CN105669779B - A kind of synthetic method improving the metal organic frame Pd contents based on Zr (IV) ion - Google Patents
A kind of synthetic method improving the metal organic frame Pd contents based on Zr (IV) ion Download PDFInfo
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Abstract
The invention discloses a kind of synthetic methods improving the metal organic frame Pd contents based on Zr (IV) ion, first by organic ligand (I) and ZrCl4Carry out coordination poly-merization, synthetic modification after then passing through product；The rear synthetic modification specific steps are as follows：Coordination poly-merization product, 2 pyridine carboxaldehydes or salicylide, catalyst formic acid press molar ratio 1:1‑4：It is reacted in 0.1 0.3 organic solvents；It after product centrifuge washing, is scattered in organic solvent, by molar ratio 1:0.8 1.2 are added palladium nitrates, are centrifuged after reaction, dry powder；Obtained powder is dispersed in water, by molar ratio 1:0.5 1.5 are added sodium borohydride, are centrifuged after reaction, wash drying, obtain product.The compound that the present invention synthesizes belongs to organo-mineral complexing supramolecular materials, and with easy to operate, at low cost and granular size in the metal organic frame of nanoscale, catalysis material and benzaldehyde catalysis material as benzyl alcohol oxidation have very high efficiency.
Description
Technical field
The present invention relates to the metal organic frames based on Zr (IV) ion (to be labeled as：Pd@UiO-68-IP) synthesis side
A kind of method, and in particular to synthetic method improving the metal organic frame Pd contents based on Zr (IV) ion.
Background technology
Benzaldehyde is one of simplest aromatic aldehyde, is widely existed in plant especially rosaceous plant, mainly with glycosides
Form be present in stem skin, leaf or the seed of plant.Benzaldehyde is to allow the food used as defined in national standard GB2076-2011
With synthetic perfume, it can be used for preparing cherry, cocoa, vanilla, almond flavour.Industrially also have been widely used, as one kind
Important industrial chemicals is used to prepare lauryl aldehyde, lauric acid, phenylacetaldehyde and Ergol etc.；As measurement ozone, phenol, life
Alkaloids and the methylene reagents by carboxyl；Can be used as special head perfume (or spice) fragrance, it is micro to be used for fragrance of a flower formula, as lilac,
In white orchid, jasmine, violet, Acacia, sunflower, sweet tea Tofu pudding, plum blossom, flores aurantii etc..It also can be used in perfumed soap；Benzaldehyde is weeding
The intermediate of agent difenzoquat, plant growth regulator inabenfide；The intermediate of medicine, dyestuff, fragrance.For producing methoxybenzene
Formaldehyde, light green, benzylideneacetone etc., for reconciling fragrance for detergents, food flavor etc..
The preparation method of benzaldehyde mainly has：1, chlorination toluene is hydrolyzing, and using toluene as raw material, carries out chlorine under light illumination
Change, mixing benzyl chloride is obtained, in the method being hydrolyzed.2, the method for benzyl alcohol oxidation.3, toluene direct oxidation method.4, it is original with benzene
Material is pressurizeing under alchlor effect, and benzene is obtained with monochlor(in)ate carbon and hcl reaction.Industrially mainly pass through the first at present
Benzaldehyde is prepared with fourth method.
Benzyl alcohol is simplest one of fragrant and mellow, and majority is present in the form of ester in essential oil in nature, such as
All contain time ingredient in jasmin oil, hyacinth oil and peru balsam.It is provided in national standard GB2760-1996 temporarily to allow
The fragrance used, but also have stringent regulation to its dosage, benzyl alcohol limits the use of preservative, research on maximum utilized quantity in components of cosmetics
It is 1%.Industrially benzyl alcohol, which also belongs to, fires dangerous material, toxic, has irritation.Benzyl alcohol has human body larger danger
Evil has anesthetic effect, has stimulation, intake that can cause to have a headache eye, the upper respiratory tract, skin, Nausea and vomiting, gastrointestinal tract
Stimulation is fainted from fear, stupor.Benzyl alcohol is subjected to catalysis oxidation, prepares no matter benzaldehyde has in industry or in environmental protection
Important foreground and meaning.The metal organic frame Pd contents that existing method is prepared are low, aoxidized in catalytic phenylmethanol
When at benzaldehyde, catalytic efficiency and low yield, and the temperature needed in catalytic process is relatively high, needs in an atmospheric pressure
Oxygen Condition under the shortcomings of can just carrying out.
