CN110665546A - Noble metal/amino MOFs selective hydrogenation catalyst, preparation method and application thereof - Google Patents
Noble metal/amino MOFs selective hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 77
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 55
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 22
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims abstract description 21
- 229940117916 cinnamic aldehyde Drugs 0.000 claims abstract description 19
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 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 description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- -1 Na2PtCl6 Inorganic materials 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical compound NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 description 1
- 229910003609 H2PtCl4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 1
- 229910020437 K2PtCl6 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000013599 spices Nutrition 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a supported noble metal/amino MOFs selective hydrogenation catalyst, a preparation method and application thereof, wherein the preparation method of the supported noble metal/amino MOFs selective hydrogenation catalyst comprises the following steps: (1) preparing monoatomic noble metal sol by low-temperature liquid phase reduction; (2) and (2) loading the monatomic noble metal sol in the step (1) into an amino MOFs material to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst. The catalyst can be used in the reaction for preparing cinnamyl alcohol by selective hydrogenation of cinnamaldehyde. The catalyst has the characteristics of high activity, high selectivity and high stability.
Description
Technical Field
The invention belongs to the field of precious metal catalytic organic matter synthesis, and particularly relates to a precious metal/amino MOFs selective hydrogenation catalyst, a preparation method and application thereof.
Background
The alpha, beta-unsaturated alcohol generated by the selective hydrogenation of the alpha, beta-unsaturated aldehyde is an important raw material and an intermediate for the production of spices, medicaments and other fine chemical products, and is widely applied to organic synthesis. Cinnamaldehyde, a representative example of α, β unsaturated aldehydes, has a benzene ring, a C ═ O double bond, and a C ═ C double bond, and forms a conjugated system, and since the bond energy (615KJ · mol-1) of the C ═ C bond is lower than that of the C ═ O bond (715KJ · mol-1), hydrogenation of the former is thermodynamically more favorable, so that selective hydrogenation on the C ═ O bond without destroying C ═ C is difficult, and hydrogenation selectivity is poor. One of the keys to solving the above problems is to design a suitable catalyst.
The activity, selectivity and stability are the main performance indexes of the catalyst, and the monatomic noble metal catalyst has high activity and high selectivity and is expected to be used for generating cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde, but the monatomic noble metal particles have small size and high surface energy, and are easy to generate agglomeration phenomenon when being loaded on a carrier, so that the catalytic activity and the stability are reduced.
Metal Organic Frameworks (MOFs) are a porous crystalline material assembled from Metal ions and Organic ligands. The material has a pore structure with extremely large specific surface area and ordered height, and the composition and the pore size are simple and adjustable, so the material is a very potential heterogeneous catalyst carrier. The inventor finds that the catalyst prepared by utilizing the high specific surface area, the confinement effect of a framework micropore cage and the adsorption effect of amino on noble metal in the amino MOFs material can stably fix the single-atom noble metal active component on the amino MOFs material without agglomeration, and the prepared catalyst can be used for the reaction of generating cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde with high activity, high selectivity and high stability.
Disclosure of Invention
The invention aims to provide a preparation method of a supported noble metal/amino MOFs selective hydrogenation catalyst, which can be used in the reaction for preparing cinnamyl alcohol by selective hydrogenation of cinnamaldehyde. The catalyst has the characteristics of high activity, high selectivity and high stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a supported noble metal/amino MOFs selective hydrogenation catalyst comprises the following steps:
(1) preparing monoatomic noble metal sol by low-temperature liquid phase reduction;
(2) and (2) loading the monatomic noble metal sol in the step (1) into an amino MOFs material to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst.
Preferably, the step (1) specifically comprises the following steps: (1a) slowly dripping the reducing agent solution into the noble metal precursor solution at the temperature of between 50 ℃ below zero and 0 ℃, and continuously reacting completely after dripping to obtain the monoatomic noble metal sol.
Preferably, in the step (1a), the noble metal is Pt, and the noble metal precursor is a soluble salt of Pt.
Preferably, the reducing agent in step (1a) is any one or a mixture of at least two of sodium borohydride, hydrazine hydrate and ascorbic acid.
Further preferably, the reducing agent in step (1a) is hydrazine hydrate.
