CN111545249B - Preparation method of conjugated microporous polymer/palladium-nickel bimetallic catalyst - Google Patents
Preparation method of conjugated microporous polymer/palladium-nickel bimetallic catalyst Download PDFInfo
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 46
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000012043 crude product Substances 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 20
- 238000002390 rotary evaporation Methods 0.000 claims description 20
- 229960001701 chloroform Drugs 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- VVTLQYQLVFNQBM-UHFFFAOYSA-N 2-[3,5-bis(2-trimethylsilylethynyl)phenyl]ethynyl-trimethylsilane Chemical compound C[Si](C)(C)C#CC1=CC(C#C[Si](C)(C)C)=CC(C#C[Si](C)(C)C)=C1 VVTLQYQLVFNQBM-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- RQEUFEKYXDPUSK-ZETCQYMHSA-N (1S)-1-phenylethanamine Chemical compound C[C@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-ZETCQYMHSA-N 0.000 claims description 7
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims description 7
- SFTFNJZWZHASAQ-UHFFFAOYSA-N 3,5-dibromobenzoic acid Chemical compound OC(=O)C1=CC(Br)=CC(Br)=C1 SFTFNJZWZHASAQ-UHFFFAOYSA-N 0.000 claims description 7
- HLAJZZSBQMLRKM-UHFFFAOYSA-N 3,5-dibromobenzoyl chloride Chemical compound ClC(=O)C1=CC(Br)=CC(Br)=C1 HLAJZZSBQMLRKM-UHFFFAOYSA-N 0.000 claims description 7
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- -1 compound 3,5-dibromobenzoic acid chloride Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/061—Chiral polymers
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention belongs to the technical field of preparation of conjugated microporous polymers, and discloses a preparation method of a conjugated microporous polymer/palladium-nickel bimetallic catalyst, which takes powdered chiral conjugated microporous polymers containing amido bonds and ethylene glycol as raw materials, and prepares a solution A by ultrasonic dispersion; with Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 Stirring and mixing O, chloroform and deionized water serving as raw materials to prepare a solution B; mixing the solution A and the solution B, and preparing a conjugated microporous polymer/palladium-nickel bimetallic catalyst through sodium borohydride reduction and room-temperature water bath reaction, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is a supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst; in conclusion, the whole reaction system is carried out in a room-temperature water bath without high-temperature calcination, so that the problems of poor stability, uneven particle size distribution, easy agglomeration, high energy consumption and the like of metal nanoparticles commonly existing in the traditional impregnation method are effectively solved.
Description
Technical Field
The invention belongs to the technical field of preparation of conjugated microporous polymers, and particularly relates to a preparation method of a conjugated microporous polymer/palladium-nickel bimetallic catalyst.
Background
The Chiral Conjugated Microporous Polymers (CCMPs) have the advantages of simple and efficient synthesis mode, multi-strategy construction means, easy functionalization, wide applicability and the like, and are extremely good carriers for further development into practical catalysts for producing optical pure organic molecules.
At present, the preparation methods of metal nanoparticles mainly include an immersion method, a sol-gel method, a chemical reduction method and the like, and the immersion method is mostly researched. Although the impregnation method is simple to operate, the problems of poor stability of metal nanoparticles, large particle size, easy agglomeration, high energy consumption and the like exist. Along with the gradual popularization of the research and application fields of the supported chiral catalyst, new problems occur, namely the problems of high cost, low catalytic efficiency, difficult catalyst recovery and the like in the using process of the supported chiral catalyst.
In conclusion, the research of the supported Chiral Conjugated Microporous Polymer (CCMPs)/palladium-nickel bimetallic nanoparticle catalyst which is low in cost, good in stability, high in catalytic activity, recyclable and simple and convenient to prepare has important research significance and scientific value.
