CN115337960A - Preparation of platinum metal nanocluster NaA molecular sieve and application of platinum metal nanocluster NaA molecular sieve in 1,2,3,4-tetrahydroquinoline synthesis - Google Patents
Preparation of platinum metal nanocluster NaA molecular sieve and application of platinum metal nanocluster NaA molecular sieve in 1,2,3,4-tetrahydroquinoline synthesis Download PDFInfo
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- CN115337960A CN115337960A CN202210999117.XA CN202210999117A CN115337960A CN 115337960 A CN115337960 A CN 115337960A CN 202210999117 A CN202210999117 A CN 202210999117A CN 115337960 A CN115337960 A CN 115337960A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 74
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 150000004687 hexahydrates Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- POTIYWUALSJREP-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydroquinoline Chemical compound N1CCCC2CCCCC21 POTIYWUALSJREP-UHFFFAOYSA-N 0.000 description 1
- YQDGQEKUTLYWJU-UHFFFAOYSA-N 5,6,7,8-tetrahydroquinoline Chemical compound C1=CC=C2CCCCC2=N1 YQDGQEKUTLYWJU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical compound [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012694 precious metal precursor Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7407—A-type
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/14—Type A
- C01B39/16—Type A from aqueous solutions of an alkali metal aluminate and an alkali metal silicate excluding any other source of alumina or silica but seeds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to preparation of a platinum metal nanocluster NaA molecular sieve and application of the platinum metal nanocluster NaA molecular sieve in 1,2,3,4-tetrahydroquinoline synthesis. The invention uses silicon source, aluminum source and alkali source, polyethylene glycol, noble metal precursor and the like as raw materials, uses (3-mercaptopropyl) trimethoxysilane as a ligand, and is prepared by hydrothermal standing crystallization, roasting and hydrogen reduction. And the prepared platinum metal nanocluster NaA molecular sieve, wherein the size of the platinum metal cluster is nanoscale, and the NaA molecular sieve belongs to an alpha cage-limited platinum nanometal cluster, and when the NaA molecular sieve is used as a catalyst for selective catalytic hydrogenation, the high selectivity of preparing 1,2,3,4-tetrahydroquinoline by selective hydrogenation can be realized by utilizing the hydrogen overflow effect of the NaA molecular sieve and the alpha cage-limited effect.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to preparation of a platinum metal nanocluster NaA molecular sieve and application of the platinum metal nanocluster NaA molecular sieve in 1,2,3,4-tetrahydroquinoline synthesis.
Background
Since 1,2,3,4-tetrahydroquinoline and its derivatives are widely used in the fields of medicines, agrochemicals, fine chemicals and the like, the preparation of 1,2,3,4-tetrahydroquinoline is also of great interest. At present, selective hydrogenation of quinoline is one of the most effective ways to obtain 1,2,3,4-tetrahydroquinoline, because the reaction is simple and convenient, and has high atomic efficiency. However, the selective hydrogenation of quinoline presents the following difficulties: the energy barrier of quinoline hydrogenation is high, so the reaction rate is low, and harsh reaction conditions are required; the hydrogenation process is accompanied by other byproducts, such as 5,6,7,8-tetrahydroquinoline and decahydroquinoline; the metal catalyst has strong coordination with nitrogen atoms in the N-heterocyclic ring of quinoline, so that the metal is easy to be poisoned, and the sustainability of the catalytic system is greatly reduced.
In view of the above-mentioned drawbacks of quinoline and its derivatives in the selective hydrogenation process, researchers have proposed many improvements, and among them, alternative metal catalysts such as transition metal or noble metal supported catalysts have attracted the most attention. There are studies using the iridium/phosphine/iodine system as an initial model for asymmetric reduction of quinoline derivatives, with selective hydrogenation of quinoline derivatives catalyzed by iridium catalysts in the presence of bidentate phosphorus ligands, where iodine has the main role of converting iridium (I) to iridium (III). However, transition metal phosphine catalysts are sensitive to air, which can lead to catalyst deactivation. The research also shows that sub-nanometer palladium metal clusters are loaded in random copolymer micelles, a plurality of palladium-containing micelles with different forms can be obtained through the crosslinking of the copolymer, the obtained latticed palladium micelles can catalyze quinoline to selectively hydrogenate to obtain 1,2,3,4-tetrahydroquinoline at room temperature and normal pressure in hydrogen atmosphere, the reaction lasts for 24 hours, and the conversion rate can reach 80%. Although the method solves the problem of easy deactivation of the catalyst to a certain extent, the required reaction time is longer. Research also shows that the Fe/Pt nanowire is subjected to acid etching in the air and then washed in methanol for multiple times to synthesize the ultrafine Pt nanowire catalyst, the catalyst is used for synthesizing 1,2,3,4-tetrahydroquinoline, the quinoline conversion rate in solvents such as water, methanol, ethanol and the like can reach 91-98%, and the selectivity of 1,2,3,4-tetrahydroquinoline can reach 93-97%. Although the conversion rate and the selectivity of the method are high, the platinum nanowire has poor tolerance to complex chemical environment and is easy to be poisoned and inactivated. Therefore, it is necessary to develop a new preparation method of 1,2,3,4-tetrahydroquinoline to overcome the above disadvantages.
