CN117258803A - Mesoporous cerium oxide loaded PdCu nanoparticle catalyst and preparation method and application thereof - Google Patents
Mesoporous cerium oxide loaded PdCu nanoparticle catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 40
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 34
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 32
- 150000002085 enols Chemical class 0.000 claims abstract description 23
- 229920000620 organic polymer Polymers 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000000703 Cerium Chemical class 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000013308 plastic optical fiber Substances 0.000 claims description 23
- 239000013309 porous organic framework Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 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 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
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- 238000006555 catalytic reaction Methods 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
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- 238000000967 suction filtration Methods 0.000 claims description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
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- 238000005882 aldol condensation reaction Methods 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 16
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- MGSORLTWPQCXQY-UHFFFAOYSA-N CCOCC#CO Chemical compound CCOCC#CO MGSORLTWPQCXQY-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- UFLHIIWVXFIJGU-ARJAWSKDSA-N (Z)-hex-3-en-1-ol Chemical compound CC\C=C/CCO UFLHIIWVXFIJGU-ARJAWSKDSA-N 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
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- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- 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
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002415 Pluronic P-123 Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical group [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UFLHIIWVXFIJGU-UHFFFAOYSA-N hex-3-en-1-ol Natural products CCC=CCCO UFLHIIWVXFIJGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000012552 review Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/02—Reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a mesoporous cerium oxide loaded PdCu nanoparticle catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts. The invention utilizes melamine and terephthalaldehyde to carry out aldehyde-amine polycondensation reaction to obtain a porous organic polymer template material; filling PdCu alloy nano particles and cerium salt precursors in holes of a porous organic polymer template material, and roasting to remove a template agent to obtain the mesoporous cerium oxide loaded PdCu nano particle catalyst. The catalyst can be used for catalyzing alkynol to prepare enol by selective hydrogenation, the conversion rate of alkynol can be up to 100%, the selectivity of enol is higher than 99%, and the catalyst can be used for at least 5 times stably.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a mesoporous cerium oxide loaded PdCu nanoparticle catalyst, and a preparation method and application thereof.
Background
The selective hydrogenation reaction of alkynols is a main way for synthesizing linalool, isophytol, 2-methyl-3-butene-2-ol, cis-3-hexene-1-ol (leaf alcohol), cis-2-butene-1, 4-diol and other enol, and the enol is a key intermediate in the industrial production of high-added value medicines, agricultural chemicals, essence and perfume. However, the process of obtaining alkenols by selective hydrogenation of alkynols is difficult and heavy, and in addition to protecting other functional groups such as C-OH in the alkynol molecule, it is important to avoid excessive hydrogenation of c≡c to C-C, and to selectively produce c=c.
In recent years, due to the interest and study of selective hydrogenation reactions of alkynes and alkynes, various metal supported catalysts (such as Pd, pt, ni, etc.) have been developed to catalyze such reactions (Catalysis Science & Technology,2020,10 (2): 327-331). However, these metal supported catalysts generally have larger metal nanoparticles and a wide range of particle size distributions, so that the metal active sites expose different crystal planes having different atomic structures. The heterogeneity of the active sites can result in poor selectivity of the catalytic reaction due to the difference in interactions between the reactants and the metal active sites during alkynyl hydrogenation (Chemical Reviews,2020,120 (2): 683-733).
Mesoporous materials are key carrier materials for constructing supported hydrogenation catalysts, wherein mesoporous cerium oxide nano materials have high specific surface area and abundant porous structures, and have important application in the fields of industrial catalysis, fuel cells, sensitive devices and the like, and the high-surface area mesoporous cerium oxide materials are mainly prepared by the following methods at present: with mesoporous carbon or mesoporous SiO 2 Mesoporous cerium oxide carrier materials (Journal of Colloid and Interface Science,436 (2014) 52-62) are prepared by a sol-gel method and a hydrothermal synthesis method by taking pluronic P123 or F127 as a hard template and taking pluronic P127 as a soft template; the existing preparation methods of the mesoporous cerium oxide carrier still have the problems of large waste liquid discharge, complicated preparation and the like in the preparation process.
