CN101791575A - Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals - Google Patents
Preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals Download PDFInfo
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Abstract
The invention relates to a preparation method of a heterogeneous catalyst of organic coordination compounds of mesoporous structure metals, belonging to a preparation method of heterogeneous catalysts. Theterogeneous catalyst prepared by the prior art has the defects that the utilization ratio of surface active composition is limited, the direction of catalytic reaction can not be controlled easily, and the activity and the selectivity can not reach the optimal effect. In the invention, the preparation method of the heterogeneous catalyst of organic coordination compounds of mesoporous structure metals comprises the following steps of: mixing zirconium tetrachloride, 1,4-terephthalic acid and N,N-dimethylformamide solvent under the condition of microwaves, and stirring the mixture at room temperature until the solution is clear; adding the solution into a microwave reactor for microwave heating, removing the supernatant solution, and washing the residual solid matters with the N,N-dimethylformamide solvent; and drying the washed matters in a vacuum mode to obtain the heterogeneous catalyst. The invention has the advantages of simple process and easy operation; the prepared heterogeneous catalyst has efficient catalytic activity; and the catalyst can be recycled, thereby reducing the production cost and decreasing the environment pollution.
Description
Technical field
The present invention relates to a kind of preparation method of heterogeneous catalyst, specifically a kind of preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals.
Technical background
Catalyst is a kind of important material during chemical industry is produced, and it plays a decisive role to the benefit of Chemical Manufacture.According to the existence form of catalyst in chemical reaction, can be divided into heterogeneous catalyst and homogeneous catalyst.Most of industrial catalysts are heterogeneous catalysts in the prior art.The advantage of heterogeneous catalyst is that the activity of such catalysts component can extensively change; The temperature range of using is wide; Catalyst separates from product easily; Realize industrialization easily.But its shortcoming is: 1, catalyst design or improvement difficulty.2, owing to the inhomogeneity on surface, the utilization rate of surface active composition is limited.3, the direction of catalytic reaction is not easy control, and active and selectivity all can not reach optimum efficiency.Corresponding with it, because the dentate in the homogeneous catalyst can suitably be selected, make the activated centre atom specific electronics and spatial property be arranged on every side, make it can have the selectivity of height at promoting a certain reaction.Activated centre atoms all in homogeneous catalyst evenly disperse, and can bring into play maximum catalytic activity.Make homogeneous catalyst have the activated centre utilization rate more much higher than heterogeneous catalyst.Homogeneous catalyst is compared with heterogeneous catalyst, reacts under the more gentle condition of low temperature, low pressure, has reduced energy loss.Though homogeneous catalyst has above-mentioned advantage, because catalyst can't reclaim, cause economic benefit low, it is extensive use of is difficult to realize.In addition because itself unstability, corrosivity, pollution target product, the difficult separation, bringing many shortcomings such as difficulty to next step reaction also is conspicuous.Thereby study the immobilized of homogeneous catalyst, all be significant in theory with in the practice.The most of homogeneous catalyst of prior art immobilized all be by part as a bridge, active sites and carrier are coupled together, reach immobilized purpose.This method can be brought some problems such as catalyst instability usually; Active sites is skewness on carrier; Sterically hindered increase, part is to change of catalytic active center microenvironment etc.In order better to address these problems, invent a kind of microwave technology of utilizing and prepare the highly active advantage of existing homogeneous catalyst, the recyclable advantage of utilizing again of heterogeneous catalyst is arranged again, and the metal heterogeneous catalyst of organic coordination compounds with meso-hole structure is very necessary.
The present invention is in catalyst technical field, and preparation first has the metal organic coordination compounds catalyst with meso-hole structure of the advantage of homogeneous catalyst high activity and heterogeneous catalyst simultaneously, has tangible novelty and creativeness; In chemical industry production, has simultaneously practicality widely.