Preferably, the molar ratio of the reducing agent to the noble metal in the noble metal precursor in step (1a) is from 5:1 to 100: 1.
Preferably, both the dropwise addition and the reaction in step (1a) are carried out under stirring at a stirring rate of 200-800 rpm.
Preferably, the step (2) specifically comprises the following steps: (2a) and (2) dipping the monoatomic noble metal sol in the step (1) in an amino MOFs material for 5-10h, alternately washing with water and ethanol, and drying at 50-100 ℃ to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst.
Preferably, the amino MOFs material in the step (2a) is one or a mixture of two of UiO66-NH2 and UiO-67-NH2, and is preferably porous UiO66-NH 2.
Further preferably, the amino MOFs material in step (1a) is porous UiO66-NH 2.
Preferably, the mass ratio of the amino MOFs material to the noble metal in the noble metal precursor in step (2a) is 1: (0.0001-0.03).
Preferably, the impregnation in step (2a) is carried out under stirring at a rate of 200 and 800 rpm.
The invention also aims to provide a supported noble metal/amino MOFs selective hydrogenation catalyst which is prepared by the method, and the active component noble metal is uniformly dispersed on the amino MOFs in an atomic scale.
Preferably, the loading amount of the noble metal is 0.01-3%, and the particle size is 0.01-1 nm.
The invention also aims to provide application of the supported noble metal/amino MOFs selective hydrogenation catalyst, and the supported noble metal/amino MOFs selective hydrogenation catalyst can be used for the reaction of preparing cinnamaldehyde by selective hydrogenation of cinnamaldehyde.
Compared with the prior art, the invention has the following beneficial effects:
the load type noble metal/amino MOFs selective hydrogenation catalyst is prepared into monatomic Pt sol by adopting a low-temperature reduction method, and the monatomic noble metal active component is stably immobilized on the amino MOFs material without agglomeration by utilizing the large specific surface area of the amino MOFs material, the confinement effect of a framework micropore cage and the adsorption effect of an amino group on noble metal. The method has the characteristics of high activity, high selectivity and high stability when being used for the reaction of preparing the cinnamaldehyde by selective hydrogenation of the cinnamaldehyde. In the performance test of the catalyst, the conversion rate of the cinnamaldehyde reaches 99.9 percent, and the selectivity of the cinnamyl alcohol reaches 99.3 percent; after the cinnamaldehyde catalyst is repeatedly used for 10 times, the conversion rate of the cinnamaldehyde reaches 98.8%, the selectivity of the cinnamyl alcohol reaches 98.7%, and the sintering and agglomeration phenomena are not generated.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The preparation method of the supported noble metal/amino MOFs selective hydrogenation catalyst comprises the following steps:
(1) preparing monoatomic noble metal sol by low-temperature liquid phase reduction;
(2) and (2) loading the monatomic noble metal sol in the step (1) into an amino MOFs material to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst.
Preferably, the step (1) specifically comprises the following steps: (1a) slowly dripping the reducing agent solution into the noble metal precursor solution at the temperature of between 50 ℃ below zero and 0 ℃, and continuously reacting completely after dripping to obtain the monoatomic noble metal sol.
Preferably, in the step (1a), the noble metal is Pt, and the noble metal precursor is a soluble salt of Pt, and may be any one of or a mixture of at least two of H2PtCl4, H2PtCl6, K2PtCl6, Na2PtCl6, K2PtCl4 and Na2PtCl4, for example.
Preferably, the concentration of the noble metal precursor solution in step (1a) is 0.0001 to 0.03mol/L, and may be, for example, 0.0001mol/L, 0.0005mol/L, 0.01mol/L, 0.02mol/L, 0.03 mol/L.
Preferably, the reducing agent in step (1a) is any one or a mixture of at least two of sodium borohydride, hydrazine hydrate and ascorbic acid.
Further preferably, the reducing agent in step (1a) is hydrazine hydrate.
Preferably, the molar ratio of the reducing agent to the noble metal in the noble metal precursor in step (1a) is from 5:1 to 100:1, and may be, for example, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60: 1. 70: 1. 80: 1. 90: 1. 100, and (2) a step of: 1.
preferably, the concentration of the reducing agent solution in step (1a) is 0.0001 to 0.02mol/L, and may be, for example, 0.0001mol/L, 0.0005mol/L, 0.01mol/L, 0.02 mol/L.
