CN116328822A - Metal-supported molecular sieve catalyst and preparation method and application thereof - Google Patents

Metal-supported molecular sieve catalyst and preparation method and application thereof Download PDF

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CN116328822A
CN116328822A CN202310326035.3A CN202310326035A CN116328822A CN 116328822 A CN116328822 A CN 116328822A CN 202310326035 A CN202310326035 A CN 202310326035A CN 116328822 A CN116328822 A CN 116328822A
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molecular sieve
zeolite
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陈锋
韩慧芬
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Yangzhou University
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Abstract

The invention discloses a metal supported molecular sieve catalyst and a preparation method and application thereof, wherein the expression is M@zeolite-T, M/L@zeolite-T or M-R/L@zeolite-T, and the expression is M@zeolite-T: m is metal Cu, au, ru, mn or Fe; r is metal Pt, pd, ru, ni, fe or Au; l is N ', N', N ', N' -tetramethyl ethylenediamine, bipyridine, triphenylphosphine, phenanthroline, tributyl phosphate or tributyl phosphite; zeolite represents molecular sieve, and is HY type molecular sieve, Y type molecular sieve, ZSM-5 type molecular sieve, SAPO type molecular sieve, beta type molecular sieve 40 A molecular sieve of the type or MOR; t is the temperature, and the value is 200 ℃, 300 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃. The invention realizes the in-situ preparation of various organoboron compounds by alcohol molecules by constructing a bifunctional catalyst and a proper catalytic system.

Description

Metal-supported molecular sieve catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a metal-supported molecular sieve catalyst, and a preparation method and application thereof.
Background
The boron-containing organic compound has wide application in the field of organic synthesis and functional materials, so that the development of a method for synthesizing the boron-containing compound has important value. Compared with other organic nucleophiles, organoboranes are most commonly used because of their stability, ease of handling, high functional group compatibility, moderate reactivity, low toxicity. Due to the ease of handling and ease of organoboraneMulti-component reactions involving C-B bond formation and conversion of various functional groups have been widely developed to obtain. The most important examples of these transformations include oxidation, halogenation, amination, carbonization reactions. In addition, organoboranes are synthetic intermediates in the synthesis of pharmaceuticals, pesticides, liquid crystals and organic light emitting diodes. The important role of organoboranes in modern synthetic chemistry has led to the rapid development of methods for synthesizing related organoboronate compounds and the like. Traditional organoboranes are synthesized based on the reaction of a grignard reagent such as organolithium, organomagnesium, etc. with a trialkylborate, followed by hydrolysis or transesterification. However, the synthetic boride process is limited due to the poor tolerance of functional groups in the formation of the reacted organolithium and organomagnesium reagents and the complex and expensive steps of protection and deprotection. To overcome these drawbacks, transition metal catalyzed boroesterification reactions have evolved and are considered one of the most efficient methods for synthesizing organoborane derivatives at the time. In recent years, with intensive research into transition metal catalytic borides, new transition metal catalytic systems have been established to address the regioselectivity and enantioselectivity of the boriding reaction. By using Re, ru, rh and Ir transition metal catalysts and B 2 pin 2 Or HBpin has also made significant progress in direct boronation of C-H bonds of alkanes, alkenes and alkynes. Accordingly, the highly selective metal-catalyzed boration of Csp3-X and Csp2-X (x= Cl, br, I, OTf) with alkoxyboranes also gives boronated products. Transition metals catalyze the carbon-boron (C-B) reaction of diboron with unsaturated carbon-carbon bonds such as alkenes, alkynes, and the like, for the synthesis of valuable polysubstituted compounds. Meanwhile, catalytic boration reactions are also expanded to use transition metals such as Ag, ni, zn, pd, fe and Cu as catalysts. In this context, transition metal catalysis is increasingly being used in the synthesis of organoboron compounds with the rapid development of metal organic chemistry. Compared with the traditional catalytic boride reaction, the transition metal catalytic boride reaction has the advantages of high reaction activity and efficiency, good stereoselectivity and regioselectivity and the like, and becomes a research hot spot in the related fields of metal organic catalysis, organic synthesis and the like at present. However, these processes also have disadvantages, such as the need for an inert atmosphere, weight in the productMetal contamination, expensive catalysts and recyclability of ligands. Thus, there is a need for more environmentally friendly and economical methods for synthesizing organoboranes. With the more and more intensive research of novel materials such as MOF, zeolite, nano materials and the like in recent years, the materials have the advantages of being capable of being repeatedly used, environment-friendly and the like, and people gradually turn the eye light into a novel composite material by combining metal and the novel material. At present, the technology of a novel composite catalytic material synthesis method is not mature, and a novel synthesis method is urgently needed to be explored.
