CN102658128B - Method for preparing ordered mesoporous Pd-TiO2 heterogeneous catalyst and application thereof - Google Patents

Method for preparing ordered mesoporous Pd-TiO2 heterogeneous catalyst and application thereof Download PDF

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CN102658128B
CN102658128B CN201110423676.8A CN201110423676A CN102658128B CN 102658128 B CN102658128 B CN 102658128B CN 201110423676 A CN201110423676 A CN 201110423676A CN 102658128 B CN102658128 B CN 102658128B
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heterogeneous catalysis
order mesoporous
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CN102658128A (en
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朱凤霞
周建峰
朱惠琴
李和兴
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Huaiyin Normal University
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Abstract

The invention discloses a method for preparing an ordered mesoporous Pd TiO2 heterogeneous catalyst and an application thereof. The method comprises the steps of: dissolving P123 in absolute ethyl alcohol, adding butyl titanate, titanium tetrachloride, and alcohol solution of PdCl2 and mixing to obtain solution A; processing the solution A by solvent evaporation-induced self-assembly to obtain solid powder A; putting the solid powder A into a muffle furnace and calcining to obtain solid powder B; and putting the solid powder B into a tube furnace and reducing it for 3-5 hours in N2 atmosphere containing 10% H2 and at a temperature of 260-300 DEG C to obtain the ordered mesoporous Pd-TiO2 heterogeneous catalyst. The heterogeneous catalyst provided by the invention has an ordered two-dimensional hexagonal mesoporous structure, a larger specific surface area, high catalytic activity, fast reaction rate, and low production cost. Moreover, the heterogeneous catalyst is recyclable and has little pollution to environment.