Preferably, the solvent of the solution in step (1a) is water and ethanol, the ethanol is 0-100% by volume of the solvent and excludes 0 and 100%, and the ethanol may be, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% by volume.
Further preferably, the solvent of the solution in the step (1a) is a mixture of water and ethanol, and the ethanol accounts for 90% of the solvent by volume.
Preferably, both the addition and the reaction in step (1a) are carried out under stirring at a stirring rate of 200 and 800rpm, which may be, for example, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800 rpm.
Preferably, the step (2) specifically comprises the following steps: (2a) and (2) dipping the monoatomic noble metal sol in the step (1) in an amino MOFs material for 5-10h, alternately washing with water and ethanol, and drying at 50-100 ℃ to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst.
Preferably, the mass ratio of the amino MOFs material to the noble metal in the noble metal precursor in step (2a) is 1: (0.0001-0.03).
Preferably, the amino MOFs material in the step (2a) is any one or a mixture of two of UiO66-NH2 and UiO-67-NH 2.
Further preferably, in the step (2a), the amino MOFs material is porous UiO66-NH2, and is prepared by the following method: uniformly mixing a zirconium source, an organic ligand and an organic solvent, carrying out ultrasonic treatment for 5min, and then carrying out hydrothermal treatment at 120 ℃ for 24h to obtain a mixture; cooling the mixture to room temperature, washing the mixture with N, N-dimethylformamide and methanol respectively for 2-3 times, and finally drying the mixture at 50-100 ℃ to obtain porous UiO-66-NH 2.
Preferably, the zirconium source is any one of zirconium chloride and zirconium nitrate or a mixture of the two. Further preferably, the zirconium source is zirconium chloride.
Preferably, the organic ligand is any one or a mixture of two of 2-amino terephthalic acid and 3-amino phthalic acid. Further preferably, the organic ligand is 2-amino terephthalic acid as an organic solvent.
Preferably, the organic solvent is any one or a mixture of at least two of N, N-dimethylformamide, methanol, ethanol, or water.
Further preferably, the organic solvent is N, N-dimethylformamide.
Preferably, the molar ratio of the zirconium source to the organic ligand is 1:1 to 1:3, and the mass-to-volume ratio of the organic solvent to the zirconium source is 1: 1-4:1.
Preferably, the impregnation in step (2a) is carried out under stirring at a rate of 200 and 800rpm, such as 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800 rpm.
The invention also aims to provide a supported noble metal/amino MOFs selective hydrogenation catalyst which is prepared by the method, and the active component noble metal is uniformly dispersed on the amino MOFs in an atomic scale.
In the supported noble metal/amino MOFs selective hydrogenation catalyst, the loading amount of the noble metal is 0.01-3%, and the particle size is 0.01-1 nm.
The supported noble metal/amino MOFs selective hydrogenation catalyst can be used for the reaction of preparing cinnamaldehyde by the selective hydrogenation of cinnamaldehyde.
The performance evaluation of the catalyst is carried out in a 50mL high-pressure reaction kettle, the solvent is 10mL of isopropanol, 5mmol of cinnamaldehyde is added, the catalyst is 0.05g, the reaction gas is hydrogen (2.5MPa), the reaction temperature is 100 ℃, and the reaction time is 3 h. After the reaction, the reaction mixture was cooled to room temperature, and the centrifuged filtrate was quantitatively measured by gas chromatography, model C of Shimadzu GC-2014.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention. The experimental methods in the examples are conventional methods unless otherwise specified; the materials used, unless otherwise specified, were purchased from conventional biochemical manufacturers.
Example 1
Preparation of porous grade UiO66-NH 2:
weighing 0.8g of ZrCl4 and 0.6g of 2-aminoterephthalic acid, and dissolving in 200mLN, N-dimethylformamide to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution for 5min, then transferring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene sleeve, and crystallizing the mixed solution for 24h at 120 ℃ to obtain a reaction product; after the reaction product is cooled to room temperature, washing the reaction product with N, N-dimethylformamide solution and methanol solution for three times respectively, and carrying out vacuum drying at 100 ℃ for 12 hours to prepare the porous UiO-66-NH 2.