Disclosure of Invention
In view of the above, the present invention is to provide a method for preparing a conjugated microporous polymer/palladium-nickel bimetallic catalyst, so as to effectively solve the problems mentioned in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a conjugated microporous polymer/palladium-nickel bimetallic catalyst takes powdered chiral conjugated microporous polymer containing amido bond and ethylene glycol as raw materials, and prepares a solution A by ultrasonic dispersion; with Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 Stirring and mixing O, chloroform and deionized water serving as raw materials to prepare a solution B; mixing the solution A and the solution B, and preparing a conjugated microporous polymer/palladium-nickel bimetallic catalyst through sodium borohydride reduction and room-temperature water bath reaction, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is a supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst;
the preparation method comprises the following steps:
s1, preparing a chiral conjugated microporous polymer containing amido bonds;
s2, grinding the polymer into fine powder by using an agate mortar, adding the powder into a two-necked bottle, adding ethylene glycol into the two-necked bottle, and performing ultrasonic dispersion on the ethylene glycol and the polymer to prepare a carrier solution A; wherein: the mixing mass ratio of the polymer to the ethylene glycol is 15-25: 1;
s3, according to the weight ratio of 1-1.3: 1 to 1.5:1: 1-2 mass ratio of mixed Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 Stirring and dissolving O, chloroform and deionized water to prepare a reagent solution B;
s4, injecting the reagent solution B prepared in the step S3 into the carrier solution A prepared in the step S2, and stirring at room temperature for 5-7 hours to obtain a solution C;
s5, adding a sodium borohydride aqueous solution into the solution C, stirring for 5-7 hours, and adjusting the pH value to be neutral to obtain a mixed solution D; wherein: the mixing mass ratio of the solution C to the sodium borohydride aqueous solution is 40-45: 1;
s6, filtering and washing the mixed solution D prepared in the step S5, and drying in vacuum to prepare the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst.
Preferably, in the step S2, the mixing mass ratio of the polymer to the ethylene glycol is 20:1.
preferably, in step S4 and step S5, the stirring time is 6 hours, and in step S5, the mixing mass ratio of the solution C to the sodium borohydride aqueous solution is 43:1.
in summary, the step S1 of preparing the chiral conjugated microporous polymer containing the amide bond includes:
s11, under the protection of nitrogen, injecting thionyl chloride into a three-necked bottle filled with 3,5-dibromobenzoic acid, mixing and heating to 70-80 ℃, stirring and reacting for 4 hours at 70-80 ℃, and then performing rotary evaporation to obtain a compound 3,5-dibromobenzoic acid chloride;
s12, under the protection of nitrogen, injecting (S) - (-) -alpha-phenylethylamine into a three-necked bottle containing 3,5-dibromobenzoyl chloride, mixing, continuously heating for 5-10 minutes by using a microwave reactor under the condition that the power is 100W, and slowly crystallizing at the temperature of 1-5 ℃ by using trichloromethane as a good solvent and n-hexane as a poor solvent to obtain a white needle-shaped crystal a;
s13, mixing 1,3,5-tribromobenzene, pd (PPh) 3 ) 2 Cl 2 CuI and PPh 3 Adding the mixture into a three-neck flask, performing nitrogen protection, adding triethylamine serving as a solvent into the three-neck flask, reacting for 15 minutes, adding trimethylsilylacetylene, stirring and reacting for 15 to 17 hours at the temperature of between 85 and 95 ℃, performing suction filtration on the solution after reaction through diatomite, and performing rotary evaporation on the filtrate after suction filtration to obtain a crude product b;
s14, purifying the crude product b by using a silica gel chromatographic column, performing rotary evaporation after purification to obtain a light yellow concentrated solution c, and cooling the concentrated solution c to separate out a crystal compound 1,3,5-tri (trimethylsilylethynyl) benzene; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.42;
s15, mixing 1,3,5-tri (trimethylsilylethynyl) benzene and K 2 CO 3 Adding the mixture into a three-neck flask, carrying out nitrogen protection, adding tetrahydrofuran and methanol into the three-neck flask after protection, stirring and reacting for 6 hours at room temperature, and then removing the tetrahydrofuran and methanol solvent through filtration and rotary evaporation to obtain a crude product d;
s16, purifying the crude product d through a silica gel chromatographic column, and then performing rotary evaporation to obtain a white solid e; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.56;
s17, adding the crystal a obtained in the step S12 and the solid e obtained in the step S16 into a three-necked bottle, and then sequentially adding Pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 Then, under the protection of nitrogen, triethylamine and dimethylformamide are injected to obtain a mixture f;
s18, placing the three-necked bottle filled with the mixture f into a microwave reactor, heating and stirring for 10-15 minutes under the condition that the power is 200W, and heating and stirring for 4-6 minutes under the condition that the power is 300W to obtain a crude product g;
and S19, washing the crude product g by using methanol, a KI aqueous solution and chloroform respectively, and drying after washing to obtain a yellow solid, namely the chiral conjugated microporous polymer containing the amido bond.