Description

Prepare order mesoporous Pd-TiO 2the method of heterogeneous catalysis and application thereof
Technical field
The present invention relates to the preparation method of catalyst, be specifically related to a kind of order mesoporous Pd-TiO for preparing 2the method of heterogeneous catalysis and application thereof.
Background technology
In recent years, carry out with water to replace organic solvent the important branch that organic synthesis becomes Green Chemistry.Suzuki and Sonogashira reaction are the organic reactions of the important formation C-C key of a class.Tradition is mainly to take precious metals pd as main for the catalyst of Suzuki reaction, and reaction medium is organic solvent.In order to overcome the solubility limits of reaction substrate in aqueous medium, develop in recent years the organic Pd catalyst of multiple solid-carrying type heterogeneous catalysis and be applied to Suzuki and Sonogashira reaction in aqueous medium, but complex steps in immobilized Pd process, and need organic ligand and a large amount of organic matters, environment is produced and pollutes, and prospects for commercial application is also very limited.So the preparation method of efficient, the economic catalyst of Development of Novel, the catalytic performance of raising catalyst, have very important theory significance and industrial value.
Transition metal-catalyzed cross-coupling reaction is the effective ways that are widely used in organic synthesis, and especially the Suzuki under palladium catalysis and Sonogashira cross-coupling reaction are one of effective ways of constructing on the Ary1-Aryl key.Such reaction is having a wide range of applications aspect agricultural chemicals, medicine, polymer, dyestuff and household chemicals.Tradition Suzuki reaction is all carried out in organic media, obviously with water to replace organic solvent, as reaction medium, is conducive to environmental contamination reduction.But, due to solubility limits, Suzuki reaction at present adopts homogeneous phase Pd (II) organo-metallic catalyst mostly.Its shortcoming is to reuse and exist heavy metal pollution.The approach solved is that homogeneous catalyst is immobilized, but, because the catalytic active site decentralization descends, catalytic activity is lower.
In recent years, utilize the carrier of ordered mesoporous material as solid-carried catalyst, realize that the clean organic synthesis in aqueous medium has caused extensive concern.Order mesoporous TiO wherein 2improve the decentralization of active sites because it has the characteristics of regular pore passage structure, be subject to vastization scholar's attention.Metallic catalyst is immobilized to order mesoporous TiO 2duct in, Suzuki reaction in the catalysis aqueous medium, utilize the regular pore structure of material self and with the advantages such as strong interaction of metal, can realize that being uniformly distributed of active site, substrate fully contact with activated centre, can realize recycling of catalyst again, finally realize the target of green catalysis.
Summary of the invention
The object of the invention is to: a kind of order mesoporous Pd-TiO for preparing is provided 2the method of heterogeneous catalysis, the Pd-TiO made by the method 2heterogeneous catalysis has the hexagonal mesoporous structure of orderly two dimension, and the catalytic activity had in aqueous medium Suzuki and Sonogashira reaction is apparently higher than Pd/P25.
For achieving the above object, preparation method of the present invention comprises the following steps:
The first step: at first 20～30 oc is dissolved in 1.7～2.2 g P123 in the absolute ethyl alcohol of 38～42 mL, then add the tetrabutyl titanate of 5.0～7.0 mL and stir 25～35 min, add again 1.8～2.2 mL titanium tetrachlorides to stir 10～20 min, finally add the 0.025 g/ mL PdCl of 3.6～4.4 mL 2alcoholic solution, 20～30 oc strong agitation 3～5h, obtain solution A;
Second step: by the solution A of step 1 gained process evaporation induced self-assembly process, respectively 20～30 oc, 35～45 oc, 95～105 oc keeps 24 h, obtains pressed powder A;
The 3rd step: step 2 gained pressed powder A is placed in to Muffle furnace, first from 20～30 oc is with 1 othe programming rate of C/min is warming up to 100 oc, then with 0.5 othe programming rate of C/min is warming up to 200 oc, finally with 0.2 othe programming rate of C/min is warming up to 350 oc, and 350 oc roasting 220～260 min, obtain pressed powder B;
The 4th step: the pressed powder B of step 3 gained is placed in to tube furnace, is containing 10% H 2n 2in air-flow in 260～300 oc reduces 3～5 h, obtains order mesoporous Pd-TiO 2heterogeneous catalysis.
The present invention has the following advantages: 1, technique is simple, and the heterogeneous catalysis of preparation has efficient catalytic activity, effectively improves reaction speed, reduce production costs, and recyclable, reduce environmental pollution; 2, in the Suzuki and Sonogashira reaction of aqueous medium, Pd-TiO 2catalyst has higher catalytic activity, and can reuse, and its superior catalytic activity is mainly owing to following factors: Pd-TiO 2catalyst has the regular orderly hexagonal mesoporous structure of two dimension and larger specific area, and these characteristics are conducive to the dispersed of active site; This catalyst has higher mechanical strength, and catalytic active center Pd and TiO 2adhesion is strong, so Pd-TiO after applying mechanically 4～5 times 2still there is comparatively orderly meso-hole structure, thereby also guaranteed catalytic activity preferably.
The accompanying drawing explanation
Fig. 1 is order mesoporous Pd-TiO 2the little angle XRD figure of catalyst.
Fig. 2 is N 2the adsorption-desorption isollaothermic chart.
Fig. 3 is Pd-TiO 2the TEM picture.
Fig. 4 catalyst is applied mechanically number of times and conversion ratio graph of a relation.
The specific embodiment
Further illustrate technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is the restriction to technical scheme.
Embodiment 1: according to following steps, prepare order mesoporous Pd-TiO 2catalyst
The first step: at first 20 oc is dissolved in 1.7 g P123 in the absolute ethyl alcohol of 38 mL, then adds the tetrabutyl titanate of 5.0 mL and stirs 25 min, then adding 1.8 mL titanium tetrachlorides to stir 10 min, finally adds the 0.025 g/mL PdCl of 3.6 mL 2alcoholic solution, 20 oc strong agitation 3h, obtain solution A;