Invention content
The purpose of the present invention is exactly to solve the above-mentioned problems, it is organic to provide a kind of metal of the raising based on Zr (IV) ion
The synthetic method of frame Pd contents, organic frame catalyst prepared by this method have when catalysis oxidation benzyl alcohol is benzaldehyde
It is easy to operate, under the conditions of low-temperature environment-friendly and the condensation reaction of benzaldehyde can be catalyzed.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of synthetic method improving the metal organic frame Pd contents based on Zr (IV) ion, first by organic ligand
(I) and ZrCl4Carry out coordination poly-merization, synthetic modification after then passing through product；The specific step of the rear synthetic modification
It is rapid as follows：
(1) organic ligand (I) and ZrCl4Carry out coordination poly-merization product, 2- pyridine carboxaldehydes or salicylide, catalyst first
Acid presses molar ratio 1:1-4：0.1-0.3 is placed in container, is reacted in organic solvent；
(2) it after the product centrifuge washing after reacting step (1), is scattered in organic solvent, by molar ratio 1:
Palladium nitrate is added in 0.8-1.2：Product after step (1) reaction：Palladium nitrate is 1:0.8-1.2), it is centrifuged after reaction, it is dry
Obtain powder；
(3) powder that the step (2) obtains is dispersed in water, by molar ratio 1:Sodium borohydride is added in 0.5-1.5
(refer to：Powder：Sodium borohydride is 1:0.5-1.5), it is centrifuged after reaction, washs drying, obtain product；The organic ligand (I) is：
Reaction condition is specially in the step (1)：For temperature at 60-80 DEG C, the time is 6-12 hours.
Reaction condition is specially in the step (2)：60-80 DEG C is stirred 0.5-1.5 hours.
Reaction condition is specially in the step (3)：It is stirred at room temperature 5-15 minutes.
Organic solvent in the step (1), (2) is ethyl alcohol, acetonitrile or tetrahydrofuran.
The organic ligand (I) and ZrCl4Coordination poly-merization is carried out, specific step is：
(1)ZrCl4, organic ligand (I) is by rate of charge (molar ratio) 1:1 is placed in DMF, and glacial acetic acid is added, and ultrasound has waited for
Machine ligand (I) be completely dissolved solution it is uniform after, which is placed in rise in baking oven at 120 DEG C in advance and place for 24 hours, is cooled to room
Temperature, centrifugation, obtains buff powder；
(2) it by dispersion DMF after buff powder washing made from step (1), is soaked for a period of time, centrifuges in 80 DEG C；
(3) product after centrifuging step (2) is soaked in ethanol solution again, and 70 DEG C are placed a period of time, finally at 80 DEG C
At a temperature of it is dry, obtain UiO-68-NH2Buff powder.
The preparation method of the organic ligand (I) is as follows：
(1) it is obtained by the coupling reaction and 4- methoxycarbonyl phenyl acid reactions of palladium chtalyst for raw material with 2,5- dibromo anilines
Intermediate A, (step is specially：2,5- dibromo anilines, 4- methoxycarbonyl group phenyl boric acids, cesium fluoride, (PPh3)4Pd is by feeding intake mole
Than 1:3:4.75:0.33 is placed in single port bottle, and anhydrous tetrahydro furan is added, stirs 48h under 80 DEG C of constant temperatures, is cooled to room
Temperature, is removed under reduced pressure solvent, and column chromatography for separation obtains the greenish yellow solid powder of intermediate A.)
Intermediate A structure is as follows：
(2) intermediate A is hydrolyzed under alkaline condition organic ligand (I) (step is specially：In being put into single port bottle
3% KOH aqueous solutions are added after solid is completely dissolved in intermediate (I), THF and MeOH, and constant temperature stirs 12h at 40 DEG C,
After being cooled to room temperature, THF and MeOH is removed under reduced pressure, distilled water is added, pH is adjusted to dilute hydrochloric acid<2.Greenish yellow solid is precipitated, and filters,
Be washed with water three times, room temperature dry compound (I) greenish yellow solid powder).
