CN103008012A - Metal organic skeleton structure material load platinum catalyst, as well as preparation method and application thereof - Google Patents
Metal organic skeleton structure material load platinum catalyst, as well as preparation method and application thereof Download PDFInfo
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- CN103008012A CN103008012A CN201210535655XA CN201210535655A CN103008012A CN 103008012 A CN103008012 A CN 103008012A CN 201210535655X A CN201210535655X A CN 201210535655XA CN 201210535655 A CN201210535655 A CN 201210535655A CN 103008012 A CN103008012 A CN 103008012A
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Abstract
The invention discloses a metal organic skeleton structure material load platinum catalyst. The metal organic skeleton structure material load platinum catalyst comprises a carrier and an active component loaded on the carrier, wherein the carrier is a metal organic skeleton structure material MIL-101, and the active component is platinum. The invention also discloses a preparation method of the metal organic skeleton structure material load platinum catalyst and a catalytic hydrogenation application thereof. The catalyst provided by the invention has a higher specific surface area and a larger porthole structure, the catalyst is suitable for application in a catalytic hydrogenation reaction, the catalyst is environmentally-friendly, the reaction conditions are gentle, and the catalyst is high in efficiency and good in stability.
Description
Technical field
The present invention relates to the catalyst with metal nanoparticles technical field, relate in particular to a kind of metallic organic framework structural material load platinum catalyst, preparation method and the application in heterogeneous catalyzed hydration thereof.
Background technology
The asymmetric hydrogenation of the chiral carbonyl compounds of diving can generate the alcohols chipal compounds, and functionalized alcohol compound is the important source material of the fine chemicals such as synthetic medicine, agricultural chemicals, spices.Two kinds of enantiomters (R) in the chiral drug molecule-similar with the physicochemical properties of (S)-isomers, but the pharmaceutically active in human body, metabolic process and toxicity exist obvious difference, in addition opposite.The research of therefore synthetic single chiral compound becomes the focus in chemical research field.
Three kinds of methods commonly used obtain the mapping pure compound of single configuration: (1) resolution of racemate; (2) natural chiral chemical modification; (3) asymmetric syntheses.Wherein, method of asymmetric synthesis can directly synthesize required any chiral product from suitable initiation material in principle.Asymmetric catalytic hydrogenation is synthesizing chiral compound one of the most effective approach up to now.The platinum catalyst that the cinchona alkaloid chirality is modified shows excellent catalytic performance in the asymmetric hydrogenation of alpha-keto ester, be a milestone (the Accounts of Chemical Research 37 (2004) 909 in Heterogeneous asymmetric catalysis field; Current Organic Chemistry 10 (2006) 1553; Chemical Reviews 107 (2007) 4863).Over nearly 20 years, be used for the carrier of loaded platinum catalyst of the functionalized latent chiral carbonyl compounds of alpha-position (take the model compound ethyl pyruvate as representative) asymmetric hydrogenation from traditional Al
2O
3, SiO
2, TiO
2Deng inorganic carrier, (Ultrasonics Sonochemistry 7 (2000) 151 to have expanded to the organic high molecular polymer materials such as MCM-41, HNaY, FDU-14; Applied Catalysis A 191 (2000) 193; CatalysisLetters 129 (2009) 194; Journal of Catalysis 239 (2006) 154; Catalysis Today 60 (2000) 167; Catalysis Letters 122 (2008) 325).Although report in the document, the platinum catalyst of carbon nanotube loaded platinum catalyst and the load of meso-porous alumina composite is to asymmetric hydrogenation performance (the Angewandte Chemie International Edition 50 (2011) 4913 of ethyl pyruvate or 2-oxygen-4-phenylbutyrate ethyl ester; ChemCatChem 2 (2010) 1303; Chinese Journal of Catalysis 32 (2011) 1677) is better than the Pt/Al of commercialization 5%
2O
3Catalyst, however because catalyst preparation process is more loaded down with trivial details, cause it to be widely used.
In addition, carbonyls reduction obtain corresponding alcohol be chemical industry and medicine synthetic in important intermediate.The amine that nitroreduction obtains is the important intermediate of dyestuff, spices, also is simultaneously the important source material of agricultural chemicals, medicine.These products all have actual practical value, and scientists is being sought more effective catalytic reaction approach always and improved the conversion ratio of above-mentioned reaction and selective, and also green production process is developed in expectation simultaneously.