Disclosure of Invention
In order to overcome the defects of the prior art, the preparation method of the platinum metal nanocluster NaA molecular sieve is used for selectively hydrogenating quinoline to generate 1,2,3,4-tetrahydroquinoline, and the selectivity of hydrogenating quinoline to generate 1,2,3,4-tetrahydroquinoline is improved.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides a preparation method of a platinum metal nanocluster NaA molecular sieve, which comprises the following steps: heating and stirring an alkali source, a silicon source, (3-mercaptopropyl) trimethoxysilane, a platinum metal precursor and polyethylene glycol in a water bath, adding an aluminum source, uniformly mixing, and then sequentially carrying out hydrothermal standing crystallization, roasting and hydrogen reduction to prepare the platinum metal nanocluster NaA molecular sieve.
According to the invention, polyethylene glycol is added into a system for synthesizing the NaA molecular sieve by using a silicon source, an aluminum source and an alkali source, and the mixture is uniformly stirred; adding a noble metal precursor in the synthesis process, and adding (3-mercaptopropyl) trimethoxysilane as a ligand to protect the platinum metal precursor; all raw materials are fully mixed and then are subjected to hydrothermal standing crystallization, roasting and hydrogen reduction treatment. The (3-mercaptopropyl) trimethoxy silane can protect the precious platinum metal precursor in the hydrothermal crystallization process of the molecular sieve, promote the growth and molding characteristics of the molecular sieve framework around the platinum metal precursor and ensure thatThe platinum metal precursor may be confined to the alpha cage of the NaA molecular sieve. The Na-type molecular sieve loaded with the noble metal nanocluster and obtained by the preparation method is an alpha-cage-limited platinum metal nanocluster NaA molecular sieve, the mass content of platinum metal is 0.1-2%, and SiO is used 2 ：Al 2 O 3 The silicon-aluminum ratio is 1-2.
Preferably, the silicon source is SiO 2 The aluminum source is NaAlO 2 In terms of NAOH, the molar ratio of the silicon source to the aluminum source to the alkali source is 1.0:0.5 to 2:0.25 to 0.8.
Preferably, the platinum metal precursor is calculated by platinum metal element, the polyethylene glycol is calculated by average molecular weight of 1450g/mol, and the silicon source is calculated by SiO 2 The molar ratio of the (3-mercaptopropyl) trimethoxysilane to the platinum metal precursor to the polyethylene glycol to the silicon source is 0.03-0.1: 0.005-0.05: 0.01 to 0.1:1, the platinum metal precursor comprises chloroplatinic acid hexahydrate.
Preferably, the temperature of the hydrothermal standing crystallization is 70-110 ℃, and the time is 1-3 days.
In order to avoid the platinum metal nanocluster from being agglomerated due to overhigh temperature while ensuring the roasting effect. Preferably, the roasting temperature is 300-500 ℃, the heating rate is 20-60 ℃/h, and the time is 3-5 days; the temperature of the hydrogen reduction is 350-450 ℃, the heating rate is 60-100 ℃/h, and the time is 3-5 days.
Preferably, the water bath heating and stirring is carried out for 0.5 to 1 hour at the temperature of between 70 and 90 ℃.
The invention provides a platinum metal nanocluster NaA molecular sieve prepared by the preparation method of the first aspect.
The third aspect of the invention provides an application of the platinum metal nanocluster NaA molecular sieve in preparation of 1,2,3,4-tetrahydroquinoline.