The metal organic frame based on Zr (IV) ion that above-mentioned synthetic method obtains, it is described based on Zr (IV) ion
Metal organic frame in the application that catalysis oxidation benzyl alcohol is benzaldehyde or is catalyzed in benzaldehyde reaction, it is specific to apply
Method is as follows：Based on the metal organic frame of Zr (IV) ion, benzyl alcohol presses rate of charge (molar ratio) 1:100 are added to first
In benzene, dimethylbenzene or acetonitrile solution, constant temperature is stirred to react under the conditions of 80 DEG C, by gas chromatograph tracking reaction process, 30
Hour catalysis oxidation yield can reach 99% or more；Or：Based on the metal organic frame of Zr (IV) ion, benzaldehyde, malononitrile
By rate of charge (molar ratio) 1:100：120 are added in methanol solution, are stirred to react at ambient temperature, pass through gas chromatograph
Tracking reaction process, catalysis oxidation yield can reach 99% or more within 7 hours.
The invention has the advantages that compound belongs to Organic-inorganic composite supramolecular materials, and with operation letter
Single, at low cost and granular size nanoscale metal organic frame, as benzyl alcohol oxidation catalysis material and
Benzaldehyde catalysis material has very high efficiency.
The synthetic method of the present invention is mainly that the chelating moieties generated by subsequent reactions are coordinated with metal Pd, is avoided existing
There is the influence of uncertain factor when introducing Pd in technology organic framework materials, obtained Pd stable contents and content is high, catalysis
The reproducibility of agent is preferable.
The subsequent reactions for the metal organic frame that the present invention was designed according to the characteristics of ligand, if change organic ligand, after
The change of reactant and ratio in modification all cannot get the Pd@UiO-68-IP of Pd stable contents.
Description of the drawings
The surface sweeping electromicroscopic photograph figure of the metal organic frame (Pd@UiO-68-IP) of Zr (IV) ion in Fig. 1 embodiments 1；
The transmission electron microscope photo figure of the metal organic frame (Pd@UiO-68-IP) of Zr (IV) ion in Fig. 2 embodiments 1；
The X-Ray powder diagrams of the metal organic frame (Pd@UiO-68-IP) of Zr (IV) ion in Fig. 3 embodiments 1；
The standard chromatogram of benzyl alcohol in Fig. 4 embodiments 2；
The standard chromatogram of benzaldehyde in Fig. 5 embodiments 2；
The chromatogram of Pd@UiO-68-IP catalysis oxidation benzyl alcohols in Fig. 6 embodiments 2；
The standard chromatogram of 2-benzylidenemalononitrile in Fig. 7 embodiments 3；
Pd@UiO-68-IP are catalyzed the chromatogram of benzaldehyde and malononitrile condensation reaction in Fig. 8 embodiments 3.
Specific implementation mode
Embodiment 1：The preparation of the metal organic frame (Pd@UiO-68-IP) of Zr (IV) ion
Under nitrogen protection, 2,5- dibromo anilines (10nmol, 2.51g), 4- methoxycarbonyl groups phenyl boric acid (30nmol, 5.4g),
Cesium fluoride (47.5nnmol, 7.22g), (PPh3)4150mL anhydrous four is added in 250mL there-necked flasks in Pd (3.3mmol, 3.8g)
Hydrogen furans stirs 48h under 80 DEG C of constant temperatures, is cooled to room temperature, and is removed under reduced pressure solvent, column chromatography for separation (silica gel,
CH2Cl2) intermediate A 2.3 grams of greenish yellow solid powder, yield：64%.
In being put into intermediate A (1.66mmol, 0.60g), THF (20mL) and MeOH (20mL) in 100mL single port bottles, wait for solid
After body is completely dissolved, the aqueous solution of 10mL KOH (3.0g, 53.6mmol) is added, constant temperature stirs 12h at 40 DEG C, is cooled to room temperature
Afterwards, THF and MeOH is removed under reduced pressure, 100mL distilled water is added, pH is adjusted to dilute hydrochloric acid<2.Greenish yellow solid is precipitated, and filters, and uses
Water washing three times, room temperature dry compound I 0.45 gram of greenish yellow solid powder, yield:81.45%.