Preferably, in the step S11, the mixing mass ratio of thionyl chloride to 3,5-dibromobenzoic acid is 4 to 5:1, heating in an oil bath at 75 ℃ for 4 hours under stirring.
Preferably, in the step S12, the mixing mass ratio of (S) - (-) - α -phenylethylamine to 3,5-dibromobenzoyl chloride is 1: 2-2.5, and when the microwave reactor is used for continuous heating, the continuous heating is 8 minutes, the crystallization temperature is 2 ℃, and the crystallization time is 12 hours.
Preferably, in the step S13, 1,3,5-tribromobenzene, pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 And the mixing mass ratio of triethylamine to trimethylsilylacetylene is 1: 65-70: 15-20: 25 to 26:35 to 36:1.5 to 2, and stirring and reacting for 16 hours at the temperature of 90 ℃ after mixing.
Preferably, in step S15, 1,3,5-tris (trimethylsilylethynyl) benzene, K 2 CO 3 And the mixing mass ratio of the tetrahydrofuran to the methanol is 1:55 to 60:12 to 15:4 to 5.
Preferably, in the step S17, the crystal a, the solid e and Pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 And the mixing mass ratio of triethylamine to dimethylformamide is 11-12: 7 to 8:100:2 to 3:6 to 7:1:1 to 1.5.
Preferably, in step S18, the heating and stirring time is 12 minutes at a power of 200W and 5 minutes at a power of 300W.
Compared with the prior art, the invention has the following beneficial effects:
in the preparation method provided by the invention, a chiral conjugated microporous polymer containing amido bond is taken as a carrier, ethylene glycol is taken as a solvent, and dispersed and mixed to prepare a carrier solution; with mixed Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 O, chloroform and deionized water are used as reagent solutions; mixing the carrier solution and the reagent solution, and preparing the palladium-nickel bimetallic nano-particles under the condition of sodium borohydride reductionThe bimetallic nanoparticles are loaded on the chiral conjugated microporous polymer, so that a loaded chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst is obtained; the whole reaction system is carried out in room-temperature water bath without high-temperature calcination, thereby effectively solving the problems of poor stability, uneven particle size distribution, easy agglomeration, high energy consumption and the like of metal nano particles commonly existing in the traditional impregnation method;
in addition, the catalyst prepared based on the method can also effectively introduce nickel metal nanoparticles, and has important significance for improving the catalytic activity, reducing the input amount of palladium and reducing the cost; and also has the advantages of good stability and high recyclability.
Drawings
FIG. 1 is an infrared spectrum of a chiral conjugated microporous polymer containing amide bonds prepared by the method of the present invention;
FIG. 2 is a scanning electron microscope image of a chiral conjugated microporous polymer containing amide bonds prepared by the method provided by the invention;
FIG. 3 is an X photoelectron spectrum of the supported chiral conjugated microporous polymer/Pd-Ni bimetallic nanoparticle catalyst prepared by the method of the present invention;
FIG. 4 is a scanning transmission electron microscope image and a high-angle annular dark field image of the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst prepared by the method provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides a preparation method of a conjugated microporous polymer/palladium-nickel bimetallic catalyst, which takes powdered chiral conjugated microporous polymer containing amido bond and ethylene glycol as raw materialsCarrying out ultrasonic dispersion on raw materials to prepare a solution A; with Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 O, chloroform and deionized water are taken as raw materials, and are stirred and mixed to prepare a solution B; mixing the solution A and the solution B, and preparing a conjugated microporous polymer/palladium-nickel bimetallic catalyst through sodium borohydride reduction and room-temperature water bath reaction, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is a supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst; the preparation method comprises the following steps:
s1, preparing a chiral conjugated microporous polymer containing amido bonds;
s11, under the protection of nitrogen, injecting thionyl chloride into a three-necked bottle filled with 3,5-dibromobenzoic acid, mixing and heating to 70-80 ℃, stirring and reacting for 4 hours at 70-80 ℃, and then performing rotary evaporation to obtain a compound 3,5-dibromobenzoic acid chloride;
in the step, the mixing mass ratio of thionyl chloride to 3,5-dibromobenzoic acid is 4-5: 1; the heating mode is preferably oil bath heating, the heating temperature can be preferably 75 ℃, and the stirring reaction time can be preferably 4 hours.