The current reaction of synthesizing organic boron compound by reacting olefin with boron reagent is most extensive, and mainly uses homogeneous metal-ligand complex catalyst and metal-free catalytic system to implement activity and selectivity control of reaction. However, the high activity of the olefin is easy to generate polymerization reaction, so that the purity of the olefin is reduced, and the difficulty in synthesizing, preparing and storing the high-purity olefin is high. The alcohol which is the main synthetic raw material of the reverse olefin is also an important organic synthetic intermediate, and has the advantages of low toxicity, easy preservation, low price and wide sources. Most of olefins can be dehydrated from alcohol, the reaction cost is low, and the system is simple, so that a plurality of novel catalysts which can directly catalyze alcohols to generate organoboron compounds through the boration reaction are designed, and the in-situ preparation of various organoboron compounds of alcohol molecules is realized through the acidity of a porous material molecular sieve and the catalytic action of an in-pore metal catalyst on olefin functionalization by constructing an acid metal bifunctional catalyst and a proper catalytic system.
Disclosure of Invention
The invention aims to provide a metal supported molecular sieve catalyst, a preparation method and application thereof, and aims to realize in-situ preparation of various organoboron compounds by alcohol molecules by constructing an acid metal bifunctional catalyst and a proper catalytic system.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a metal supported molecular sieve catalyst having the expression m@zeolite-T, M/l@zeolite-T or M-R/l@zeolite-T, wherein: m is metal Cu, au, ru, mn or Fe; r is metal Pt, pd, ru, niFe or Au; l is N ', N', N ', N' -tetramethyl ethylenediamine, bipyridine, triphenylphosphine, phenanthroline, tributyl phosphate or tributyl phosphite; zeolite represents molecular sieve, and is HY type molecular sieve, Y type molecular sieve, ZSM-5 type molecular sieve, SAPO type molecular sieve, beta type molecular sieve 40 A molecular sieve of the type or MOR; t is the temperature, and the value is 200 ℃, 300 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃.
For M@zeolite-T, the mass contents of the components are as follows: m: 0.5-4% and the balance molecular sieve; for M/L@zeolite-T, the mass contents of the components are as follows: m:0.5 to 4 percent, L: 2-16%, the rest is molecular sieve; for M-R/L@zeolite-T, the mass contents of the components are as follows: m:0.5 to 4 percent, R:0.5 to 4 percent, L: 2-16% and the balance molecular sieve.
The preparation method of the metal supported molecular sieve catalyst comprises any one of the first to third methods:
the method I comprises the following steps:
step A1, loading metal elements on a molecular sieve by using an impregnation technology, and drying to obtain an M@zeolite-T precursor;
step B1, taking part of catalyst precursor and roasting to obtain a catalyst M@zeolite-T;
step C1, treating the rest M@zeolite-T precursor in a reducing atmosphere to obtain a reduced catalyst M@zeolite-T;
the second method comprises the following steps:
step A2, loading metal salt and ligand on a molecular sieve together by using an impregnation technology, and drying to obtain an M/L@zeolite-T precursor;
step B2, taking part of catalyst precursor and roasting to obtain a catalyst M/L@zeolite-T;
step C2, treating the rest M/L@zeolite-T precursor in a reducing atmosphere to obtain a reduced catalyst M/L@zeolite-T;
the third method comprises the following steps:
step A3, loading two different metal elements and ligands on a molecular sieve together by utilizing a hydrothermal technology, and drying to obtain an M-R/L@zeolite-T precursor;
step B3, taking part of catalyst precursor and roasting to obtain a catalyst M-R/L@zeolite-T;
and C3, treating the rest M-R/L@zeolite-T precursor in a reducing atmosphere to obtain a reduced catalyst M-R/L@zeolite-T.
In the steps A1, A2 and A3, the roasting conditions are as follows: roasting at 200-800 deg.c in air for 3-8 hr.
In the steps B1, B2 and B3, the roasting conditions are as follows: roasting at 200-800 deg.c in reducing atmosphere for 3-8 hr.
In the steps B1, B2 and B3, the reducing gas is hydrogen and argon in a volume ratio of 5%:95% of mixed gas and the space velocity of the reducing gas is 100-10000 ml/g catalyst/h.