2005, the people such as F é rey synthesize have mesoporous micropore composite pore structural, the metal-organic framework materials MIL-101 (Science 309 (2005) 2040) of high thermal stability and hydrothermal stability and stronger resistance to acids and bases relatively.These features are so that MIL-101 can be used as the carrier of desirable loaded catalyst.MIL-101 is directly used in catalysis or is used for the existing relevant report of catalytic reaction as carrier-supported precious metal, the silicon cyanation that directly is used for aldehyde such as MIL-101 as catalyst, load P d nanometer is used for the hydrogenation reaction to hydrogenation and the ketone carbonyl of unsaturated compounds carbon-carbon double bond, and load Au nano particle is used for Alcohol oxidation, and (Chemical Communications (2008) 4192; Chemistry A European Journal 17 (2011) 8071; Journal of Physical Chemistry C 114 (2010) 13362).But take MIL-101 as carrier loaded Pt catalyst and use it for the alpha-keto ester asymmetric catalytic hydrogenation and the catalytic hydrogenation of benzaldehyde, nitro benzene and its derivative not yet has report.Among the present invention, metal platinum nano-particle loads on the asymmetric hydrogenation that the Pt/MIL-101 catalyst for preparing on this carrier is used for alpha-keto ester, has obtained preferably activity and optical selective.In addition, the hydrogenation of all right catalysis benzaldehyde of Pt/MIL-101 catalyst and nitro benzene and its derivative has also obtained preferably catalytic performance.
Summary of the invention
The object of the invention is to the application of expanded metal organic framework material MIL-101 in heterogeneous catalysis.This carrier has very high specific area and composite pore structural, and has stronger resistance to acids and bases, hydrothermal stability and heat endurance.
Catalyst provided by the present invention is take metal-organic framework materials MIL-101 as carrier, adopts immersion reduction method carried metal Pt nano particle to be prepared from, and wherein the mass percent of Pt metal is 0.5-10wt.%.The selected catalyst carrier MOF of the present invention has possessed three large essential conditions of good catalyst: one, this MOF material has very high specific area and larger pore passage structure, be conducive to reactive metal Uniform Dispersion on carrier, be conducive to simultaneously absorption and the mass transfer of reaction molecular; Its two, this metal-organic framework materials MIL-101 itself has a large amount of unsatuated metal Cr positions, removing terminal water of coordination molecule can provide Lewis acid position; Its three, this metal-organic framework materials MIL-101 has preferably heat endurance and hydrothermal stability, and stronger resistance to acids and bases, can stable existence in water and majority of organic solvent.
The object of the invention is achieved through the following technical solutions:
The invention provides a kind of metallic organic framework structural material load platinum catalyst, it comprises carrier and is carried on active constituent on the carrier; Wherein, described carrier is metallic organic framework structural material MIL-101, and described active constituent is platinum.
Wherein, the loading of described platinum is 0.5-10.0wt.%, and described platinum is 24.2-78.6% at the decentralization of described carrier surface, and the average grain diameter of described platinum is 1.4-4.6nm.
The present invention also provides the preparation method of above-mentioned metallic organic framework structural material load platinum catalyst, take six hydration chloroplatinic acids as the active constituent precursor, described metallic organic framework structural material MIL-101 is carrier, at room temperature stir dipping, solvent evaporated, reduction obtains described metallic organic framework structural material load platinum catalyst under 60-100 ℃ of temperature conditions again.Comprise the steps: particularly
(1) preparation of metallic organic framework structural material: with Cr (NO
3)
39H
2O, HF, terephthalic acid (TPA) and deionized water are take mol ratio as 1: 1: 1: 265 ratio kept 7-10 hour in 453K-503K constant temperature in hydrothermal reaction kettle; Filter after naturally cooling to room temperature, obtain solid; Then this solid is removed terephthalic acid (TPA) through organic solvent washing, wash with small molecular alcohol again.Dry in the freeze-day with constant temperature baking oven at last, can obtain metallic organic framework structural material MIL-101;
(2) preparation of catalyst: take six hydration chloroplatinic acids as the Pt source, being dissolved in certain solvent (water, ethanol etc.) is the active constituent precursor, adding described metallic organic framework structural material is carrier, the loading of control platinum is 0.5-10wt.%, solvent evaporated after 15-35 ℃ of lower dipping stirs, then dry in baking oven; Use again reducing agent (sodium borohydride aqueous solution, hydrazine hydrate, formaldehyde, aqueous sodium formate solution) reduction.Dry in baking oven at last, can obtain metallic organic framework structural material load platinum catalyst.
