (Ac) having a concentration of 21.20mg/mL was added 2 ·4H 2 O methanol solution is stirred for 12h at normal temperature, then 2.25mL sodium borohydride methanol solution with concentration of 0.4M is added into the system dropwise, and the mixture is stirred for 1h, so that Ni in the system is obtained 2+ Reducing the catalyst into Ni NPs, centrifuging, taking precipitate, washing with methanol, centrifuging, removing supernatant, and vacuum drying at 60deg.C to obtain Ce-UiO-66 composite Ni NPs catalyst product, wherein the scanning electron microscope diagram of the product is shown in figure 2.
Effect examples
DCPD conversion and THDCPD selectivity of the Ce-UIO-66 composite Ni NPs catalysts prepared in examples 1-2 and comparative example 1 were measured.
20mg of the catalyst prepared in examples 1-3 was weighed and placed in a 50mL hydrogenation reactor, and 200. Mu.L CPD and 5mL cyclohexane were added respectively to react at 100℃under a hydrogen pressure of 2MPa at a rotation speed of 600rpm for 2 hours.
Then 50. Mu.L of the reacted liquid was taken and placed in a 1.5mL sample bottle, diluted with ethanol, and characterized by liquid chromatography to obtain the percentages of the reactants and the respective products in the reaction product, from which the DCPD conversion and THDCPD selectivity of the catalyst product of each example were calculated.
The results of the measurement of the Ce-UiO-66 composite Ni NPs catalysts of each example and comparative example are shown in Table 1.
Table 1 catalyst performance test results table
| Group of | DCPD conversion (%) | THDCPD Selectivity (%) |
| Example 1 | 100 | 89.8 |
| Example 2 | 100 | 100 |
| Comparative example 1 | 100 | 25.4 |
| Comparative example 2 | 31.6 | 5.4 |
| Comparative example 3 | 100 | 75.6 |
As can be seen from Table 1, the Ce-UIO-66 composite Ni NPs catalyst provided by the invention has 100% conversion rate in dicyclopentadiene hydrogenation reaction, and simultaneously has 100% tetrahydrodicyclopentadiene selectivity in dicyclopentadiene hydrogenation reaction, and therefore, the Ce-UIO-66 composite Ni NPs catalyst prepared by the method provided by the invention has good catalytic performance.
As can be seen from further combination of the scanning electron microscope images of the examples and the comparative examples, when the concentration of the sodium borohydride methanol solution in the reaction process is increased, the particle size and the agglomeration degree of the catalyst as a product are further increased, so that the selectivity of THDCPD of the catalyst is further reduced, and the selectivity of nickel salt in the preparation process also affects the performance of the finally prepared catalyst.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (12)
1. The preparation method of the Ce-UiO-66 composite NiNPs catalyst is characterized by comprising the following steps of:
(1) Mixing cerium salt solution with DMF solution of terephthalic acid, stirring, heating for reaction, centrifuging, washing and drying the reaction product to obtain Ce-UiO-66;
(2) Dipping Ce-UiO-66 in a methanol solution of nickel salt, and stirring for reaction;
(3) Adding sodium borohydride methanol solution, stirring for reaction, centrifuging, taking precipitate, washing and drying to obtain the Ce-UiO-66 composite Ni NPs catalyst product.
2. The method for preparing a catalyst according to claim 1, wherein the cerium salt in the cerium salt solution is cerium nitrate.
3. The method for preparing a catalyst according to claim 1, wherein in the step (1), the mass ratio of cerium ions to terephthalic acid in the cerium salt is 1:2 to 2:1, preferably the mass ratio is 1:1.
4. The method for preparing a catalyst according to claim 1, wherein in the step (1), the heating reaction is carried out at a temperature of 90 to 110 ℃ for a reaction time of 15 to 20 minutes, preferably at a temperature of 100 ℃ for a reaction time of 20 minutes.
5. The method for preparing a catalyst according to claim 1, wherein in the step (1), the washing step is washing with DMF and anhydrous methanol in this order.
6. The method for preparing a catalyst according to claim 1, wherein in the step (2), the nickel salt is nickel chloride.
7. The method for producing a catalyst according to claim 6, wherein in the step (2), the addition amount of the nickel salt is 5% by mass of Ce-UiO-66.
8. The method for preparing a catalyst according to claim 1, wherein in the step (2), the stirring reaction time is 4 to 12 hours, preferably, the stirring reaction time is 4 hours.
9. The method for preparing a catalyst according to claim 1, wherein in the step (3), the stirring reaction time is 0.5 to 1.5 hours, preferably, the stirring reaction time is 1 hour.
10. The method for preparing the catalyst according to claim 1, wherein the mass ratio of the sodium borohydride added in the step (3) to the nickel ions in the nickel salt added in the step (2) is 7-11:1, and the preferred mass ratio is 10:1; the concentration of the sodium borohydride solution is 0.2-0.4M, and the concentration of the sodium borohydride solution is preferably 0.4M.
11. A Ce-UiO-66 composite Ni NPs catalyst, characterized in that it is prepared by the method of any one of claims 1-10.
12. Use of the Ce-UiO-66 composite NiNPs catalyst according to claim 11 for catalyzing dicyclopentadiene hydrogenation reactions.
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| CN117126319A (en) * | 2023-10-26 | 2023-11-28 | 传化智联股份有限公司 | Pre-catalyst, rare earth catalyst and preparation of polybutadiene |
| CN117126319B (en) * | 2023-10-26 | 2024-02-13 | 传化智联股份有限公司 | Pre-catalyst, rare earth catalyst and preparation of polybutadiene |
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