The metal supported molecular sieve catalyst is applied to catalyzing the boronation reaction of alcohol compounds.
The alcohol compound is 1-phenethyl alcohol substituted by an electron donating group or an electron withdrawing group, and the electron donating group or the electron withdrawing group is one of methyl, isopropyl, methoxy and halogen (F, cl, br, I).
The boration reaction is to make alcohol compound and dipyrniol diboron (B) 2 pin 2 ) Mixing, and reacting in tetrahydrofuran or 1, 4-dioxane reagent under the catalysis of the metal supported molecular sieve catalyst.
The bippinacol diboron (B) 2 pin 2 ) The structural formula is as follows:
Figure BDA0004153327710000041
the reaction temperature of the boration reaction is 50-130 ℃.
The molar ratio of the alcohol compound to the dipyruvate diboron to the metal-supported molecular sieve catalyst is 10-20:10-20:1. The beneficial effects are that: the method has the advantages of simple process for preparing the catalyst, obvious yield improvement, and capability of recycling for multiple times by using cheap metal as the catalyst, and can obviously reduce the cost.
Drawings
FIG. 1 is an M/L@HY-T Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image: (a) SEM images of HY-type molecular sieve supports; (b) TEM images of HY-type molecular sieve carriers; (c) SEM image of M/L@HY-T catalyst; (d) TEM image of M/L@HY-T catalyst;
FIG. 2 is a polycrystalline X-ray diffraction (XRD) pattern of M/L@HY-T: an XRD pattern of (a) HY; (b) XRD pattern of M/L@HY-T.
Detailed Description
The invention is further explained below with reference to the drawings.
The invention discloses a double-function acid metal catalyst synthesized by taking a series of transition non-noble metal salts, molecular sieves and the like as raw materials through a hydrothermal method and calcination. The material can catalyze a series of direct boration reactions of 1-phenethyl alcohol and derivative substrates thereof to synthesize boric acid ester.
Example 1: preparation of the catalyst
(1) The HY type molecular sieve is hydrothermally impregnated with a soluble salt (CuX) aqueous solution containing Cu ions for 24 hours by using a conventional hydrothermal method technology. After water was removed by centrifugation, the mixture was dried in an oven at 110℃for 12 hours, and heated to T (T: 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃) at a rate of 5℃per minute in a muffle furnace and calcined for 5 hours, respectively, to obtain the M (CuX) @ HY-T catalyst.
(2) The M (CuX) @ HY-T precursor prepared by the hydrothermal impregnation method is heated to T (T is 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃) in a muffle furnace at a speed of 5 ℃/min under a reducing atmosphere, and baked for 5 hours to obtain a reduced Cu/HY-T catalyst.
(3) The M (CuX) @ HY-T precursor prepared by a hydrothermal soaking method is soaked by adding a ligand L, then dried for 12 hours at 110 ℃ in an oven, and heated to T (200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃) respectively at a rate of 5 ℃/min in a muffle furnace under air and baked for 5 hours to prepare the M (CuX)/L@HY-T catalyst. Or respectively heating to T (T is 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃) in a muffle furnace at a speed of 5 ℃/min under the atmosphere of a mixed gas of hydrogen and argon, and roasting for 5 hours to perform reduction treatment, thus obtaining the reduced Cu/L@HY-T catalyst.
Example 2: evaluation of catalyst reactivity
The acid-metal bifunctional catalyst can catalyze phenethyl alcohol to synthesize boric acid ester. The method comprises the following specific steps: in a Schlenk reaction tube, adding a catalyst and phenethyl alcohol, and heating and reacting for 4 hours under the condition of air atmosphere by taking Tetrahydrofuran (THF) as a solvent; then adding into the reaction system t BuOK、B 2 pin 2 The prepared borate is reacted for 10 hours at the same temperature as the first step, the product is purified by a chromatographic column, the yield is 85%, the structure is measured by nuclear magnetism, and the product is determined to be the borate. The nuclear magnetic data of the obtained product are as follows:
4,5,5-tetramethyl-2-phenethyl-1,3,2-dioxaborolane(2a)