The fourth aspect of the invention provides a method for preparing 1,2,3,4-tetrahydroquinoline, which is characterized in that under a hydrogen atmosphere, the platinum metal nanocluster NaA molecular sieve of claim 6 is used as a catalyst to catalyze selective hydrogenation of quinoline to generate 1,2,3,4-tetrahydroquinoline.
The aperture of the NaA molecular sieve is smaller than the diameter of a quinoline molecule (the NaA molecular sieve consists of a benzene ring and a pyridine ring, wherein the diameter of the benzene ring is about 0.55nm, namely the diameter of the quinoline molecule is larger than that of the benzene ring and is also larger than that of the NaA molecular sieve), so that the quinoline molecule cannot enter the NaA molecular sieve to be directly contacted with the platinum metal nanocluster and can only be subjected to catalytic hydrogenation through hydrogen overflow of the molecular sieve, and when the selective catalytic hydrogenation is carried out on quinoline, the hydrogen overflow effect of the NaA molecular sieve and the domain-limited effect of an alpha cage can be utilized, and the selectivity of 3262 zxft 3238-tetrahydroquinoline is obviously improved. In addition, because the aperture of the NaA molecular sieve is smaller than the diameter of a quinoline molecule, the framework structure of the molecular sieve can effectively prevent the direct contact of the quinoline molecule and metal platinum, and the problem of strong coordination of nitrogen atoms in quinoline and metal is avoided, so that the problems of poor tolerance and easy poisoning and inactivation of the catalyst are solved.
Preferably, the molar ratio of quinoline to metal platinum in the platinum metal nanocluster NaA molecular sieve is 30-70.
Preferably, the temperature of the catalytic reaction is 100-160 ℃, the pressure of the hydrogen is 1.5-2.5 MPa, and the time is 40-90 min.
Preferably, the catalytic reaction takes ethanol as a solvent, and the mass of the ethanol is 100 to 300 times of that of quinoline.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a platinum metal nanocluster NaA molecular sieve, which is prepared by using a silicon source, an aluminum source, an alkali source, polyethylene glycol, a precious metal precursor and the like as raw materials and (3-mercaptopropyl) trimethoxysilane as a ligand through hydrothermal standing crystallization, roasting and hydrogen reduction. And the prepared platinum metal nanocluster NaA molecular sieve is nanoscale, belongs to an alpha cage limited platinum nanocluster, and can be used as a catalyst for selective catalytic hydrogenation to realize high selectivity of 1,2,3,4-tetrahydroquinoline by utilizing the hydrogen overflow effect and the alpha cage limited effect of the NaA molecular sieve.
Drawings
FIG. 1 is a schematic view of a model of the microcell structure of a sample of example 1;
FIG. 2 is a schematic diagram of the structure of an alpha cage in a NaA molecular sieve;
FIG. 3 is an XRD spectrum of a sample of example 1;
FIG. 4 is a TEM photograph and a particle size distribution chart of a sample of example 1;
FIG. 5 is a TEM photograph and a particle size distribution chart of a sample of comparative example 1.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 Synthesis of platinum Metal nanocluster NaA molecular sieves
(1) 11.5g of sodium metaaluminate (NaAlO) are taken 2 ) Dissolved in 16g H 2 O to obtain solution A; 2.3g of sodium hydroxide (NaOH) is dissolved in 8.0g H 2 Adding 0.8g of (3-mercaptopropyl) trimethoxy silane into the solution O to prepare a solution B; dissolving chloroplatinic acid hexahydrate 0.5g in 4g H 2 O, to obtain solution C.
(2) Stirring solution B at room temperature for 10min, adding solution C, 3.54g polyethylene glycol and 18g silica sol (LUDOX-30) under vigorous stirring, heating in water bath to 80 deg.C, and stirring for 30min until the solution is clear. And slowly dripping the solution A after the mixed solution is cooled, and uniformly stirring at room temperature to obtain the synthesized mixed solution, namely the platinum metal nanocluster NaA molecular sieve system.
In the platinum metal nanocluster NaA molecular sieve system: siO 2 2 、NaAlO 2 The molar ratio of NaOH is 1.0:1.56:0.64; (3-mercaptopropyl) trimethoxysilane, chloroplatinic acid hexahydrate, polyethylene glycol and silica sol (made of SiO) 2 Calculated) was 0.045:0.01:0.027:1.