Aiming at the technical bottlenecks in the fields of selective hydrogenation of alkynols and research of the current mesoporous cerium oxide catalytic materials with high specific surface area, the development of an efficient mesoporous cerium oxide supported catalyst for synthesizing enol by catalyzing alkynol hydrogenation with high selectivity has important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a mesoporous cerium oxide loaded PdCu nanoparticle catalyst, and a preparation method and application thereof. The invention adopts porous organic polymer as a template, and the pores of the porous organic polymer are pre-filled with PdCu alloy nano particles and cerium salt precursors, and the polymer template is removed by roasting, and then the catalyst in the PdCu alloy anchored Yu Jiekong cerium oxide pores is prepared by reduction, and the method for preparing enol by selectively catalyzing alkynol hydrogenation has the following reaction equation:
in order to achieve the above purpose, the present invention provides the following technical solutions:
the technical scheme is as follows: mesoporous cerium oxide loaded PdCu nanoparticle catalyst, wherein the mass ratio of each component in the mesoporous cerium oxide loaded PdCu nanoparticle catalyst is Pd, cu and CeO 2 = (1-4) to 100. The specific surface area of the mesoporous cerium oxide loaded PdCu nanoparticle catalyst is 68m 2 Per g, pore size distribution of 5-60nm, pore volume of 0.3cm 3 /g。
"active site isolation" is the improvement of the selectivity of a catalyst in a catalytic reaction by homogenizing the metal active sites by isolating them to inhibit side reactions that may be caused by metal aggregation. The present invention adjusts the composition and structure of the metal active sites in the catalyst by using the second metallic copper as a modifier. In bi-or multi-metallic nanoparticles, interactions between components alter the complex structure of the catalytic sites and change the electronic structure of the active metal by forms such as charge transfer. These two influencing factors determine the manner and strength of the binding of the reactants/intermediates/products at the active site, which directly influences the selectivity of the catalyst. As a metal having a high electron density and low cost, the present invention uses Cu as a second metal doping to change the properties of an active metal.
The second technical scheme is as follows: a mesoporous cerium oxide supported PdCu nanoparticle catalyst preparation method, utilize melamine and terephthalaldehyde to carry on aldehyde amine condensation polymerization, get porous organic polymer template material (POFs); filling PdCu alloy nano particles and cerium salt precursors in holes of a porous organic polymer template material, and roasting to remove a template agent to obtain the mesoporous cerium oxide loaded PdCu nano particle catalyst.
Further, the preparation method specifically comprises the following steps: weighing melamine and terephthalaldehydePerforming aldehyde amine polycondensation reaction to obtain a porous organic polymer template material; ultrasonically dispersing a porous organic polymer template material in a mixed aqueous solution of palladium acetate and copper nitrate, and dropwise adding a sodium borohydride solution for reduction to obtain a PdCu-POFs material of PdCu bimetallic nano particles; dispersing PdCu-POFs material into aqueous solution of cerium nitrate by ultrasonic, slowly dripping NaOH solution under intense stirring, reacting for 3 hours, removing solvent by suction filtration, drying the obtained solid sample, placing the solid sample in a muffle furnace, heating to 600 ℃ in an argon atmosphere at a speed of 4 ℃/min for 2 hours, then roasting in air at 600 ℃ for 2 hours, and cooling to 400 ℃ for H 2 Reducing Ar for 2 hours to obtain PdCu-CeO 2 A catalyst.
Further, the preparation method of the porous organic polymer template material comprises the following steps: 5g of melamine (99%) and 8g of terephthalaldehyde (99%) were added to 250mL of dimethyl sulfoxide (99.9%) and heated to 180℃at a rate of 20℃per minute under argon atmosphere, and reacted for 72 hours with stirring at this temperature, followed by filtering to remove the solvent and washing the yellow solid sample three times with ethanol, and vacuum drying at 80℃for 6 hours, to obtain porous organic polymer POFs materials.
Further, the mass ratio of the PdCu-POFs material to the cerium nitrate is 1:2.6. The aqueous solution of cerium nitrate was prepared by dissolving 2.6g of cerium nitrate in 50mL of water.