1 H NMR(400MHz,CDCl 3 )δ(ppm)7.26–7.18(m,4H),7.18–7.11(m,1H),2.78–2.70(m,2H),1.21(s,12H),1.17–1.11(m,2H).
13 C NMR(101MHz,CDCl 3 )δ(ppm)144.4,128.2,128.0,125.5,83.1,29.9,24.8.
example 3
By exploring the above reaction optimum conditions through experiments, the substrate range of the prepared catalyst catalytic method was evaluated, and as shown in fig. 1, various alcohols having an electron donating group or an electron withdrawing group on a benzene ring can be converted into corresponding products in moderate to good yields under the current heterogeneous boronation system. The nuclear magnetic data of the obtained product are as follows:
4,4,5,5-tetramethyl-2-(2-methylphenethyl)-1,3,2-dioxaborolane(2b)
1 H NMR(400MHz,CDCl 3 )δ(ppm)7.21(s,1H),7.12(m,3H),2.77–2.70(m,2H),2.33(s,3H),1.25(s,12H),1.15–1.09(m,2H).
13 C NMR(101MHz,CDCl 3 )δ(ppm)142.6,135.9,130.1,128.1,126.0,125.7,83.2,27.3,24.9,19.4.
4,4,5,5-tetramethyl-2-(4-methylphenethyl)-1,3,2-dioxaborolane(2c)
1 H NMR(400MHz,CDCl 3 )δ(ppm)δ7.11(q,J＝8.0Hz,4H),2.71(t,J＝8.0Hz,2H),2.32(s,3H),1.25(s,12H),1.15(t,J＝8.0Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)141.3,134.8,128.8,127.8,83.0,29.5,24.8,20.9.
2-(3-methoxyphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2d)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.20–7.15(m,1H),6.84–6.77(m,2H),6.73–6.68(m,1H),3.79(s,3H),2.74(t,J＝8.0 Hz,2H),1.23(s,12H),1.14(t,J＝8.0 Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)159.6,146.2,129.2,120.5,113.7,111.1,83.2,55.1,30.1,24.9.
2-(4-isopropylphenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2e)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.18–7.10(m,4H),2.92–2.83(m,1H),2.68(t,J＝8.1 Hz,2H),1.27–1.21(m,18H),1.14(t,J＝8.1 Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)146.1,141.9,128.0,126.3,83.2,33.8,29.6,24.9,24.2.
2-(3-fluorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2f)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.24–7.16(m,1H),7.02–6.90(m,2H),6.88–6.81(m,1H),2.74(t,J＝8.0 Hz,2H),1.22(s,12H),1.13(t,J＝8.0 Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)163.0(d,J＝242.4 Hz),147.2(d,J＝7.1 Hz),129.7(d,J＝8.3 Hz),123.8(d,J＝2.7 Hz),114.9(d,J＝20.8 Hz),112.5(d,J＝21.1Hz),83.3,29.9(d,J＝1.0 Hz),24.9.
2-(4-chlorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2g)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.25–7.18(m,2H),7.18–7.09(m,2H),2.71(t,J＝8.1 Hz,2H),1.21(s,12H),1.11(t,J＝8.1 Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)142.8,131.1,129.3,128.2,83.1,29.3,24.8.2-(3-chlorophenethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2h)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.26–7.05(m,4H),2.72(t,J＝8.0 Hz,2H),1.22(s,12H),1.12(t,J＝8.0 Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)146.5,134.0,129.5,128.4,126.3,125.8,83.3,29.8,24.9.
4,4,5,5-tetramethyl-2-(2-(naphthalen-2-yl)ethyl)-1,3,2-dioxaborolane(2i)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.88–7.78(m,3H),7.72(s,1H),7.53–7.40(m,3H),3.00(t,J＝8.1 Hz,2H),1.36–1.25(m,14H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)142.0,133.7,132.0,127.8,127.6,127.5,127.3,125.76,125.75,125.0,83.2,30.2,24.9.
2-(2-(benzo[d][1,3]dioxol-5-yl)ethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(2j) 1 H NMR(400 MHz,CDCl 3 )δ(ppm)6.76–6.61(m,3H),5.94–5.85(m,2H),2.70–2.60(m,2H),1.22(s,12H),1.14–1.04(m,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)147.3,145.3,138.4,120.5,108.6,107.9,100.6,83.1,29.7,24.8.
methyl 4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl)benzoate(2k)
1 H NMR(400 MHz,CDCl 3 )δ(ppm)7.92(d,J＝8.3 Hz,2H),7.27(d,J＝8.6 Hz,2H),3.88(s,3H),2.78(t,J＝8.0 Hz,2H),1.20(s,12H),1.14(t,J＝8.1 Hz,2H).