Summary of the invention
The object of the present invention is to provide a kind of microwave technology of utilizing to prepare the highly active advantage of existing homogeneous catalyst, the recyclable advantage of utilizing again of heterogeneous catalyst is arranged again, have the preparation method of the metal heterogeneous catalyst of organic coordination compounds of meso-hole structure.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals the steps include:
(1) under microwave condition, with zirconium chloride, 1,4-terephthalic acid (TPA), N, the dinethylformamide solvent, zirconium chloride wherein, terephthalic acid (TPA), N, the mol ratio of dinethylformamide is 1.2: 1: 1749; Be stirred to the solution clarification under the room temperature;
(2) clear solutions is joined in the microwave reactor, supernatant liquor is removed in 400W heating using microwave 2-4 minute, remaining solid matter N, and dinethylformamide washs 3 times;
(3), make metal organic coordination compounds heterogeneous catalysis with the material vacuum drying treatment after the above-mentioned washing.
Microwave condition is that power is 400-1000W, time 1-10 minute in the step (1).
Earlier zirconium chloride and terephthalic acid (TPA) are dissolved in N respectively in the step (1), in the dinethylformamide, after two solution mixed continue to stir 0.5h.
Step (1) is 25 ℃, mixes solvent 0.5h.
Step (2) contains zirconium chloride, 1 with 20mL, 4-terephthalic acid (TPA), N, and the clarification mixed solution of dinethylformamide is slowly poured in the microwave reactor, microwave power 400W, 4 minutes time, the product N that obtains, dinethylformamide washing, centrifugal discards supernatant liquor, repeats 3 times.
The vacuum drying temperature is 160 ℃ described in the step (3), time 24h.
Main points of the present invention are: utilize the microwave technology preparation to have the metal heterogeneous catalyst of organic coordination compounds of meso-hole structure.
(1) under microwave condition, earlier with zirconium chloride and 1, the 4-terephthalic acid (TPA) is dissolved in N respectively, among the dinethylformamide DMF, two solution is mixed the lasting 0.5h of stirring again, and is even to solution;
(2) will mix the back clear solutions and join in the microwave reactor, under microwave condition, react, and wait reaction to remove supernatant liquor after finishing, remaining solid matter N, dinethylformamide repeatedly washs;
(3) will wash resulting solid is vacuum drying 24h under 160 ℃ the condition in temperature, makes the metal heterogeneous catalyst of organic coordination compounds with meso-hole structure.
The microwave reactor model of using among the present invention is MDS-6.
The concrete operations of the inventive method are:
Under 25 ℃ condition, respectively with zirconium chloride and 1, the 4-terephthalic acid (TPA) is dissolved among the DMF, two solution is mixed to be incorporated in again to continue to stir this mixture 0.5h under this temperature, clarifies to mixed solution; Be placed in the microwave reactor microwave 4mins under 400W then; The reactor taking-up is naturally cooled to room temperature, again that reacted solution is centrifugal; Discard the upper strata stillness of night, relaunder more than 3 times, at last the solid of washes clean is placed 160 ℃ of vacuum drying 24h, make metal heterogeneous catalyst of organic coordination compounds with meso-hole structure with DMF.
The present invention utilizes microwave technology one step to synthesize a kind of metal heterogeneous catalyst of organic coordination compounds Zr-MOF with mesoporous characteristic, and this catalyst can be applicable to the generation of flavone compound under the condition of no solvent, has embodied good catalytic activity, this be because:
(1) metal zirconium ion and carboxylic acid part carry out condensation reaction and form the networked compound with meso-hole structure under microwave condition, and the zirconium ion catalytic active site evenly disperses, and has improved catalytic efficiency;
(2) owing to be reaction under the condition of no solvent, and this catalyst has porous again, makes organic reactant react under high concentration, thereby improved catalytic efficiency.
Compared with prior art, beneficial effect of the present invention is:
1, the inventive method, technology is simple, processing ease, preparation speed is fast.
2, Zhi Bei heterogeneous catalyst has the catalytic activity of high-efficient and lasting, can effectively improve chemical reaction velocity, improves product quality.
3, Zhi Bei heterogeneous catalyst is recyclable, reduces production costs, and reduces environmental pollution.
Description of drawings
Fig. 1 is the wide-angle XRD spectra of product of the present invention;
Fig. 2 is the SEM photo of product of the present invention;
Fig. 3 is the N of product of the present invention
2The adsorption desorption thermoisopleth.
The specific embodiment
The present invention will be further described below in conjunction with the specific embodiment.