(3) Placing the mixed solution into a stainless steel hot kettle with a polytetrafluoroethylene lining, and standing and crystallizing for 2 days at 80 ℃. And after crystallization, centrifuging, washing and drying the crystallized product. And roasting the obtained sample in a tubular furnace in an air atmosphere at the roasting temperature of 400 ℃ for 4h at the heating rate of 40 ℃/h. And finally, reducing in a hydrogen atmosphere at 400 ℃ for 4h at the heating rate of 80 ℃/h to obtain the NaA molecular sieve sample A1. In sample A1, the silicon to aluminum ratio (SiO) 2 ：Al 2 O 3 ) Is 1.28:1, the mass fraction of platinum is about 1.5%. As shown in figure 1, the prepared NaA molecular sieve is of a three-dimensional porous structure with eight-membered rings.
Fig. 3 is an XRD spectrogram of the sample A1, which shows that the prepared molecular sieve is a platinum-loaded NaA molecular sieve, and the spectrogram of the platinum-loaded molecular sieve has no significant characteristic peak of platinum element, and indirectly shows that the platinum loaded by the molecular sieve has no significant agglomeration, and the structure of the NaA molecular sieve itself is not significantly damaged.
Fig. 4 is a TEM photograph and a particle size distribution diagram of the sample A1, in which white bright spots are platinum nanoclusters, and it can be seen from fig. 4 that the platinum nanoclusters are uniformly dispersed in the crystal of the NaA molecular sieve. From the particle size analysis result, it can be seen that the diameter distribution of the platinum nanoclusters is relatively uniform, the average diameter is about 1.1nm, the diameter of the platinum nanoclusters is close to that of an alpha cage (as shown in fig. 2) of the NaA molecular sieve, but the pore diameter is only about 0.4nm, which indirectly indicates that the sample A1 is the platinum metal nanocluster NaA molecular sieve with an alpha cage confinement.
Example 2 Synthesis of platinum Metal nanocluster NaA molecular sieves
The preparation method is the same as in example 1, except that the calcination temperature in step (3) is 350 ℃ and the reduction temperature is 350 ℃, and the obtained sample is denoted as A2.
The sample A2 also has the structural features of fig. 1 and 2, and the XRD spectrum and TEM photograph of the sample A2 also have the features of fig. 3 and 4.
Comparative example 1 preparation of platinum Metal nanocluster NaA molecular sieves
Unlike example 1, in this comparative example, the platinum metal nanocluster NaA molecular sieve is prepared without in-situ encapsulation, that is, no metal precursor is added during the crystallization of the molecular sieve, and the platinum nanocluster is loaded by impregnation after the molecular sieve is synthesized. The preparation method of the comparative example comprises the following steps:
(1) In the mixing stage of raw materials, chloroplatinic acid hexahydrate and (3-mercaptopropyl) trimethoxysilane are not added, and a pure NaA molecular sieve is firstly prepared: 11.5g of sodium metaaluminate (NaAlO) are taken 2 ) Dissolved in 16g H 2 O to obtain solution A; 2.3g of sodium hydroxide (NaOH) is dissolved in 8.0g H 2 Preparing solution B in O;
adding the solution B, 3.54g of polyethylene glycol and 18g of silica sol (LUDOX-30) into the solution A in sequence, heating the mixture to 80 ℃ in a water bath, and stirring the mixture for 30min until the solution is clear.
(2) After the same crystallization, calcination and hydrogen atmosphere reduction as in the step (3) of example 1, the prepared NaA molecular sieve was dehydrated and degassed in a vacuum oven at 80 ℃, and then a chloroplatinic acid hexahydrate solution (0.5 g chloroplatinic acid hexahydrate in 4g H) was used 2 O), carrying out impregnation treatment, sealing and stirring for 1h under the condition of heating in a water bath at 60 ℃, and evaporating the solution at the same temperature to obtain an impregnated product. The impregnated product was again subjected to the same calcination and hydrogen atmosphere reduction operation as in the step (3) of example 1, to obtain a surface-supported platinum metal nanocluster NaA molecular sieve, denoted as D1. Sample D1, silicon to aluminum ratio (SiO) 2 ：Al 2 O 3 ) Is 1.28:1, the mass fraction of platinum is about 1.5%.
Fig. 5 is a TEM photograph and a particle size distribution diagram of the sample D1, and it can be seen from the drawing that the platinum nanoclusters in the sample D1 are not uniformly distributed, and have an average diameter of about 2nm, and meanwhile, there exist large-sized nanoparticles with a diameter close to 5nm, which are larger than the diameter of the α cage in the NaA molecular sieve, which indicates that the platinum metal nanoclusters NaA molecular sieve with α cage domains are not obtained in this comparative example.
