CN111744550A - Preparation method of two-dimensional nanosheet layer hydrogenation catalyst - Google Patents
Preparation method of two-dimensional nanosheet layer hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000002135 nanosheet Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 23
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 22
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- 150000002940 palladium Chemical class 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 57
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910021389 graphene Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 150000002828 nitro derivatives Chemical class 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 8
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to a preparation method of a two-dimensional nanosheet layer hydrogenation catalyst, and belongs to the technical field of catalysis. Firstly, dissolving divalent palladium salt and polyvinylpyrrolidone in a solvent respectively, and performing reduction reaction by using a mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide to prepare polyvinylpyrrolidone-coated Pd nanoparticles; and then, adding the Pd nano particles wrapped by polyvinylpyrrolidone in the process of forming the two-dimensional ZIF-L-GO composite nanosheets to prepare the three-element Pd-ZIF-L-GO catalyst with the two-dimensional nanosheet structure. The invention has the advantages that the prepared composite catalyst has a two-dimensional nanosheet-sheet structure, which is beneficial to the dispersion of active components and the diffusion of reactants; the Pd-ZIF-L-GO is uniformly dispersed under the synergistic action, the catalyst has good stability, and the catalyst shows excellent catalytic performance in the hydrogenation reaction of nitro-compounds.
Description
Technical Field
The invention relates to a preparation method of a two-dimensional nanosheet layer catalyst, in particular to a preparation method of a two-dimensional nanosheet layer hydrogenation catalyst, and belongs to the technical field of catalysis.
Background
In recent years, graphene and metal sulfides (e.g., MoS) have been used2) The two-dimensional nanomaterials as represented have attracted great attention due to their unique physicochemical properties. Different from the fact that the active sites of the three-dimensional nano material are mainly in the pore channels, the active sites of the two-dimensional nano material can be exposed on the surface of the sheet layer in a large amount, so that the contact between active components and reactant molecules is facilitated, the surface electron transmission capability is enhanced, and the three-dimensional nano material has great potential in the fields of heterogeneous catalysis, gas adsorption, chemical/biological sensing and the like. The graphene-based composite material is one of important research directions in the application field of two-dimensional nano materials, and the addition of the two-dimensional graphene is proved to improve the performance of the composite material and expand the new application field. Patent (CN 104437572 a) reports a preparation method of a graphene-supported nano nickel phosphide hydrogenation catalyst, which uses graphene oxide with a unique two-dimensional structure and rich oxygen-containing groups as a carrier to support nickel phosphide, thereby realizing high dispersion of a nickel source and effectively improving the catalytic and conductive properties of the material.
Zeolite Imidazolate Framework (ZIFs) is a novel MOFs material with a zeolite topological structure formed by complexing divalent transition metal ions such as Zn/Co and the like and imidazolyl, and is widely applied due to the characteristics of high specific surface area, good stability, uniform and adjustable pore channels and the like. Recently, research on ZIFs/graphene composite materials is increasing. Researches show that the composition of the ZIFs and the graphene not only has unique performances (CN108927174A) of the two materials, but also derives the properties which are not possessed by any component, and has unique superiority in the aspects of being used as a catalyst carrier and the like. Although some documents about three-dimensional ZIFs and graphene composite materials exist at present, in most cases, graphene nanosheets are freely dispersed in micron-sized ZIFs crystals or serve as carriers of ZIFs nanocrystals, and the design and synthesis of two-dimensional ZIFs and graphene nanosheets are not reported. Compared with a three-dimensional ZIFs-two-dimensional graphene-based composite carrier, the catalyst prepared by taking the two-dimensional nanosheet composite material as the carrier is more beneficial to rapid mass transfer between substrate molecules and active sites, so that the catalytic performance is improved.