Embodiment 1:
The preparation method of mesoporous metal heterogeneous catalyst of organic coordination compounds:
With 0.33g ZrCl
4Be dissolved among the 6ml DMF; With 0.20g H
2BDC is dissolved among the 6ml DMF; Two solution are mixed, stir 0.5h down at 25 ℃.Subsequently this mixed solution is transferred in the MDS-6 polytetrafluoroethylene (PTFE) microwave reactor, reacts 4mins under the 400W condition.Reactor taken out naturally cool to room temperature, more after filtration, the DMF washing; Put into the dry 24h of 160 ℃ of vacuum drying ovens; Obtain white solid catalyst Zr-MOF.
The Zr-MOF catalyst structure parameter that is determined by the BET method is listed in the table below:
| ??S BET(m 2/g) | ??V p(cm 3/g) | ??D p(nm) |
| ??510 | ??0.39 | ??3.1 |
The reaction of formation process that this catalyst Zr-MOF is applied to flavone compound under the condition of no solvent is as follows:
In the 10ml round-bottomed flask, add trisphenol between 1.0mmo l, the 1.2mmol ethyl acetoacetate, 0.05g catalyst Zr-MOF, 25 ℃ are reacted 10mins down, and products therefrom carries out product analysis by GC-MAS, result such as following table after dividing 3 extractions with 10ml ethyl acetate:
| ??Catalyst | ??Zr?content(wt％) | ??Conv(％) | ??Sel(％) | ?Yield(％) |
| ??Zr-MOF | ??0.18 | ??93 | ??94 | ?87 |
After reaction is finished, heterogeneous catalyst is filtered to isolate, and wash 3 times with ethyl acetate and deionized water respectively, 80 ℃ of following vacuum drying, after 80 ℃ of vacuum drying, apply mechanically experiment again, the result shows that the Zr-MOF heterogeneous catalyst repeats to apply mechanically still has good catalytic activity after 8 times, and efficiency of pcr product remains on more than 80%.
Embodiment 2:
With 0.66g ZrCl
4Be dissolved among the 12ml DMF; With 0.40g H
2BDC is dissolved among the 12ml DMF; Two solution are mixed.25 ℃ are stirred 0.5h down, then this mixed solution are transferred in the polytetrafluoroethylene (PTFE) MDS-6 microwave reactor, react 4mins under the 400W condition.Reactor taken out naturally cool to room temperature, more after filtration, the DMF washing, obtain white solid catalyst Zr-MOF after putting into the dry 24h of 160 ℃ of vacuum drying ovens.The Zr-MOF catalyst structure parameter that is determined by the BET method is listed in the table below:
| ??S BET(m 2/g) | ??V p(cm 3/g) | ??D p(nm) |
| ??510 | ??0.39 | ??3.1 |
Listed specific embodiments of the present invention above, under the situation that does not deviate from the spirit and scope of the present invention, those skilled in the art can modify and revise it, but these modifications and modification all should drop in protection scope of the present invention.
Claims (6)
1. the preparation method of a heterogeneous catalyst of organic coordination compounds of mesoporous structure metals the steps include:
(1) under microwave condition, with zirconium chloride, 1,4-terephthalic acid (TPA), N, the dinethylformamide solvent, zirconium chloride wherein, terephthalic acid (TPA), N, the mol ratio of dinethylformamide is 1.2: 1: 1749; Be stirred to the solution clarification under the room temperature;
(2) clear solutions is joined in the microwave reactor, supernatant liquor is removed in 400W heating using microwave 4-10 minute, remaining solid matter N, dinethylformamide washing 3 times;
(3), make metal organic coordination compounds heterogeneous catalysis with the material vacuum drying treatment after the above-mentioned washing.
2. heterogeneous catalyst of organic coordination compounds of mesoporous structure metals preparation method according to claim 1 is characterized in that: microwave condition is that power is 400-1000W, time 1-10 minute in the step (1).
3. heterogeneous catalyst of organic coordination compounds of mesoporous structure metals preparation method according to claim 1, it is characterized in that: earlier zirconium chloride and terephthalic acid (TPA) are dissolved in N respectively in the step (1), in the dinethylformamide, after two solution mixed continue to stir 0.5h.