S12, under the protection of nitrogen, injecting (S) - (-) -alpha-phenylethylamine into a three-necked bottle containing 3,5-dibromobenzoyl chloride, mixing, continuously heating for 5-10 minutes by using a microwave reactor under the condition that the power is 100W, and slowly crystallizing at the temperature of 1-5 ℃ by using trichloromethane as a good solvent and n-hexane as a poor solvent to obtain a white needle-shaped crystal a;
in the step, the mixing mass ratio of (S) - (-) -alpha-phenylethylamine to 3,5-dibromobenzoyl chloride is 1:2 to 2.5, and when the heating is continued using a microwave reactor, the duration of the heating may preferably be 8 minutes, the crystallization temperature may preferably be 2 ℃, and the crystallization time may preferably be 12 hours.
S13, mixing 1,3,5-tribromobenzene, pd (PPh) 3 ) 2 Cl 2 CuI and PPh 3 Adding the mixture into a three-neck flask, performing nitrogen protection, adding triethylamine serving as a solvent into the three-neck flask, reacting for 15 minutes, adding trimethylsilylacetylene, stirring and reacting for 15 to 17 hours at the temperature of between 85 and 95 ℃, and performing suction filtration on the solution after reaction by using diatomiteCarrying out rotary evaporation on the filtrate obtained by suction filtration to obtain a crude product b;
in this step, 1,3,5-tribromobenzene, pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 The mixing mass ratio of triethylamine to trimethylsilylacetylene may preferably be 1: 65-70: 15-20: 25 to 26:35 to 36:1.5 to 2, and further preferably 1:68:18:25.8:35.2:1.8, and stirring the mixture to react for 16 hours at 90 ℃.
S14, purifying the crude product b by using a silica gel chromatographic column, performing rotary evaporation after purification to obtain a light yellow concentrated solution c, and cooling the concentrated solution c to separate out a crystal compound 1,3,5-tri (trimethylsilylethynyl) benzene; wherein: in the purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.42.
S15, mixing 1,3,5-tri (trimethylsilylethynyl) benzene and K 2 CO 3 Adding the mixture into a three-neck flask, carrying out nitrogen protection, adding tetrahydrofuran and methanol into the three-neck flask after protection, stirring and reacting for 6 hours at room temperature, and then removing the tetrahydrofuran and methanol solvent through filtration and rotary evaporation to obtain a crude product d;
in this step, 1,3,5-tris (trimethylsilylethynyl) benzene, K 2 CO 3 The mixing mass ratio of tetrahydrofuran to methanol may preferably be 1:55 to 60:12 to 15:4 to 5, and further preferably 1:57:14.4:4.3.
s16, purifying the crude product d by a silica gel chromatographic column, and then performing rotary evaporation to obtain a white solid e; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.5.
S17, adding the crystal a obtained in the step S12 and the solid e obtained in the step S16 into a three-necked bottle, and then sequentially adding Pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 Then, under the protection of nitrogen, triethylamine and dimethylformamide are injected to obtain a mixture f;
in this step, crystals a, solid e, pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 The mixing mass ratio of triethylamine to dimethylformamide may preferably be 11 to 12:7 to 8:100:2 to 3:6 to 7:1:1 to 15, further still preferably 11.3:7.1:100:2.7:6.3:1:1.4.
s18, placing the three-necked bottle filled with the mixture f into a microwave reactor, heating and stirring for 10-15 minutes under the condition of power of 200W, and heating and stirring for 4-6 minutes under the condition of power of 300W to obtain a crude product g;
in this step, it is preferable that the heating and stirring time is 12 minutes at a power of 200W and 5 minutes at a power of 300W.