The technical scheme is as follows: the preparation method of the enol takes alkynol as a raw material, takes the mesoporous cerium oxide loaded PdCu nanoparticle catalyst as a catalyst, takes ethanol as a solvent, and carries out catalytic reaction under normal pressure and room temperature hydrogen atmosphere to obtain the enol. The catalyst has the catalytic active site of PdCu alloy nano particles in the catalytic hydrogenation reaction, and the selectivity of a reaction product can be remarkably improved by regulating and controlling the electronic performance of Cu on active metal Pd. The conversion rate of alkynol and the selectivity of enol are detected by gas chromatography or gas chromatograph-mass spectrometer analysis, the conversion rate of alkynol can reach 100%, the selectivity of enol is higher than 99%, and the catalyst can be used (recycled) for at least 5 times stably.
Further, the dosage ratio of the alkynol to the mesoporous cerium oxide loaded PdCu nanoparticle catalyst is 1mmol to 10mg. The hydrogen pressure was 1atm.
The technical scheme is as follows: the enol prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and technical effects:
1. PdCu-CeO prepared by the invention 2 The catalyst is prepared by using a POFs template sacrificial method, so that the catalyst has high specific surface area and large pore size distribution; and Cu metal is used as a second metal to adjust the electronic structure of the active metal Pd and the composition of the active site, so that the selectivity of synthesizing enol by hydrogenating alkynol is improved.
2. Takes alkynol as raw material, hydrogen as reducer, and PdCu-CeO is used as catalyst 2 The catalyst is used for synthesizing enol by selective catalytic hydrogenation at normal temperature and normal pressure, the reaction temperature is room temperature, no toxic or harmful waste is discharged in the reaction process, and the method for synthesizing alkynol by selective catalytic hydrogenation is more environment-friendly.
3. Mesoporous PdCu-CeO provided by the invention 2 The catalyst and the method for synthesizing enol by catalyzing alkynol to be selectively catalyzed and hydrogenated are simple in operation, easy to control, high in product selectivity, green and economical, and easy for industrial mass production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 shows PdCu-CeO prepared in example 1 of the present invention 2 A catalyst transmission electron microscope image; wherein: (a) and (b) are transmission electron microscope pictures with different magnifications, and (c) is PdCu-CeO 2 A dark field transmission electron microscope image of the catalyst;
FIG. 2 shows PdCu-CeO prepared in example 1 of the present invention 2 Nitrogen adsorption and desorption of the catalyst and pore size distribution diagram;
FIG. 3 is a PdCu-CeO prepared in example 3 of the present invention 2 And (3) a catalyst reuse effect diagram.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
As used herein, the term "room temperature" is defined as 20℃unless otherwise specified.
The raw materials used in the following examples of the present invention are all commercially available.
The invention provides mesoporous cerium oxide loaded PdCu nanoparticleThe preparation method of the granular catalyst mainly comprises the steps of carrying out aldehyde-amine polycondensation reaction on melamine and terephthalaldehyde to obtain porous organic polymer template materials (POFs); filling PdCu alloy nano particles and cerium salt precursors in the holes of the porous organic polymer template material, removing POFs template by roasting, and reducing to obtain PdCu-CeO with the PdCu nano particles anchored in mesoporous cerium oxide holes 2 A catalyst.
The preparation method of the porous organic polymer template material comprises the following steps: 5g of melamine (the active ingredient is 99%) and 8g of terephthalaldehyde (the active ingredient is 99%) are added into 250mL of dimethyl sulfoxide (the active ingredient is 99.9%), the mixture is heated to 180 ℃ at a speed of 20 ℃/min in argon atmosphere, stirred and reacted for 72 hours at the temperature, then the solvent is removed by suction filtration, a yellow solid sample is washed three times by ethanol, and the mixture is dried in vacuum at 80 ℃ for 6 hours, thus obtaining the porous organic polymer POFs material.