4. the preparation method of heterogeneous catalyst of organic coordination compounds of mesoporous structure metals according to claim 1, it is characterized in that: step (1) is 25 ℃, mixes solvent 0.5h.
5. heterogeneous catalyst of organic coordination compounds of mesoporous structure metals preparation method according to claim 1, it is characterized in that: step (2) contains zirconium chloride, 1 with 20mL, 4-terephthalic acid (TPA), N, the clarification mixed solution of dinethylformamide is slowly poured in the microwave reactor, microwave power 400W, 4 minutes time, the product N that obtains, dinethylformamide washing, centrifugal discards supernatant liquor, repeats 3 times.
6. heterogeneous catalyst of organic coordination compounds of mesoporous structure metals preparation method according to claim 1 is characterized in that: the vacuum drying temperature is 160 ℃ described in the step (3), time 24h.
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Cited By (9)
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| CN104525266A (en) * | 2014-12-30 | 2015-04-22 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
| CN104744501A (en) * | 2015-02-06 | 2015-07-01 | 桂林电子科技大学 | Method for preparing metal-organic framework material Uio-66 with microwave solvothermal method and hydrogen storage property of Uio-6 |
| CN105688997A (en) * | 2016-03-04 | 2016-06-22 | 河北工程大学 | High-selectivity catalyst and preparation method thereof |
| CN105907033A (en) * | 2016-06-22 | 2016-08-31 | 金华知产婺源信息技术有限公司 | Preparation method of flame-retardant artificial stone containing nano perovskite oxide |
| CN105949581A (en) * | 2016-06-23 | 2016-09-21 | 温州泓呈祥科技有限公司 | Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 |
| CN106861758A (en) * | 2017-01-25 | 2017-06-20 | 天津大学 | A kind of preparation method of the MOF catalyst for PHOTOCATALYTIC AIR-PURIFYING |
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| CN104525266B (en) * | 2014-12-30 | 2017-04-12 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
| CN104525266A (en) * | 2014-12-30 | 2015-04-22 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
| CN104744501A (en) * | 2015-02-06 | 2015-07-01 | 桂林电子科技大学 | Method for preparing metal-organic framework material Uio-66 with microwave solvothermal method and hydrogen storage property of Uio-6 |
| CN105688997A (en) * | 2016-03-04 | 2016-06-22 | 河北工程大学 | High-selectivity catalyst and preparation method thereof |
| CN105907033B (en) * | 2016-06-22 | 2018-07-17 | 广西利升石业有限公司 | A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide |
| CN105907033A (en) * | 2016-06-22 | 2016-08-31 | 金华知产婺源信息技术有限公司 | Preparation method of flame-retardant artificial stone containing nano perovskite oxide |
| CN108455902A (en) * | 2016-06-22 | 2018-08-28 | 金华知产婺源信息技术有限公司 | A kind of preparation method of the fire retardant man-made stone comprising nano-perovskite oxide |
| CN108455902B (en) * | 2016-06-22 | 2021-01-01 | 余笑眉 | Preparation method of flame-retardant artificial stone containing nano perovskite oxide |
| CN105949581A (en) * | 2016-06-23 | 2016-09-21 | 温州泓呈祥科技有限公司 | Preparation method and application of flame-retardant cable insulating material comprising nano perovskite oxide LaxSr[1-x]CoO3 |
| CN106861758A (en) * | 2017-01-25 | 2017-06-20 | 天津大学 | A kind of preparation method of the MOF catalyst for PHOTOCATALYTIC AIR-PURIFYING |
| CN106861758B (en) * | 2017-01-25 | 2019-05-31 | 天津大学 | A kind of preparation method of the MOF catalyst for PHOTOCATALYTIC AIR-PURIFYING |
| CN107511134A (en) * | 2017-06-29 | 2017-12-26 | 湖南大学 | A kind of mesoporous Zr polymerization of olefin using catalyst polymer and its preparation and application |
| CN107790184A (en) * | 2017-09-05 | 2018-03-13 | 中山大学 | A kind of catalyst of Pd/UiO 66 of Pd metal nanocrystal kernels with controllable appearance and preparation method thereof |
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