S19, washing the crude product g by using methanol, KI aqueous solution and trichloromethane respectively, and drying after washing to obtain a yellow solid, namely the chiral conjugated microporous polymer containing amido bonds
S2, grinding the polymer into fine powder by using an agate mortar, adding the powder into a two-necked bottle, adding ethylene glycol into the two-necked bottle, and performing ultrasonic dispersion on the ethylene glycol and the polymer to prepare a carrier solution A; wherein: the mixing mass ratio of the polymer to the ethylene glycol is 15-25: 1;
in this step, the mixing mass ratio of the polymer to ethylene glycol may preferably be 20:1.
s3, according to the weight ratio of 1-1.3: 1 to 1.5:1: 1-2 mass ratio of mixed Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 Stirring and dissolving O, chloroform and deionized water to prepare a reagent solution B;
in this step, pd (OAC) 2 、Ni(OAC) 2 ·4H 2 The mixing mass ratio of O, chloroform and deionized water is further preferably 1:1.2:1:1.6.
s4, injecting the reagent solution B prepared in the step S3 into the carrier solution A prepared in the step S2, and stirring for 5-7 hours at room temperature to obtain a solution C.
S5, adding a sodium borohydride aqueous solution into the solution C, stirring for 5-7 hours, and adjusting the pH value to be neutral to obtain a mixed solution D; wherein: the mixing mass ratio of the solution C to the sodium borohydride aqueous solution is 40-45: 1.
in summary, in step S4 and step S5, the stirring time is 6 hours, and in step S5, the mixing mass ratio of the solution C and the sodium borohydride aqueous solution may be preferably 43:1.
s6, filtering and washing the mixed solution D prepared in the step S5, and drying in vacuum to prepare the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst.
In summary, with respect to the above preparation method, based on further preferred reaction data, the following specific preparation examples are provided in this example:
(1) Under the protection of nitrogen, thionyl chloride (5.00 mL) is injected into a three-neck flask filled with 3,5-dibromobenzoic acid (1.19g, 6.80mmol), the three-neck flask is heated to 75 ℃ through an oil bath, stirred and reacted for 4 hours, and then the mixture is subjected to rotary evaporation to obtain a compound 3,5-dibromobenzoyl chloride;
(2) Under the protection of nitrogen, injecting (S) - (-) -alpha-phenylethylamine (0.880 mL,6.80 mmol) into a three-neck bottle containing 3,5-dibromobenzoyl chloride (2.03g, 6.80 mmol), mixing, continuously heating for 8 minutes by using a microwave reactor under the condition that the power is 100W, and slowly crystallizing at the condition of 2 ℃ by using trichloromethane as a good solvent and n-hexane as a poor solvent to obtain white needle-shaped crystals a;
(3) 1,3,5-tribromobenzene (5.00g, 15.9mmol), pd (PPh) 3 ) 2 Cl 2 (340mg, 0.490mmol), cuI (90.0mg, 0.490mmol) and PPh 3 (129mg, 0.490mmol) is added into a three-neck flask, nitrogen protection is carried out, then 176mL of triethylamine is added into the three-neck flask as a solvent, 9.00mL of trimethylsilylacetylene is added after reaction is carried out for 15 minutes, stirring is carried out for reaction for 16 hours at the temperature of 90 ℃, the solution after reaction is subjected to suction filtration through diatomite, and the filtrate after suction filtration is subjected to rotary evaporation to obtain a crude product b; after obtaining a crude product b, purifying the crude product b by a silica gel chromatographic column, performing rotary evaporation after purification to obtain a light yellow concentrated solution c, and cooling the concentrated solution c to separate out a crystal compound 1,3,5-tri (trimethylsilylethynyl) benzene; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.42;
(4) 1,3,5-tris (trimethylsilylethynyl) benzene (1.00g, 2.73mmol) and K 2 CO 3 (57.0 mg, 0.410mmol) was charged into a three-necked flask, and nitrogen protectedAfter protection, adding 14.4mL of tetrahydrofuran and 4.30mL of methanol into a three-neck flask, stirring at room temperature for reaction for 6 hours, and then removing the tetrahydrofuran and methanol solvent through filtration and rotary evaporation to obtain a crude product d; after a crude product d is obtained, purifying the crude product d by a silica gel chromatographic column, and then performing rotary evaporation to obtain a white solid e; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.56;