The PdCu-CeO 2 The preparation method of the catalyst comprises the following steps: 1g of POFs material is ultrasonically dispersed in a mixed aqueous solution of palladium acetate and copper nitrate, and is dripped with a sodium borohydride dilute solution to be reduced, so that the PdCu-POFs material of the PdCu bimetallic nano-particles is obtained; 2.6g Ce (NO) 3 ) 3 ·6H 2 O is dissolved in 50mL of water, 1g of PdCu-POFs is added into the solution, the mixture is ultrasonically treated for 60 minutes, then NaOH solution is slowly added dropwise under the condition of intense stirring for 3 hours, the solvent is removed by filtration, the obtained solid sample is dried and then is placed in a muffle furnace to be roasted for 2 hours at the speed of 4 ℃/min to 600 ℃ in the argon atmosphere, then is roasted for 2 hours at the temperature of 600 ℃ in the air, and is cooled to 400 ℃ to be treated by H with the volume ratio of 1:3 2 Reducing Ar mixed gas for 2 hours to obtain PdCu-CeO 2 A catalyst.
The PdCu-CeO prepared is 2 The specific surface area of the catalyst is 68m 2 Per g, pore size distribution of 5-60nm, pore volume of 0.3cm 3 /g。PdCu-CeO 2 The mass ratio of each component in the catalyst is Pd, cu and CeO 2 = (1-4) to 100. Preferably 2:2:100.
The PdCu-CeO obtained by the preparation 2 Adding catalyst, alkynol and solvent ethanol into a reactor, extractingAnd (3) using normal-pressure hydrogen as a hydrogen source, and carrying out catalytic reaction at room temperature to obtain enol. In the reaction process of synthesizing enol by selective catalytic hydrogenation of alkynol, the hydrogen pressure is 1atm, and the reaction temperature is room temperature. The conversion rate of alkynol and the selectivity of enol are detected by gas chromatography or gas chromatograph-mass spectrometer analysis, the conversion rate of alkynol can reach 100%, the selectivity of enol is higher than 99%, and the catalyst can be stably recycled for 5 times at least. The catalytic hydrogenation reaction has the catalytic active site of PdCu alloy nano particles, and the selectivity of a reaction product can be obviously improved by regulating and controlling the electronic performance of Cu on active metal Pd.
The following examples serve as further illustrations of the technical solutions of the invention.
Example 1
Preparation of mesoporous cerium oxide loaded PdCu nanoparticle catalyst:
1) Preparation of POFs template material: 5g of melamine (99%) and 8g of terephthalaldehyde (99%) were added to 250mL of dimethyl sulfoxide (99.9%) and heated to 180℃at a rate of 20℃per minute under argon atmosphere, and reacted for 72 hours with stirring at this temperature, followed by filtering to remove the solvent and washing the yellow solid sample three times with ethanol, and vacuum drying at 80℃for 6 hours, to obtain porous organic polymer POFs materials.
2)PdCu-CeO 2 Preparation of the catalyst: 1g of POFs material is ultrasonically dispersed in 10mL of mixed aqueous solution of palladium acetate and copper nitrate (the mass ratio of palladium acetate to copper nitrate to water is 0.002:0.002:1), 2mL of 0.1mol/L sodium borohydride dilute solution is added dropwise for reduction, and 1g of PdCu-POFs material of PdCu bimetallic nano-particles is obtained; 2.6g of Ce (NO 3 ) 3 ·6H 2 O is dissolved in 50mL of water, 1g of PdCu-POFs is added into the solution, the mixture is sonicated for 60 minutes, 10mL of 2mol/L NaOH solution is slowly added dropwise under the condition of intense stirring for reaction for 3 hours, the solvent is removed by filtration, the mixture is baked for 2 hours under argon atmosphere after being dried, the temperature is increased to 600 ℃ at the speed of 4 ℃ per minute, then the mixture is baked for 2 hours in air at 600 ℃, and the temperature is reduced to 400 ℃ by H 2 Ar (volume ratio is 1:3) is reduced for 2 hours, and the mass ratio of the components is Pd, cu and CeO 2 PdCu-CeO=2:2:100 2 Catalyst 1g.
FIG. 1 shows PdCu-CeO prepared in example 1 of the present invention 2 A catalyst transmission electron microscope image; wherein: (a) and (b) are transmission electron microscope pictures with different magnifications, and (c) is PdCu-CeO 2 A dark field transmission electron microscope image of the catalyst; as can be seen from the figure, pd and Cu elements are uniformly distributed in CeO 2 And (3) on a carrier.