The invention discloses a preparation method of a ternary Pd-ZIF-L-GO catalyst by taking a two-dimensional nanosheet layer ZIF-L-GO as a carrier, and the preparation method specifically comprises the steps of adding Pd nanoparticles wrapped by polyvinylpyrrolidone in the process of forming a ZIF-L-GO composite nanosheet, wherein the Pd nanoparticles can be effectively anchored by the presence of oxygen-containing functional groups on the surface of GO, so that the Pd nanoparticles are prevented from being aggregated and lost, and meanwhile, the dispersion of the Pd nanoparticles is effectively improved by the coordination of ZIF-L and GO. The method for preparing the Pd-ZIF-L-GO composite catalyst is simple to operate, and the two-dimensional nanosheet structure and the synergistic effect of the Pd-ZIF-L-GO are beneficial to the exposure and the stability of Pd nanoparticles, so that the Pd-ZIF-L-GO composite catalyst shows excellent catalytic performance in the reaction of nitro-compound hydrogenation.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional nanosheet hydrogenation catalyst, which is characterized in that a ZIF-L-GO carrier with a two-dimensional nanosheet structure is prepared by adopting an in-situ synthesis method, and a Pd nanoparticle coated with polyvinylpyrrolidone is added in the carrier construction process to prepare the catalyst for the reaction of a high-performance nitro-compound.
The technical scheme of the invention is as follows: a preparation method of a two-dimensional nanosheet layer hydrogenation catalyst comprises the following specific steps:
(1) adding polyvinylpyrrolidone (PVP) solution into a divalent palladium salt solution, adding a mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide for reduction reaction to prepare Pd nano-particles coated by PVP, and dispersing the Pd nano-particles in the aqueous solution to form PVP-Pd sol;
(2) ultrasonically dispersing graphene oxide GO powder in an aqueous solution to obtain a uniformly dispersed graphene oxide solution;
(3) mixing zinc nitrate and a graphene oxide solution to obtain an intermediate Zn-GO solution;
(4) mixing the PVP-Pd sol obtained in the step (1), a 2-methylimidazole water solution and the intermediate Zn-GO solution obtained in the step (3), and reacting at a certain temperature;
(5) washing the sample obtained in the step (4) with deionized water for a plurality of times, and drying in an oven; obtaining the two-dimensional nano-sheet hydrogenation catalyst.
Preferably, in the step (1), the divalent palladium salt is palladium acetate, palladium chloride or palladium nitrate; the concentration of the divalent palladium salt is 5-30 mmol/L; the molar ratio of the divalent palladium salt to the polyvinylpyrrolidone is 1 (10-40); the solvents in the divalent palladium salt solution and the polyvinylpyrrolidone solution are dichloromethane or toluene; the concentration of the PVP-Pd sol is 4-6 mmol/L.
Preferably, the reducing solution is a mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide; the concentration of hydrazine hydrate in the reducing solution is 25-100 mmol/L, the molar ratio of hydrazine hydrate to potassium borohydride is 0.15-27: 1, and the molar ratio of hydrazine hydrate to sodium hydroxide is 3-5: 1; the time of the reduction reaction is 2-6 h.
Preferably, the concentration of the graphene oxide solution in the step (2) is 0.03-2.5 mg/mL.
Preferably, the concentration of zinc nitrate in the intermediate Zn-GO solution in the step (3) is 25-50 mmol/L.
Preferably, the volume ratio of the PVP-Pd sol to the Zn-GO solution in the step (4) is 1 (5-10), the molar ratio of 2-methylimidazole to zinc nitrate in the Zn-GO solution is 8-25: 1; the reaction temperature is 20-45 ℃, and the reaction time is 4-48 h.
Preferably, the deionized water washing times in the step (5) are 2-5 times; the drying temperature of the oven is 50-80 ℃, and the drying time is 8-36 h.
The invention adopts p-nitrophenol as a model reaction to evaluate the catalytic performance of the prepared catalyst. The specific process is as follows:
the reaction was carried out in a 100ml round bottom flask. 0.20g of p-nitrophenol, 25ml of deionized water, 25ml of ethanol, 0.2g of catalyst, 0.6625g of sodium borohydride were added in this order to a round-bottom flask. The reaction temperature is maintained at 30 ℃ by using a constant-temperature water bath, and the reaction is stopped after the reaction is carried out for 60 min. And (4) diluting the reaction product, analyzing by using a high performance liquid chromatography, and calculating the conversion rate of the raw material and the selectivity of the product according to a standard curve.