(5) The crystal a (79.0 mg, 223. Mu. Mol) obtained in (2) and the solid e (57.0 mg, 0.410mmol) obtained in (4) were put into a three-necked flask, and then Pd (PPh) was added thereto successively 3 ) 2 Cl 2 （700g，100μmol）、CuI（19.0mg，100μmol）、PPh 3 (44.0 mg, 170. Mu. Mol), followed by injection of 7mL triethylamine and 10mL dimethylformamide under nitrogen to afford mixture f; placing the three-necked bottle filled with the mixture f into a microwave reactor, heating and stirring for 12 minutes under the condition of the power of 200W, and heating and stirring for 5 minutes under the condition of the power of 300W to obtain a crude product g;
(6) Washing the crude product g by using methanol, KI aqueous solution and chloroform respectively, and drying after washing to obtain yellow solid, namely the chiral conjugated microporous polymer containing amido bonds;
(7) Grinding the polymer (100 mg) obtained in the step (6) to fine powder by using an agate mortar, adding the powder into a two-necked bottle, adding ethylene glycol (5 ml) into the two-necked bottle, and performing ultrasonic dispersion on the ethylene glycol and the polymer to prepare a carrier solution A;
(8) Pd (OAC) 2 (5.27mg，0.0230mmol)、Ni(OAC) 2 ·4H 2 Adding O (5.78mg, 0.0230 mol) into a mixed solution of chloroform (5 ml) and deionized water (8 ml), stirring and dissolving to prepare a reagent solution B;
(9) Injecting the reagent solution B prepared in the step (8) into the carrier solution A prepared in the step (7), and stirring for 6 hours at room temperature to obtain a solution C; adding 1M sodium borohydride aqueous solution (3 ml) into the solution C, stirring for 6 hours, and adjusting the pH value to be neutral to obtain mixed solution D;
(10) And (4) filtering and washing the mixed solution D prepared in the step (9), and drying in vacuum to prepare the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst.
Based on the preparation process of the specific preparation example, the infrared scanning, the electron microscope scanning, the X-ray scanning and the transmission scanning are carried out on the raw materials; specifically, the method comprises the following steps:
FIG. 1 shows an infrared spectrum of a chiral conjugated microporous polymer containing amide bonds;
as shown in FIG. 1, 3420cm -1 Has a characteristic peak of hydrogen bonding, 2982cm -1 In the presence of CH 3 The stretching vibration peak of (1); 2220cm -1 The peak of stretching vibration of C ≡ C appears at 1720cm -1 The peak of the expansion vibration of C = O in amide appears, 1586cm -1 The stretching vibration peak of benzene ring is 1250cm -1 The stretching vibration peak of C-N in amide appears, so that the amide bond-containing chiral conjugated microporous polymer can be determined to be successfully synthesized.
FIG. 2 is a scanning electron micrograph of a chiral conjugated microporous polymer containing amide linkages;
as shown in FIG. 2, the size of the prepared polymer is about 100nm, the morphology of the polymer is nano-particles, and the polymer has a large specific surface area.
An X photoelectron energy spectrum when palladium-nickel nanoparticles are loaded on the amide bond-containing chiral conjugated microporous polymer shown in fig. 3 (i.e., an X photoelectron energy spectrum of the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst);
as can be seen from FIG. 3, the palladium loading was 1.77wt% as measured by XPS, and the XPS spectrum of Pd3d, as seen in FIG. 3a, was Pd for the catalyst at 335.4ev peak, 340.7ev peak, respectively 0 3d 5/2 And Pd 0 3d 3/2 From this, the valence of palladium is 0. As can be seen in FIG. 3b, there are two valence states of nickel, ni2P, which is 0-valent nickel at 853.5ev peak, 870.4ev peak, respectively 3/2 And Ni2P 1/2 (ii) a Ni of nickel in higher oxidation state at 859.3ev peak and 877.3ev peak, respectively a 2P 3/2 And Ni a 2P 1/2 This effectively proves that the palladium-nickel nanoparticles are successfully loaded into the amide bond-containing chiral conjugated microporous polymer.