FIG. 2 shows PdCu-CeO prepared in example 1 of the present invention 2 Nitrogen adsorption and desorption of the catalyst and pore size distribution diagram; as can be seen from the figure, the PdCu-CeO was prepared 2 The specific surface area of the catalyst is 68m 2 Per g, pore size distribution of 5-60nm, pore volume of 0.3cm 3 /g。
Example 2
The method for preparing enol by catalyzing selective hydrogenation of alkynol comprises the following steps: 10mg of PdCu-CeO prepared in example 1 2 Catalyst, 1mmol of ethoxypropynol is added into a 10mL round bottom flask containing 5mL of absolute ethyl alcohol, normal pressure hydrogen is introduced, stirring reaction is carried out at 70 ℃, the product yield is detected by gas chromatography analysis, after 60min of reaction, the conversion rate of the ethoxypropynol is 94%, and the selectivity of the ethoxypropynol is 98%.
Example 3
PdCu-CeO recovered by filtration and separation in example 2 2 The catalyst is used for catalyzing alkynol to be hydrogenated selectively to prepare enol again, and the specific method is as follows:
the recovered PdCu-CeO 2 Adding the catalyst and 1mmol of ethoxypropynyl alcohol into a 10mL round bottom flask containing 5mL of ethanol, introducing normal pressure hydrogen, stirring at 70 ℃ for reaction, and detecting the product yield by gas chromatography analysis, pdCu-CeO 2 The catalyst is used for 5 times (each reaction time is 60 min), the conversion rate of the ethoxypropynol is higher than 90%, and the selectivity of the ethoxypropynol is higher than 95% (see figure 3).
Examples 4 to 11
PdCu-CeO prepared in example 1 was used 2 The catalyst catalyzes selective catalytic hydrogenation of various alkynols, and the specific method is as follows:
10mg of PdCu-CeO was added 2 Catalyst, 1mmol of alkynol, added toIn a 10mL round bottom flask containing 5mL of ethanol, normal pressure hydrogen was introduced, the reaction was stirred at 70℃and the product yield was measured by gas chromatography, and the specific reaction results are shown in Table 1.
TABLE 1 PdCu-CeO 2 Catalyzing selective hydrogenation reaction of different substituted alkynols.
PdCu-CeO prepared in this example 2 The catalyst is used for catalyzing alkynol selective catalytic hydrogenation reaction, and the specific method is the same as that of example 2, so that the reaction conversion rate is higher than 98%, and the product selectivity is 90%.
Example 12
As in example 1, 1.7. 1.7gCe (NO 3 ) 3 ·6H 2 O was dissolved in 50mL of water, and then 0.5g of PdCu-POFs prepared in example 1 was added to the solution to give PdCu-CeO 2 Catalyst (mass ratio of each component is Pd: cu: ceO) 2 ＝1∶1∶100)。
PdCu-CeO prepared in this example 2 The specific method for synthesizing ethoxypropenol by catalytic hydrogenation of ethoxypropenol by catalyst is the same as that of example 2, and the result shows that the reaction conversion rate is 86% and the product selectivity is 98%.
Example 13
As in example 1, 1.7g Ce (NO 3 ) 3 ·6H 2 O was dissolved in 50mL of water, and 1.5g of PdCu-POFs prepared in example 1 was added to the solution to give PdCu-CeO 2 Catalyst (mass ratio of each component is Pd: cu: ceO) 2 ＝3∶3∶100)。
PdCu-CeO prepared in this example 2 The specific method for synthesizing ethoxypropenol by catalytic hydrogenation of ethoxypropenol by catalyst is the same as that of example 2, and the result shows that the reaction conversion rate is 99% and the product selectivity is 92%.
Example 14
As in example 1, 1.7. 1.7gCe (NO 3 ) 3 ·6H 2 O was dissolved in 50mL of water, and then 2g of PdCu-POFs prepared in example 1 was added to the solution to give PdCu-CeO 2 Catalyst (mass ratio of each component is Pd: cu: ceO) 2 ＝4∶4∶100)。
PdCu-CeO prepared in this example 2 The specific method for synthesizing ethoxypropenol by catalytic hydrogenation of ethoxypropenol by catalyst is the same as that of example 2, and the result shows that the reaction conversion rate is 100%, and the product selectivity is 87%.