ZrCl4(0.080mmol, 19.20mg), compound I (0.080mmol, 26.64mg) are placed in 3.2mL DMF, add
Enter 240 μ L glacial acetic acid, after solid is completely dissolved, which is placed in rises in the baking oven at a temperature of 120 DEG C ultrasonic 20min in advance
It places for 24 hours, is cooled to room temperature, centrifuge.Buff powder is washed with DMF and is redispersed in three times in fresh DMF, in 80 DEG C of leachings
Steep 6h, centrifugation.Buff powder is soaked in ethanol solution again, and 60 DEG C are placed 2 days, wherein it is molten to replace an ethyl alcohol within every 12 hours
Liquid, it is finally dry at a temperature of 80 DEG C, obtain UiO-68-NH2Buff powder.
UiO-68-NH2(0.67mmol, 0.30g), 2- pyridine carboxaldehydes (2.7mmol, 0.29g) press rate of charge molar ratio (1:
4) it is placed in single port bottle, the drop formic acid of ethyl alcohol 60mL and 3 is added, 70 DEG C are stirred 10 hours.Centrifugation, is washed with ethyl alcohol and is dried three times
Afterwards, it is scattered in 60mL acetonitrile solutions, palladium nitrate (0.70mmol, 0.16g) is added and presses rate of charge (molar ratio) 1:1.70 DEG C are stirred
After mixing 1 hour, centrifugation, dry yellow powder after washing 3 times with acetonitrile.Yellow powder (0.50mmol, 0.30g), hydroboration
Sodium (0.50mmol, 0.0019g) presses rate of charge (molar ratio) 1:1 is placed in 40mL water, is stirred at room temperature after ten minutes, centrifuges, uses
Deionized water is dry after washing 3 times, obtains black powder Pd@UiO-68-IP.
The metal organic frame (Pd@UiO-68-IP) of Zr obtained (IV) ion is used into Gemini Zeiss SupraTM
Sem test, testing result are as shown in Figure 1.
The metal organic frame (Pd@UiO-68-IP) of Zr obtained (IV) ion is surveyed using JEM-2100 transmission electron microscopes
Examination, testing result are as shown in Figure 2.
The metal organic frame (Pd@UiO-68-IP) of Zr obtained (IV) ion is used into Brooker D8ADVANCE X-
Raypowder diffractometer with CuKa radiation diffractometers are tested, and testing result is as shown in Figure 3.
Embodiment 2：The metal organic frame (Pd@UiO-68-IP) of Zr (IV) ion is used as benzyl alcohol oxidation catalysis material
Application
Pd@UiO-68-IP (10mg, 1mol%), benzyl alcohol (1.0mmol) press rate of charge (molar ratio) 1:100 are added to
In 2mL toluene solutions, constant temperature stirs 30h under the conditions of 80 DEG C, passes through gas chromatograph tracking reaction process, 20 hours catalysis oxygen
Change yield and can reach 99% or more.
Metal organic frame (Pd@UiO-68-IP) catalytic phenylmethanol of Zr (IV) ion is aoxidized, is chased after with gas chromatogram
Track reaction result, testing result are as shown in Figure 6.
Embodiment 3：The metal organic frame (Pd@UiO-68-IP) of Zr (IV) ion is used as benzaldehyde catalysis material
Application
Pd@UiO-68-IP (10mg, 1mol%), benzaldehyde (1.0mmol), malononitrile (1.0mmol) (rub by rate of charge
That ratio) 1:100：120 are added in methanol solution, stir at ambient temperature, by gas chromatograph tracking reaction process, 7
Hour catalysis oxidation yield can reach 99% or more.