This comparative example illustrates that the present invention uses in-situ encapsulation technology to play a key role in the alpha-caged platinum metal nanocluster by participating (3-mercaptopropyl) trimethoxysilane in the preparation process of the noble metal supported NaA molecular sieve.
Experimental example 1 application of platinum metal nanocluster NaA molecular sieve in synthesis of 1,2,3,4-tetrahydroquinoline
(1) Taking 0.1mmol of quinoline, adding the molecular sieve sample A1 prepared in example 1 according to the molar ratio of the quinoline to platinum in the platinum metal nanocluster NaA molecular sieve catalyst being 50 2 And (3) carrying out catalytic reaction for 60min under the condition, centrifuging after reaction, taking supernate, diluting, and detecting by using GC-MS (gas chromatography-mass spectrometry), wherein the obtained conversion rate is about 50% and the selectivity is about 98%. It can be seen that the conversion rate has reached 50% under the condition of 1 hour of reaction time, and it can be presumed that the conversion rate can reach more than 95% under the condition of 3 to 5 hours of reaction time, and that the selectivity of more than 98% is ensured.
(2) Taking 0.1mmol of quinoline, adding the molecular sieve sample D1 prepared in the comparative example 1 according to the molar ratio of the quinoline to the platinum in the catalyst of 50 2 After the conditional catalytic reaction is carried out for 60min, the supernatant is centrifuged and diluted, and then GC-MS is used for detection, so that the conversion rate is about 91 percent, and the selectivity is about 55 percent. Furthermore, the selectivity remained essentially unchanged with increasing reaction time, with no tendency to increase.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of a platinum metal nanocluster NaA molecular sieve is characterized in that an alkali source, a silicon source, (3-mercaptopropyl) trimethoxysilane, a platinum metal precursor and polyethylene glycol are heated in a water bath, stirred and mixed uniformly, then an aluminum source is added and mixed uniformly, and then the platinum metal nanocluster NaA molecular sieve is prepared through hydrothermal standing crystallization, roasting and hydrogen reduction successively.
2. The method for preparing a platinum metal nanocluster NaA molecular sieve as claimed in claim 1, wherein the silicon source is SiO 2 The aluminum source is NaAlO 2 In terms of NAOH, the molar ratio of the silicon source to the aluminum source to the alkali source is 1.0:0.5 to 2:0.25 to 0.8.
3. The method of claim 1, wherein the platinum metal precursor is platinum metal, the polyethylene glycol is polyethylene glycol with an average molecular weight of 1450g/mol, and the silicon source is SiO 2 In 0.4, the molar ratio of the (3-mercaptopropyl) trimethoxysilane to the platinum metal precursor to the polyethylene glycol to the silicon source is 0.03-0.1: 0.005-0.05: 0.01 to 0.1:1, the platinum metal precursor comprises chloroplatinic acid hexahydrate.
4. The method for preparing the platinum metal nanocluster NaA molecular sieve as claimed in claim 1, wherein the temperature of the hydrothermal standing crystallization is 70-110 ℃ and the time is 1-3 days.
5. The method for preparing the platinum metal nanocluster NaA molecular sieve as claimed in claim 1, wherein the roasting temperature is 300-500 ℃, the heating rate is 20-60 ℃/h, and the time is 3-5 days; the temperature of the hydrogen reduction is 350-450 ℃, the heating rate is 60-100 ℃/h, and the time is 3-5 days.
6. The platinum metal nanocluster NaA molecular sieve prepared by the preparation method of any one of claims 1 to 5.
7. The use of the platinum metal nanocluster NaA molecular sieve as claimed in claim 6 for the preparation of 1,2,3,4-tetrahydroquinoline.
8. A method for preparing 1,2,3,4-tetrahydroquinoline, which is characterized in that under hydrogen atmosphere, the platinum metal nanocluster NaA molecular sieve of claim 6 is used as a catalyst to catalyze selective hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline.
9. The method for preparing 1,2,3,4-tetrahydroquinoline of claim 8, wherein the molar ratio of quinoline to platinum in the platinum metal nanocluster NaA molecular sieve is 30 to 70.
10. The method for preparing 1,2,3,4-tetrahydroquinoline according to claim 8, wherein the temperature of the catalytic reaction is 100-160 ℃, the pressure of hydrogen is 1.5-2.5 MPa, and the time is 40-90 min.
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