Comparative example 1
The same procedure as in example 1 was followed except that palladium acetate was replaced with platinum acetate in equal amounts.
The catalyst prepared in the comparative example is used for catalyzing alkynol selective catalytic hydrogenation reaction, and the specific method is the same as that of example 2, so that the reaction conversion rate is higher than 85%, and the product selectivity is 95%.
Comparative example 2
The same procedure as in example 2 was followed except that the copper nitrate was replaced with palladium acetate in equal amounts.
The palladium-supported catalyst prepared in the comparative example is used for catalyzing alkynol selective catalytic hydrogenation reaction, and the specific method is the same as that in example 2, so that the reaction conversion rate is higher than 99%, and the product selectivity is 84%.
Comparative example 3
As in example 2, pdCu-CeO is different from 2 The catalyst was added in an amount of 8mg.
PdCu-CeO prepared in this comparative example 2 The catalyst catalyzes alkynol to perform selective catalytic hydrogenation reaction, and as a result, the reaction conversion rate is higher than 86%, and the product selectivity is 98%.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. Mesoporous oxidationThe cerium-loaded PdCu nanoparticle catalyst is characterized in that the mass ratio of each component in the mesoporous cerium oxide-loaded PdCu nanoparticle catalyst is Pd, cu and CeO 2 ＝(1-4)∶(1-4)∶100。
2. The mesoporous cerium oxide supported PdCu nanoparticle catalyst of claim 1, wherein the mesoporous cerium oxide supported PdCu nanoparticle catalyst has a specific surface area of 68m 2 Per g, pore size distribution of 5-60nm, pore volume of 0.3cm 3 /g。
3. A method for preparing the mesoporous cerium oxide supported PdCu nanoparticle catalyst of claim 1 or 2, characterized in that melamine and terephthalaldehyde are utilized to carry out aldol condensation polymerization to obtain a porous organic polymer template material; filling PdCu alloy nano particles and cerium salt precursors in the holes of the porous organic polymer template material; roasting to remove the template agent to obtain the mesoporous cerium oxide loaded PdCu nanoparticle catalyst.
4. The method for preparing a mesoporous cerium oxide supported PdCu nanoparticle catalyst of claim 3, wherein the method for filling PdCu alloy nanoparticles and cerium salt precursors comprises the steps of:
ultrasonically dispersing a porous organic polymer template material in a mixed aqueous solution of palladium acetate and copper nitrate, and dropwise adding a sodium borohydride solution for reduction to obtain a PdCu-POFs material of PdCu bimetallic nano particles;
dispersing PdCu-POFs material into aqueous solution of cerium nitrate by ultrasonic, dropwise adding NaOH solution under stirring, reacting for 3h, removing solvent by suction filtration, and drying the obtained solid sample.
5. The method for preparing a mesoporous cerium oxide supported PdCu nanoparticle catalyst of claim 3, wherein the method for calcining comprises the following steps: sequentially heating to 600 deg.C in argon and air atmosphere, calcining for 2 hr, cooling to 400 deg.C, and using H 2 Ar reduction.
6. The method for preparing a mesoporous cerium oxide supported PdCu nanoparticle catalyst according to claim 3, wherein the mass ratio of melamine to terephthalaldehyde is 5:8.
7. The method for preparing mesoporous cerium oxide supported PdCu nanoparticle catalyst according to claim 4, wherein the mass ratio of PdCu-POFs material to cerium nitrate is 1:2.6.
8. The preparation method of the enol is characterized in that alkynol is used as a raw material, the mesoporous cerium oxide loaded PdCu nanoparticle catalyst as defined in claim 1 or 2 is used as a catalyst, ethanol is used as a solvent, and catalytic reaction is carried out under the atmosphere of normal pressure and room temperature hydrogen to obtain the enol.
9. The preparation method according to claim 8, wherein the dosage ratio of the alkynol to the mesoporous cerium oxide supported PdCu nanoparticle catalyst is 1mmol to 10mg.
10. An enol prepared by the process of claim 8 or 9.
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