13 C NMR(101 MHz,CDCl 3 )δ(ppm)167.4,150.1,129.7,128.2,127.7,83.4,52.1,30.2,24.9.
the results of catalyzing various alcohol compounds using the acid-metal bi-functional catalyst are shown in table 1 below:
TABLE 1
Figure BDA0004153327710000081
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A metal supported molecular sieve catalyst characterized by: the expression is M@zeolite-T, M/L@zeolite-T or M-R/L@zeolite-T, wherein: m is metal Cu, au, ru, mn or Fe; r is metal Pt, pd, ru, ni, fe or Au; l is N ', N', N ', N' -tetramethyl ethylenediamine, bipyridine, triphenylphosphine, phenanthroline, tributyl phosphate or tributyl phosphite; zeolite represents molecular sieve, and is HY type molecular sieve, Y type molecular sieve, ZSM-5 type molecular sieve, SAPO type molecular sieve, beta type molecular sieve 40 A molecular sieve of the type or MOR; t is the temperature, and the value is 200 ℃, 300 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃.
2. The metal supported molecular sieve catalyst of claim 1, wherein: for M@zeolite-T, the mass contents of the components are as follows: m: 0.5-4% and the balance molecular sieve; for M/L@zeolite-T, the mass contents of the components are as follows: m:0.5 to 4 percent, L: 2-16%, the rest is molecular sieve; for M-R/L@zeolite-T, the mass contents of the components are as follows: m:0.5 to 4 percent, R:0.5 to 4 percent, L: 2-16% and the balance molecular sieve.
3. A method for preparing the metal supported molecular sieve catalyst of claim 1 or 2, characterized in that: is any one of methods one to three:
the method I comprises the following steps:
step A1, loading metal elements on a molecular sieve by using an impregnation technology, and drying to obtain an M@zeolite-T precursor;
step B1, taking part of catalyst precursor and roasting to obtain a catalyst M@zeolite-T;
step C1, treating the rest M@zeolite-T precursor in a reducing atmosphere to obtain a reduced catalyst M@zeolite-T;
the second method comprises the following steps:
step A2, loading metal salt and ligand on a molecular sieve together by using an impregnation technology, and drying to obtain an M/L@zeolite-T precursor;
step B2, taking part of catalyst precursor and roasting to obtain a catalyst M/L@zeolite-T;
step C2, treating the rest M/L@zeolite-T precursor in a reducing atmosphere to obtain a reduced catalyst M/L@zeolite-T;
the third method comprises the following steps:
step A3, loading two different metal elements and ligands on a molecular sieve together by utilizing a hydrothermal technology, and drying to obtain an M-R/L@zeolite-T precursor;
step B3, taking part of catalyst precursor and roasting to obtain a catalyst M-R/L@zeolite-T;
and C3, treating the rest M-R/L@zeolite-T precursor in a reducing atmosphere to obtain a reduced catalyst M-R/L@zeolite-T.
4. A method for preparing a metal supported molecular sieve catalyst according to claim 3, wherein: in the steps A1, A2 and A3, the roasting conditions are as follows: roasting in air for 3-8 hours at 200-800 ℃; in the steps B1, B2 and B3, the roasting conditions are as follows: roasting at 200-800 deg.c in reducing atmosphere for 3-8 hr.
5. A method for preparing a metal supported molecular sieve catalyst according to claim 3, wherein: in the steps B1, B2 and B3, the reducing gas is hydrogen and argon in a volume ratio of 5%:95% of mixed gas and the space velocity of the reducing gas is 100-10000 ml/g catalyst/h.
6. Use of the metal-supported molecular sieve catalyst of claim 1 or 2 for catalyzing the boration of alcohol compounds.
7. The use according to claim 6, characterized in that: the alcohol compound is 1-phenethyl alcohol substituted by an electron donating group or an electron withdrawing group, and the electron donating group or the electron withdrawing group is one of methyl, isopropyl, methoxy and halogen.
8. The use according to claim 6, characterized in that: the boration reaction is to make alcohol compound and dipyrniol diboron (B) 2 pin 2 ) Mixing, and reacting in tetrahydrofuran or 1, 4-dioxane reagent under the catalysis of the metal supported molecular sieve catalyst.
9. Use according to any one of claims 6 to 8, characterized in that: the reaction temperature of the boration reaction is 50-130 ℃.
10. The use according to claim 8, characterized in that: the molar ratio of the alcohol compound to the dipyruvate diboron to the metal-supported molecular sieve catalyst is 10-20:10-20:1.
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