Fig. 4 shows a scanning transmission electron microscope image and a high-angle annular dark field image of the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst when palladium-nickel nanoparticles are supported by the amide bond-containing chiral conjugated microporous polymer (pd — ni — pd — bi-metal nanoparticle).
FIG. 4a is a graph showing an image of a scanning transmission electron microscope showing palladium nanoparticles in a crystal phase, from which it can be seen that the interplanar spacing is 0.224nm, and thus can correspond to the FCC (111) interplanar of palladium;
in addition, as can be seen from fig. 4b and 4c, the lighter parts in the high-angle annular dark field image are palladium atoms and nickel atoms with larger atomic numbers, and the palladium atoms and nickel atoms can be effectively observed to be uniformly dispersed on the chiral conjugated microporous polymer support, thereby further confirming that the palladium-nickel nanoparticles are successfully loaded in the amide bond-containing chiral conjugated microporous polymer.
In conclusion, the method is proved to be capable of effectively completing the preparation of the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a conjugated microporous polymer/palladium-nickel bimetallic catalyst is characterized by comprising the following steps: taking a powdery chiral conjugated microporous polymer containing amido bonds and ethylene glycol as raw materials, and performing ultrasonic dispersion to prepare a solution A; with Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 Stirring and mixing O, chloroform and deionized water serving as raw materials to prepare a solution B; mixing the solution A and the solution B, and preparing a conjugated microporous polymer/palladium-nickel bimetallic catalyst through sodium borohydride reduction and room-temperature water bath reaction, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is a supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst;
the preparation method comprises the following steps:
s1, preparing a chiral conjugated microporous polymer containing amido bonds;
s2, grinding the polymer into fine powder by using an agate mortar, adding the powder into a two-necked bottle, adding ethylene glycol into the two-necked bottle, and performing ultrasonic dispersion on the ethylene glycol and the polymer to prepare a carrier solution A; wherein: the mixing mass ratio of the polymer to the ethylene glycol is 15-25: 1;
s3, according to the weight ratio of 1-1.3: 1 to 1.5:1: 1-2 mass ratio of mixed Pd (OAC) 2 、Ni(OAC) 2 ·4H 2 Stirring and dissolving O, chloroform and deionized water to prepare a reagent solution B;
s4, injecting the reagent solution B prepared in the step S3 into the carrier solution A prepared in the step S2, and stirring at room temperature for 5-7 hours to obtain a solution C;
s5, adding a sodium borohydride aqueous solution into the solution C, stirring for 5-7 hours, and adjusting the pH value to be neutral to obtain a mixed solution D; wherein: the mixing mass ratio of the solution C to the sodium borohydride aqueous solution is 40-45: 1;
s6, filtering and washing the mixed solution D prepared in the step S5, and drying in vacuum to prepare the supported chiral conjugated microporous polymer/palladium-nickel bimetallic nanoparticle catalyst.
2. The method of claim 1, wherein the method comprises the steps of: in the step S2, the mixing mass ratio of the polymer to the ethylene glycol is 20:1.
3. the method of claim 1, wherein the method comprises the steps of: in the step S4 and the step S5, the stirring time is 6 hours, and in the step S5, the mixing mass ratio of the solution C to the sodium borohydride aqueous solution is 43:1.