Has the advantages that:
1. the Pd-ZIF-L-GO catalyst prepared by the invention has a unique two-dimensional nanosheet-sheet structure, compared with the traditional porous material, the structure is beneficial to high exposure of active sites, and meanwhile, the internal diffusion of reactants and products in pore channels can be eliminated, so that the catalytic reaction rate is improved;
2. the Pd-ZIF-L-GO prepared by the method disclosed by the invention is highly dispersed and stable due to the interaction between the Pd-ZIF-L-GO, and shows good catalytic activity and reusability in a nitro hydrogenation reaction.
Drawings
FIG. 1 is a transmission electron micrograph of Pd-ZIF-L-GO prepared in example 1;
FIG. 2 is a schematic of the interaction force of Pd-ZIF-L-GO prepared in example 1.
Detailed Description
The method and the catalyst of the present invention will be described in detail by the following examples, which are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) Preparation of PVP-Pd
Adding 20ml of 500mmol/L polyvinylpyrrolidone dichloromethane solution into 20ml of 25mmol/L palladium acetate dichloromethane solution (molar ratio of palladium acetate to polyvinylpyrrolidone is 1: 20); then adding 11mL of mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide, wherein the concentration of the hydrazine hydrate is 72mmol/L, the molar ratio of the hydrazine hydrate to the potassium borohydride is 27:1, and the molar ratio of the hydrazine hydrate to the sodium hydroxide is 4.5:1, and stirring the mixed solution at room temperature for 4 hours to carry out reduction reaction. And after the reduction is finished, taking the Pd nano-particles on the upper layer, and dispersing the Pd nano-particles in 100mL of deionized water to prepare the PVP-Pd sol.
(2) Preparation of Pd-ZIF-L-GO catalyst
And ultrasonically dispersing the graphene oxide powder in an aqueous solution to obtain a graphene oxide solution with the concentration of 2.32 mg/mL. Taking zinc nitrate and 100mL of 2.32mixing mg/mL graphene oxide solutions to prepare a Zn-GO solution (the concentration of zinc nitrate in the graphene oxide solution is 25mmol/L), then mixing 10mL of 5mmol/L PVP-Pd sol, 100mL of 500 mmol/L2-methylimidazole water solution (the molar ratio of 2-methylimidazole to zinc nitrate is 20:1) and 100mL of Zn-GO solution (the volume ratio of PVP-Pd sol: 2-methylimidazole water solution: Zn-GO solution is 1: 10: 10), and then placing at 30 ℃ for reaction for 48 hours. Washing the obtained product with deionized water, centrifuging for 3 times, and drying in an oven at 60 ℃ for 24 hours to obtain the Pd-ZIF-L-GO composite catalyst. FIG. 1 is a transmission electron microscope image among three elements of Pd-ZIF-L-GO, from which it can be clearly seen that Pd-ZIF-L-GO presents a two-dimensional nanosheet-sheet structure; and the Pd nano-particles have good dispersibility, which is mainly caused by the synergistic effect among three phases of Pd-ZIF-L-GO. FIG. 2 is a schematic diagram of the interaction between the three elements Pd-ZIF-L-GO, wherein polyvinylpyrrolidone is wrapped in Pd nanoparticles, and the pyrrolidone ring (C ═ O) from PVP is bonded with Pd and simultaneously with Zn in ZIF crystal2+A weak coordination effect exists, and a hydrogen bond is formed between C ═ O and an oxygen-containing functional group in graphene oxide; in addition, coordination exists between the surface oxygen-containing group and zinc in the graphene oxide.
The catalyst Pd-ZIF-L-GO is applied to a p-nitrophenol hydrogenation experiment, the conversion rate is 100% after the reaction is carried out for 60min, and the selectivity is 100%.