The present invention also provides the application of described metallic organic framework structural material load platinum catalyst, uses it for the asymmetric catalytic hydrogenation reaction to the chiral carbonyl compounds of diving, and described latent chiral carbonyl compounds comprises ethyl pyruvate and 2-oxygen-4-phenylbutyrate ethyl ester.Wherein, preliminary treatment in the hydrogen atmosphere of described metal-organic framework materials load platinum catalyst under the 503K temperature.
Described catalytic hydrogenation is to carry out in pressure is the pure hydrogen of 4.0 MPas, and reaction dissolvent is water, acetic acid, ethanol or their mixed solvent, and reaction temperature is room temperature.
Catalyst provided by the present invention can be used for the diving water hydrogenation catalyst reaction of asymmetric hydrogenation and general unsaturated compound of chipal compounds is included in the application in (asymmetric) catalytic hydrogenation of (chirality of diving) unsaturated carbonyl or nitro compound.
Catalyst provided by the present invention is as follows to the asymmetric hydrogenation condition of alpha-keto ester: the 503K preliminary treatment 2 hours under hydrogen atmosphere of a certain amount of catalyst, then be transferred in the reactor with an amount of solvent after under hydrogen atmosphere, being cooled to room temperature, mix with substrate and chiral modifier at a certain temperature, be filled with the pure hydrogen of certain pressure, react under the electromagnetic agitation.Preferred reaction conditions is: catalyst amount is 50mg, the 1.0mL substrate, and the 10mg cinchonidine, the 20mL solvent, 4 MPa Hydrogen Vapor Pressures, room temperature reaction is 30 minutes under the electromagnetic agitation.
Catalyst provided by the present invention is as follows to benzaldehyde and derivatives catalysis hydrogenation condition thereof: the 503K preliminary treatment 2 hours under hydrogen atmosphere of a certain amount of catalyst, then be transferred in the reactor with an amount of solvent after under hydrogen atmosphere, being cooled to room temperature, mix with substrate at a certain temperature, be filled with the pure hydrogen of certain pressure, react under the electromagnetic agitation.Preferred reaction conditions is: catalyst amount is 50mg, the derivative of 21mmol benzaldehyde or benzaldehyde, and 20mL water, 4 MPa Hydrogen Vapor Pressures, room temperature reaction is 1 hour under the electromagnetic agitation.
The catalytic hydrogenation condition of catalyst p-nitrophenyl provided by the present invention and derivative thereof is as follows: the 503K preliminary treatment 2 hours under hydrogen atmosphere of a certain amount of catalyst, then be transferred in the reactor with an amount of solvent after under hydrogen atmosphere, being cooled to room temperature, mix with substrate at a certain temperature, be filled with the pure hydrogen of certain pressure, react under the electromagnetic agitation.Preferred reaction conditions is: catalyst amount is 50mg, the derivative of 21mmol nitrobenzene or nitrobenzene, and 20mL water, 4 MPa Hydrogen Vapor Pressures, room temperature reaction is 30 minutes under the electromagnetic agitation.
Among the present invention, take metal-organic framework materials MIL-101 as carrier, with H
2PtCl
6Ethanolic solution be presoma, reduce Kaolinite Preparation of Catalyst by dipping and sodium formate solution.The catalyst of the method preparation has kept the characteristics of carrier high-specific surface area and high stability, and Pt particle high degree of dispersion.Catalyst system and catalyzing of the present invention has the advantages such as gentle, the efficient and good stability of environmental friendliness, reaction condition.This catalyst has very high specific area and larger pore passage structure, is conducive to absorption and the mass transfer of reaction molecular; This catalyst has preferably heat endurance and good chemical stability, all can stable existence in water and majority of organic solvent.The method is used for the catalyst of preparation (asymmetric) catalytic hydrogenation of (chirality of diving) unsaturated carbonyl or nitro compound under the condition of high pressure room temperature, obtained preferably activity and selectivity, and can repeatedly recycle.
Description of drawings
Fig. 1 is the MIL-101 carrier of the embodiment of the invention 1 preparation and the XRD figure of the 5wt.%Pt/MIL-101 catalyst that embodiment 2 prepares.
Fig. 2 is the transmission electron microscope photo of the 5wt.%Pt/MIL-101 catalyst of the embodiment of the invention 2 preparations.
Fig. 3 is the MIL-101 carrier of the embodiment of the invention 1 preparation and the N of the 5wt.%Pt/MIL-101 catalyst that embodiment 2 prepares
2Adsorption/desorption figure and BJH graph of pore diameter distribution.