Second step: by the solution A of step 1 gained process evaporation induced self-assembly process, respectively 20 oc, 35 oc, 95 oc keeps 24 h, obtains pressed powder A;
The 3rd step: step 2 gained pressed powder A is placed in to Muffle furnace, first from 20 oc is with 1 othe programming rate of C/min is warming up to 100 oc, then with 0.5 othe programming rate of C/min is warming up to 200 oc, finally with 0.2 othe programming rate of C/min is warming up to 350 oc, and 350 oc roasting 220 min, obtain pressed powder B;
The 4th step: the pressed powder B of step 3 gained is placed in to tube furnace, is containing 10% H 2n 2in air-flow in 260 oc reduces 5 h, obtains order mesoporous Pd-TiO 2heterogeneous catalysis.
The order mesoporous Pd-TiO obtained 2the little angle XRD of catalyst schemes as shown in Figure 1, N 2as shown in Figure 2, TEM schemes as shown in Figure 3 the adsorption-desorption isollaothermic chart.
Measure by the BET method the order mesoporous Pd-TiO that above-described embodiment 1 obtains 2the specific area of catalyst is 137 m 2/ g, aperture 7.2 nm, pore volume is 0.27 cm 3/ g, as shown in table 1.
Little angle XRD figure and N as depicted in figs. 1 and 2 2the adsorption-desorption isollaothermic chart can be found out, prepared order mesoporous Pd-TiO 2catalyst has the hexagonal mesoporous structure of orderly two dimension, and pore-size distribution is homogeneous comparatively, and has larger specific area.
Embodiment 2: according to following steps, prepare order mesoporous Pd-TiO 2catalyst
The first step: at first 25 oc is dissolved in 1.95 g P123 in the absolute ethyl alcohol of 40 mL, then adds the tetrabutyl titanate of 6.0 mL and stirs 30 min, then adding 2.0 mL titanium tetrachlorides to stir 15min, finally adds the 0.025 g/mL PdCl of 4.0 mL 2alcoholic solution, 25 oc strong agitation 4h, obtain solution A;
Second step: by the solution A of step 1 gained process evaporation induced self-assembly process, respectively 25 oc, 40 oc, 100 oc keeps 24 h, obtains pressed powder A;
The 3rd step: step 2 gained pressed powder A is placed in to Muffle furnace, first from 25 oc is with 1 othe programming rate of C/min is warming up to 100 oc, then with 0.5 othe programming rate of C/min is warming up to 200 oc, finally with 0.2 othe programming rate of C/min is warming up to 350 oc, and 350 oc roasting 240 min, obtain pressed powder B;
The 4th step: the pressed powder B of step 3 gained is placed in to tube furnace, is containing 10% H 2n 2in air-flow in 280 oc reduces 4 h, obtains order mesoporous Pd-TiO 2heterogeneous catalysis.
Embodiment 3: according to following steps, prepare order mesoporous Pd-TiO 2catalyst
The first step: at first 30 oc is dissolved in 2.2 g P123 in the absolute ethyl alcohol of 42 mL, then adds the tetrabutyl titanate of 7.0 mL and stirs 35 min, then adding 2.2 mL titanium tetrachlorides to stir 20 min, finally adds the 0.025 g/mL PdCl of 4.4 mL 2alcoholic solution, 30 oc strong agitation 5h, obtain solution A;
Second step: by the solution A of step 1 gained process evaporation induced self-assembly process, respectively 30 oc, 45 oc, 105 oc keeps 24 h, obtains pressed powder A;
The 3rd step: step 2 gained pressed powder A is placed in to Muffle furnace, first from 30 oc is with 1 othe programming rate of C/min is warming up to 100 oc, then with 0.5 othe programming rate of C/min is warming up to 200 oc, finally with 0.2 othe programming rate of C/min is warming up to 350 oc, and 350 oc roasting 260 min, obtain pressed powder B;
The 4th step: the pressed powder B of step 3 gained is placed in to tube furnace, is containing 10% H 2n 2in air-flow in 300 oc reduces 3 h, obtains order mesoporous Pd-TiO 2heterogeneous catalysis.
Below, select two carbon carbon coupling reaction test Pd-TiO 2the catalytic performance of heterogeneous catalysis:
application examples 1:by the resulting order mesoporous Pd-TiO of embodiment 1 2catalyst is for aqueous medium Suzuki reaction, and detailed process is as follows: in the 10 ml round-bottomed flasks with reflux condensing tube, add the Pd-TiO that 4.0 mL deionized waters, Pd content are 0.0072 mmol 2heterogeneous catalysis, 0.058 ml iodobenzene, 0.73 g phenyl boric acid, positive nonane (internal standard compound), 80 oc reacts 6 h, and products therefrom is with after 10 ml ethyl acetate extractions, by gas-chromatography, carrying out product analysis;
Reaction equation as shown in the formula:
Figure DEST_PATH_RE-DEST_PATH_IMAGE002
application examples 2: by the resulting order mesoporous Pd-TiO of embodiment 3 2catalyst is for aqueous medium Sonagashira reaction, and detailed process is as follows: in the 10 mL round-bottomed flasks with reflux condensing tube, add the Pd-TiO that 4.0 mL deionized waters, Pd content are 0.0012 mmol 2heterogeneous catalysis, positive nonane (internal standard compound), 0.058 mL iodobenzene, 0.73 g phenyl boric acid, 80 oc reacts 6 h, and products therefrom is with after 10 mL ethyl acetate extractions, by gas-chromatography, carrying out product analysis;
Reaction equation as shown in the formula:
。
Determine Pd-TiO by the BET method 2with Pd/ TiO 2the structural parameters of heterogeneous catalysis are listed in table 1:
Table 1. Pd-TiO 2the BET parameter
From XRD figure (as Fig. 1) and N 2adsorption-desorption thermoisopleth (as Fig. 3) can find out, prepared carrier and heterogeneous catalysis all have the regular orderly hexagonal mesoporous structure of two dimension, pore-size distribution comparatively homogeneous and larger specific area.
By Pd-TiO 2heterogeneous catalysis is applied to the clean organic reaction in aqueous medium, chooses in aqueous medium Suzuki and Sonogashira reaction as probe, and active result is as table 2:
Table 2. Pd-TiO 2catalytic activity table in Pd/P25, aqueous medium Suzuki and Sonogashira being reacted
Figure DEST_PATH_1
Can find out, under identical reaction condition, Pd-TiO 2the catalytic activity of heterogeneous catalysis is apparently higher than Pd/P25.
By deionized water washing 3 times for remaining heterogeneous catalysis after every secondary response, then through 70-90 oapplied mechanically experiment after the C vacuum drying, its catalytic activity is shown in Fig. 4.
As can be seen from Figure 4, after repeating to apply mechanically 5 times, Pd-TiO 2heterogeneous catalysis still has catalytic activity preferably, and selectively almost remaining unchanged of target product, be 86% after the conversion ratio of reactant is applied mechanically 5 times.