Example 2
Preparation of a supported noble metal/amino MOFs selective hydrogenation catalyst:
configuration 10mL of 0.0001MH2PtCl6Solution and 50ml of 0.001M hydrazine hydrate solution, H2PtCl6The solvent of the solution and the hydrazine hydrate solution is a mixture of water and ethanol according to the volume ratio of 1: 9.
H is to be2PtCl6Putting the solution and hydrazine hydrate solution into a high-low temperature box, slowly dripping the hydrazine hydrate solution into H when the temperature is reduced to-50 DEG C2PtCl6And (3) after the dropwise addition is finished, continuously reacting for 2 hours at-50 ℃ to obtain the monoatomic Pt sol.
Weighing 1.95g of porous UiO66-NH2, adding into the monoatomic Pt sol, stirring for 10h, alternately washing with water and ethanol, and vacuum drying at 100 ℃ for 12h to prepare the supported noble metal/amino MOFs selective hydrogenation catalyst.
Example 3
The procedure of example 2 was repeated except that: dropwise adding H2PtCl6The concentration of the solution was changed to 0.0005M.
Example 4
The procedure of example 2 was repeated except that: dropwise adding H2PtCl6The concentration of the solution was changed to 0.03M.
Example 5
The procedure of example 2 was repeated except that: the reduction reaction temperature was 0 ℃.
Example 6
The procedure of example 2 was repeated except that: the reduction reaction temperature was-20 ℃.
The supported noble metal/amino MOFs selective hydrogenation catalysts of examples 1-6 were used in the reaction for preparing cinnamaldehyde by selective hydrogenation of cinnamaldehyde, and the results are shown in table 1.
Table 1: catalyst Performance test data
As can be seen from Table 1, the supported noble metal/amino MOFs selective hydrogenation catalyst provided by the invention is used in the reaction for preparing cinnamaldehyde by selective hydrogenation of cinnamaldehyde, and has the characteristics of high activity and high selectivity, and the catalyst is repeatedly used for many times, has no sintering agglomeration phenomenon, has no obvious reduction in activity and selectivity, and has the characteristic of high stability.
The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a supported noble metal/amino MOFs selective hydrogenation catalyst comprises the following steps:
(1) preparing monoatomic noble metal sol by low-temperature liquid phase reduction;
(2) and (2) loading the monatomic noble metal sol in the step (1) into an amino MOFs material to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst.
2. The method according to claim 1, wherein the step (1) comprises the steps of: slowly dripping the reducing agent solution into the noble metal precursor solution at the temperature of between 50 ℃ below zero and 0 ℃, and continuously reacting completely after dripping to obtain the monoatomic noble metal sol.
3. The method according to claim 2, wherein the noble metal is Pt and the noble metal precursor is a soluble salt of Pt.
4. The method according to claim 2, wherein the reducing agent is any one or a mixture of at least two of sodium borohydride, hydrazine hydrate and ascorbic acid, preferably hydrazine hydrate.
5. The production method according to claim 2, wherein the molar ratio of the reducing agent to the noble metal in the noble metal precursor is 5:1 to 100: 1.
6. The method according to claim 1, wherein the step (2) comprises the steps of: and (2) dipping the monoatomic noble metal sol in the step (1) in an amino MOFs material for 5-10h, alternately washing with water and ethanol, and drying at 50-100 ℃ to obtain the supported noble metal/amino MOFs selective hydrogenation catalyst.
7. The preparation method of claim 6, wherein the amino MOFs material is one or a mixture of two of UiO66-NH2 and UiO-67-NH2, and is preferably porous UiO66-NH 2.
8. The method according to claim 6, wherein the mass ratio of the mass of the amino MOFs material to the mass of the noble metal in the noble metal precursor is 1: (0.0001-0.03).
9. A supported noble metal/amino MOFs selective hydrogenation catalyst, characterized in that, the supported noble metal/amino MOFs selective hydrogenation catalyst is prepared according to the preparation method of any one of claims 1 to 8, and the active component noble metal is uniformly dispersed on the amino MOFs in an atomic scale.
10. The application of the supported noble metal/amino MOFs selective hydrogenation catalyst is characterized in that the supported noble metal/amino MOFs selective hydrogenation catalyst can be used for the reaction of preparing cinnamaldehyde by selective hydrogenation of cinnamaldehyde.
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