Example 2
(1) Preparation of PVP-Pd
20ml of a 300mmol/L polyvinylpyrrolidone toluene solution was added to 20ml of a 30mmol/L palladium nitrate toluene solution (molar ratio of palladium nitrate to polyvinylpyrrolidone 1: 10); then adding 11mL of mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide, wherein the concentration of the hydrazine hydrate is 100mmol/L, the molar ratio of the hydrazine hydrate to the potassium borohydride is 27:1, and the molar ratio of the hydrazine hydrate to the sodium hydroxide is 5:1, and stirring the mixed solution at room temperature for 2h for reduction reaction. And after the reduction is finished, taking the Pd nano-particles on the upper layer, and dispersing the Pd nano-particles in 100mL of deionized water to prepare the PVP-Pd sol.
(2) Preparation of Pd-ZIF-L-GO catalyst
And ultrasonically dispersing graphene oxide powder in an aqueous solution to obtain a graphene oxide solution with the concentration of 0.03 mg/mL. Mixing zinc nitrate with 50mL of 0.03mg/mL graphene oxide solution to prepare a Zn-GO solution (the concentration of the zinc nitrate in the graphene oxide solution is 50mmol/L), then mixing 10mL of 6mmol/L PVP-Pd sol, 50mL of 400 mmol/L2-methylimidazole water solution (the molar ratio of 2-methylimidazole to zinc nitrate is 8:1) and 50mL of Zn-GO solution (the volume ratio of the PVP-Pd sol: 2-methylimidazole water solution: Zn-GO solution is 1: 5: 5), and then placing at 45 ℃ for reaction for 4 hours. Washing the obtained product with deionized water, centrifuging for 5 times, and drying in an oven at 80 ℃ for 8 hours to obtain the Pd-ZIF-L-GO composite catalyst.
The catalyst Pd-ZIF-L-GO is applied to a p-nitrophenol hydrogenation experiment, the conversion rate is 47.9% after the reaction is carried out for 60min, and the selectivity is 100%.
Example 3
(1) Preparation of PVP-Pd
Adding 20ml of 200mmol/L polyvinylpyrrolidone dichloromethane solution into 20ml of 5mmol/L palladium chloride dichloromethane solution (molar ratio of palladium nitrate to polyvinylpyrrolidone is 1: 40); then adding 11mL of mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide, wherein the concentration of the hydrazine hydrate is 25mmol/L, the molar ratio of the hydrazine hydrate to the potassium borohydride is 0.15:1, and the molar ratio of the hydrazine hydrate to the sodium hydroxide is 3:1, and stirring the mixed solution at room temperature for 6h to perform reduction reaction. And after the reduction is finished, taking the Pd nanoparticles on the upper layer, and dispersing the Pd nanoparticles in 25mL of deionized water.
(2) Preparation of Pd-ZIF-L-GO catalyst
And ultrasonically dispersing graphene oxide powder in an aqueous solution to obtain a graphene oxide solution with the concentration of 2.5 mg/mL. Mixing zinc nitrate with 100mL of 2.5mg/mL graphene oxide solution to prepare a Zn-GO solution (the concentration of the zinc nitrate in the graphene oxide solution is 25mmol/L), then mixing 10mL of 4mmol/L PVP-Pd sol, 100mL of 625 mmol/L2-methylimidazole water solution (the molar ratio of 2-methylimidazole to zinc nitrate is 25:1) and 100mL of Zn-GO solution (the volume ratio of the PVP-Pd sol: 2-methylimidazole water solution: Zn-GO solution is 1: 10: 10), and then placing at 20 ℃ for reaction for 24 hours. Washing the obtained product with deionized water, centrifuging for 2 times, and drying in an oven at 50 ℃ for 36 hours to obtain the Pd-ZIF-L-GO composite catalyst.
The catalyst Pd-ZIF-L-GO is applied to a p-nitrophenol hydrogenation experiment, the conversion rate is 78.3% after the reaction is carried out for 60min, and the selectivity is 100%.