By metal organic frame (Pd@UiO-68-IP) the catalysis benzaldehyde reaction of Zr (IV) ion, gas-chromatography is used
Figure following response is as a result, testing result is as shown in Figure 8.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (9)
1. a kind of synthetic method improving the metal organic frame Pd contents based on Zr (IV) ion, it is characterized in that：To have first
Machine ligand (I) and ZrCl4Carry out coordination poly-merization, synthetic modification after then passing through product；The rear synthetic modification tool
The step of body, is as follows：
(1) organic ligand (I) and ZrCl4Coordination poly-merization product is carried out, 2- pyridine carboxaldehydes or salicylide, catalyst formic acid are pressed
Molar ratio 1:1-4：0.1-0.3 is placed in container, is reacted in organic solvent；
(2) it after the product centrifuge washing after reacting step (1), is scattered in organic solvent, by molar ratio 1:0.8-1.2
Palladium nitrate is added, is centrifuged after reaction, dry powder；
(3) powder that the step (2) obtains is dispersed in water, by molar ratio 1:Sodium borohydride, reaction is added in 0.5-1.5
After centrifuge, wash drying, obtain product；The organic ligand (I) is：
The organic ligand (I) and ZrCl4Coordination poly-merization is carried out, specific step is：
(a)ZrCl4, organic ligand (I) in molar ratio 1:1 is placed in DMF, and glacial acetic acid is added, and ultrasound waits for that organic ligand (I) is complete
After solvent soln is uniform, which is placed in rise in the baking oven at 120 DEG C in advance and place for 24 hours, is cooled to room temperature, and centrifuges, obtains shallow
Yellow powder；
(b) it by dispersion DMF after buff powder washing made from step (a), is soaked for a period of time, centrifuges in 80 DEG C；
(c) product after centrifuging step (b) is soaked in ethanol solution again, and 70 DEG C are placed a period of time, finally in 80 DEG C of temperature
Lower drying, obtains UiO-68-NH2Buff powder.
2. synthetic method as described in claim 1, it is characterized in that：Reaction condition is specially in the step (1)：Temperature exists
60-80 DEG C, the time is 6-12 hours.
3. synthetic method as described in claim 1, it is characterized in that：Reaction condition is specially in the step (2)：60-80℃
Stirring 0.5-1.5 hours.
4. synthetic method as described in claim 1, it is characterized in that：Reaction condition is specially in the step (3)：It is stirred at room temperature
5-15 minutes.
5. synthetic method as described in claim 1, it is characterized in that：Organic solvent in the step (1), (2) is ethyl alcohol, second
Nitrile or tetrahydrofuran.
6. synthetic method as described in claim 1, it is characterized in that：The preparation method of the organic ligand (I) is as follows：
(1) it is obtained by the coupling reaction and 4- methoxycarbonyl phenyl acid reactions of palladium chtalyst intermediate for raw material with 2,5- dibromo anilines
Body A, intermediate A structure are as follows：
(2) intermediate A is hydrolyzed to obtain organic ligand (I) under alkaline condition.
7. the metal organic frame based on Zr (IV) ion that claim 1-6 any one of them synthetic methods obtain.
8. as claimed in claim 7 based on Zr (IV) ion metal organic frame catalysis oxidation benzyl alcohol be benzaldehyde or
The application being catalyzed in benzaldehyde reaction.
9. application as claimed in claim 8, it is characterized in that：Specifically application process is as follows：Claim 1-7 is any described
The obtained metal organic frame based on Zr (IV) ion of synthetic method, benzyl alcohol presses molar ratio 1:100 are added to first
In benzene, dimethylbenzene or acetonitrile solution, constant temperature is stirred to react under the conditions of 80 DEG C；
Or：The metal organic frame based on Zr (IV) ion that any synthetic methods of claim 1-7 obtain, benzene first
Aldehyde, malononitrile press molar ratio 1:100：120 are added in methanol solution, are stirred to react at ambient temperature.
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| CN108640906B (en) * | 2018-04-03 | 2020-05-29 | 山东师范大学 | Bifunctional composite catalyst and preparation method and application thereof |
| CN109928966B (en) * | 2019-02-15 | 2021-04-02 | 山东师范大学 | Metal organic framework material based on phenothiazine and preparation method and application thereof |
| CN111701619B (en) * | 2020-03-16 | 2023-08-25 | 南昌大学 | Immobilized catalyst for synthesizing KH-560 silane coupling agent and preparation method thereof |
| CN111518143A (en) * | 2020-05-22 | 2020-08-11 | 江南大学 | Simple and rapid preparation of syringyl metal organic framework material and application thereof |
| CN114105901B (en) * | 2020-08-27 | 2022-12-02 | 江西省科学院应用化学研究所 | Metal organic framework based on Cd (II), composite catalyst, preparation method and application thereof |
| CN112337509B (en) * | 2020-11-05 | 2023-05-26 | 北京化工大学 | MOF-based transition metal single-atom catalyst for selective hydrogenation of carbon-carbon triple bond and preparation method thereof |
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