4. the method for preparing a conjugated microporous polymer/palladium-nickel bimetallic catalyst according to any one of claims 1 to 3, wherein the step S1 of preparing the chiral conjugated microporous polymer containing amide bonds comprises:
s11, under the protection of nitrogen, injecting thionyl chloride into a three-necked bottle filled with 3,5-dibromobenzoic acid, mixing and heating to 70-80 ℃, stirring and reacting for 4 hours at 70-80 ℃, and then performing rotary evaporation to obtain a compound 3,5-dibromobenzoic acid chloride;
s12, under the protection of nitrogen, injecting (S) - (-) -alpha-phenylethylamine into a three-necked bottle containing 3,5-dibromobenzoyl chloride, mixing, continuously heating for 5-10 minutes by using a microwave reactor under the condition that the power is 100W, and slowly crystallizing at the temperature of 1-5 ℃ by using trichloromethane as a good solvent and n-hexane as a poor solvent to obtain a white needle-shaped crystal a;
s13, mixing 1,3,5-tribromobenzene, pd (PPh) 3 ) 2 Cl 2 CuI and PPh 3 Adding the mixture into a three-neck flask, performing nitrogen protection, adding triethylamine serving as a solvent into the three-neck flask, reacting for 15 minutes, adding trimethylsilylacetylene, stirring and reacting for 15 to 17 hours at the temperature of between 85 and 95 ℃, performing suction filtration on the solution after reaction through diatomite, and performing rotary evaporation on the filtrate after suction filtration to obtain a crude product b;
s14, purifying the crude product b by using a silica gel chromatographic column, performing rotary evaporation after purification to obtain a light yellow concentrated solution c, and cooling the concentrated solution c to separate out a crystal compound 1,3,5-tri (trimethylsilylethynyl) benzene; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.42;
s15, mixing 1,3,5-tri (trimethylsilylethynyl) benzene and K 2 CO 3 Adding the mixture into a three-neck flask, carrying out nitrogen protection, adding tetrahydrofuran and methanol into the three-neck flask after protection, stirring and reacting for 6 hours at room temperature, and then removing the tetrahydrofuran and methanol solvent through filtration and rotary evaporation to obtain a crude product d;
s16, purifying the crude product d by a silica gel chromatographic column, and then performing rotary evaporation to obtain a white solid e; wherein: during purification, the purification eluent is n-hexane, and the Rf value of the n-hexane is 0.56;
s17, adding the crystal a obtained in the step S12 and the solid e obtained in the step S16 into a three-necked bottle, and then sequentially adding Pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 Then, under the protection of nitrogen, triethylamine and dimethylformamide are injected to obtain a mixture f;
s18, placing the three-necked bottle filled with the mixture f into a microwave reactor, heating and stirring for 10-15 minutes under the condition that the power is 200W, and heating and stirring for 4-6 minutes under the condition that the power is 300W to obtain a crude product g;
and S19, washing the crude product g by using methanol, a KI aqueous solution and chloroform respectively, and drying after washing to obtain a yellow solid, namely the chiral conjugated microporous polymer containing the amido bond.
5. The method of claim 4, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is prepared by the following steps: in the step S11, the mixing mass ratio of thionyl chloride to 3,5-dibromobenzoic acid is 4-5: 1, heating in an oil bath at 75 ℃ for 4 hours under stirring.
6. The method of claim 4, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is prepared by the following steps: in the step S12, the mixing mass ratio of (S) - (-) -alpha-phenylethylamine to 3,5-dibromobenzoyl chloride is 1: 2-2.5, and when the microwave reactor is used for continuous heating, the continuous heating is 8 minutes, the crystallization temperature is 2 ℃, and the crystallization time is 12 hours.
7. The method of claim 4, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is prepared by the following steps: in the step S13, 1,3,5-tribromobenzene, pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 And the mixing mass ratio of triethylamine to trimethylsilylacetylene is 1: 65-70: 15-20: 25 to 26:35 to 36:1.5 to 2, and stirring and reacting for 16 hours at the temperature of 90 ℃ after mixing.
8. The method of claim 4, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is prepared by the following steps: in the step S15, 1,3,5-tri (trimethylsilylethynyl) benzene and K 2 CO 3 And the mixing mass ratio of the tetrahydrofuran to the methanol is 1:55 to 60:12 to 15:4 to 5.
9. The method of claim 4, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is prepared by the following steps: in the step S17, crystal a, solid e and Pd (PPh) 3 ) 2 Cl 2 、CuI、PPh 3 And the mixing mass ratio of triethylamine to dimethylformamide is 11-12: 7 to 8:100:2 to 3:6 to 7:1:1 to 1.5.
10. The method of claim 4, wherein the conjugated microporous polymer/palladium-nickel bimetallic catalyst is prepared by the following steps: in step S18, the heating and stirring time is 12 minutes at a power of 200W and 5 minutes at a power of 300W.
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