Claims (7)
1. A preparation method of a two-dimensional nanosheet layer hydrogenation catalyst comprises the following specific steps:
(1) adding a polyvinylpyrrolidone solution into a divalent palladium salt solution, adding a reducing solution for reduction reaction to prepare PVP-coated Pd nanoparticles, and dispersing the PVP-coated Pd nanoparticles in an aqueous solution to form PVP-Pd sol;
(2) ultrasonically dispersing graphene oxide GO powder in an aqueous solution to obtain a uniformly dispersed graphene oxide solution;
(3) mixing zinc nitrate with the graphene oxide solution obtained in the step (2) to obtain an intermediate Zn-GO solution;
(4) mixing the PVP-Pd sol obtained in the step (1), a 2-methylimidazole water solution and the intermediate Zn-GO solution obtained in the step (3), and reacting at a certain temperature;
(5) and (4) washing the sample obtained in the step (4) with deionized water, and drying the sample in an oven to obtain the two-dimensional nanosheet layer hydrogenation catalyst.
2. The production method according to claim 1, characterized in that the divalent palladium salt in step (1) is palladium acetate, palladium chloride or palladium nitrate; the concentration of the divalent palladium salt is 5-30 mmol/L; the molar ratio of the divalent palladium salt to the polyvinylpyrrolidone is 1 (10-40); the solvents in the divalent palladium salt solution and the polyvinylpyrrolidone solution are dichloromethane or toluene; the concentration of the PVP-Pd sol is 4-6 mmol/L.
3. The method according to claim 1, wherein the reducing solution is a mixed aqueous solution of hydrazine hydrate, potassium borohydride and sodium hydroxide; the concentration of hydrazine hydrate in the reducing solution is 25-100 mmol/L, the molar ratio of hydrazine hydrate to potassium borohydride is 0.15-27: 1, and the molar ratio of hydrazine hydrate to sodium hydroxide is 3-5: 1; the time of the reduction reaction is 2-6 h.
4. The method according to claim 1, wherein the concentration of the graphene oxide solution in the step (2) is 0.03-2.5 mg/mL.
5. The preparation method of claim 1, wherein the concentration of zinc nitrate in the intermediate Zn-GO solution in the step (3) is 25-50 mmol/L.
6. The preparation method according to claim 1, wherein the volume ratio of the PVP-Pd sol to the Zn-GO solution in the step (4) is 1 (5-10), and the molar ratio of 2-methylimidazole to zinc nitrate in the Zn-GO solution is 8-25: 1; the reaction temperature is 20-45 ℃, and the reaction time is 4-48 h.
7. The method according to claim 1, wherein the number of washing with deionized water in the step (5) is 2 to 5; the drying temperature of the oven is 50-80 ℃, and the drying time is 8-36 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113967740A (en) * | 2021-10-11 | 2022-01-25 | 先进能源产业研究院(广州)有限公司 | Preparation method and application of two-dimensional Pd nanosheet aggregate |
| CN114367314A (en) * | 2022-01-10 | 2022-04-19 | 南京工业大学 | Application of Pd-ZIF-GO catalyst in preparation of 1, 3-cyclohexanedione by hydrogenation of resorcinol |
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| CN103394373A (en) * | 2013-04-27 | 2013-11-20 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN106040302A (en) * | 2016-06-23 | 2016-10-26 | 南京工业大学 | Hydrogenation catalyst |
| CN107857328A (en) * | 2017-11-03 | 2018-03-30 | 宁夏大学 | A kind of method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption |
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| CN103394373A (en) * | 2013-04-27 | 2013-11-20 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN106040302A (en) * | 2016-06-23 | 2016-10-26 | 南京工业大学 | Hydrogenation catalyst |
| CN107857328A (en) * | 2017-11-03 | 2018-03-30 | 宁夏大学 | A kind of method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113967740A (en) * | 2021-10-11 | 2022-01-25 | 先进能源产业研究院(广州)有限公司 | Preparation method and application of two-dimensional Pd nanosheet aggregate |
| CN113967740B (en) * | 2021-10-11 | 2023-08-15 | 先进能源产业研究院(广州)有限公司 | Preparation method and application of two-dimensional Pd nano-sheet aggregate |
| CN114367314A (en) * | 2022-01-10 | 2022-04-19 | 南京工业大学 | Application of Pd-ZIF-GO catalyst in preparation of 1, 3-cyclohexanedione by hydrogenation of resorcinol |
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