Claims (3)

1. prepare order mesoporous Pd-TiO 2the method of heterogeneous catalysis is characterized in that this preparation method comprises the following steps:
The first step: at first 20～30 oc is dissolved in 1.7～2.2 g P123 in the absolute ethyl alcohol of 38～42 mL, then add the tetrabutyl titanate of 5.0～7.0 mL and stir 25～35 min, add again 1.8～2.2 mL titanium tetrachlorides to stir 10～20 min, finally add the 0.025 g/ mL PdCl of 3.6～4.4 mL 2alcoholic solution, 20～30 oc strong agitation 3～5h, obtain solution;
Second step: by the solution of step 1 gained process evaporation induced self-assembly process, respectively 20～30 oc, 35～45 oc, 95～105 oc keeps 24 h, obtains pressed powder A;
The 3rd step: step 2 gained pressed powder A is placed in to Muffle furnace, first from 20～30 oc is with 1 othe programming rate of C/min is warming up to 100 oc, then with 0.5 othe programming rate of C/min is warming up to 200 oc, finally with 0.2 othe programming rate of C/min is warming up to 350 oc, and 350 oc roasting 220～260 min, obtain pressed powder B;
The 4th step: the pressed powder B of step 3 gained is placed in to tube furnace, is containing 10% H 2n 2in air-flow in 260～300 oc reduces 3～5 h, obtains order mesoporous Pd-TiO 2heterogeneous catalysis.
2. order mesoporous Pd-TiO 2the application process of heterogeneous catalysis, order mesoporous Pd-TiO 2heterogeneous catalysis is made by the described method of claim 1, it is characterized in that: this application process is by order mesoporous Pd-TiO 2heterogeneous catalysis is for aqueous medium Suzuki reaction, and detailed process is as follows: in the 10 mL round-bottomed flasks with reflux condensing tube, add the Pd-TiO that 4.0 mL deionized waters, Pd content are 0.0072 mmol 2heterogeneous catalysis, 0.058 mL iodobenzene, 0.73 g phenyl boric acid, positive nonane internal standard compound, 80 oc reacts 6 h, and products therefrom is with after 10 mL ethyl acetate extractions, by gas-chromatography, carrying out product analysis;
Reaction equation as shown in the formula:
Figure 2011104236768100001DEST_PATH_IMAGE001
。
3. order mesoporous Pd-TiO 2the application process of heterogeneous catalysis, order mesoporous Pd-TiO 2heterogeneous catalysis is made by the described method of claim 1, it is characterized in that: this application process is by order mesoporous Pd-TiO 2catalyst is for aqueous medium Sonagashira reaction, and detailed process is as follows: in the 10 mL round-bottomed flasks with reflux condensing tube, add the Pd-TiO that 4.0 mL deionized waters, Pd content are 0.0012 mmol 2heterogeneous catalysis, positive nonane internal standard compound, 0.058 mL iodobenzene, 0.73 g phenylacetylene, 80 oc reacts 6 h, and products therefrom is with after 10 mL ethyl acetate extractions, by gas-chromatography, carrying out product analysis;
Reaction equation as shown in the formula:
Figure 2011104236768100001DEST_PATH_IMAGE002
。
CN201110423676.8A 2011-12-17 2011-12-17 Method for preparing ordered mesoporous Pd-TiO2 heterogeneous catalyst and application thereof Expired - Fee Related CN102658128B (en)

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