Fig. 4 be in the embodiment of the invention 5wt.%Pt/MIL-101 catalyst reuse the result.
The specific embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content of mentioning specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Embodiment 1
With Cr (NO
3)
39H
2O, HF, terephthalic acid (TPA) and deionized water are take mol ratio as 1: 1: 1: 265 ratio in hydrothermal reaction kettle in 493K isothermal reaction 8 hours; Filter after naturally cooling to room temperature, obtain the green solid powder; Then filter while hot after this pressed powder being washed respectively each washing with organic solvent and small molecular alcohol, the last MIL-101 powder that drying obtains in the freeze-day with constant temperature baking oven namely is metallic organic framework structural material MIL-101.With 0.5mL H
2PtCl
6Ethanolic solution (1g six hydration chloroplatinic acids are dissolved in ethanol preparation 25mL solution) dropwise adds on the MIL-101 powder of the above-mentioned preparation of 1.500g, adds 10-12mL ethanol again, stirring at room dipping 4-6 hour, and mixing speed is about 600 rev/mins.Solvent evaporated after dipping finishes, dry in 353-393K.Then be to add an amount of sodium formate and deionized water at 1: 10 by platinum and sodium formate mol ratio, 368K backflow reductase 12 hour, wash away chlorion with a large amount of deionized waters after the cooling, dry at 353-393K again, preparing loading is the Pt/MIL-101 catalyst of 0.5wt.%.
Prepare the Pt/MIL-101 catalyst that the Pt load capacity is 5wt.% according to optimum condition in the present embodiment:
The preparation method of metallic organic framework structural material MIL-101 is substantially the same manner as Example 1.With 2.0mL H
2PtCl
6Ethanolic solution (1g six hydration chloroplatinic acids are dissolved in ethanol preparation 25mL chloroplatinic acid ethanolic solution) dropwise joins on the 573.4mg MIL-101 powder, adds 5-8mL ethanol again, stirring at room dipping 4-6 hour, and mixing speed is about 600 rev/mins.Solvent evaporated after dipping finishes, dry in 353-393K.Then be to add an amount of sodium formate and deionized water at 1: 10 by platinum and sodium formate mol ratio, 368K backflow reductase 12 hour, wash away chlorion with a large amount of deionized waters after the cooling, can get the Pt/MIL-101 catalyst that loading is 5wt.% in the 353-393K drying again.
Fig. 1 is the XRD figure of carrier MIL-101 and the 5wt.%Pt/MIL-101 catalyst that embodiment 2 prepares of embodiment 1 preparation.As can be seen from Figure 1, load the structural integrity of carrier after the Pt, and do not observe the crystalline phase peak of Pt metal, illustrate that nano platinum particle is as active component high degree of dispersion on carrier.
Fig. 2 is TEM (transmission electron microscope) photo of the 5wt.%Pt/MIL-101 catalyst of embodiment 2 preparations, can see that platinum particles is dispersed on the carrier MIL-101, and particle size is even, and average particle size is 1.8nm, and decentralization is 61.1%.
Fig. 3 is the carrier MIL-101 of embodiment 1 preparation and the N of the 5wt.%Pt/MIL-101 catalyst that embodiment 2 prepares
2Adsorption/desorption curve map and BJH graph of pore diameter distribution.Fig. 3 can find out, compare with carrier, load the catalyst after the Pt still kept higher BET specific area.
Embodiment 3
The preparation method of metallic organic framework structural material MIL-101 is substantially the same manner as Example 1.With 3.0mL H
2PtCl
6Ethanolic solution (1g six hydration chloroplatinic acids are dissolved in ethanol preparation 25mL chloroplatinic acid ethanolic solution) dropwise joins on the 407mg MIL-101 powder, adds 4-7mL ethanol again, stirring at room dipping 4-6 hour, and mixing speed is about 600 rev/mins.Solvent evaporated after dipping finishes, dry in 353-393K.Then be to add an amount of sodium formate and deionized water at 1: 10 by platinum and sodium formate mol ratio, 368K backflow reductase 12 h washs away chlorion with a large amount of deionized waters after the cooling, can get the Pt/MIL-101 catalyst that loading is 10wt.% in the 353-393K drying again.
Embodiment 4
The Pt/MIL-101 catalyst of embodiment 2 preparations is used under the modification of cinchonidine at the Heterogeneous asymmetric catalysis hydrogenation of different solvents to ethyl pyruvate (ETPY).The below is described in further detail application of the present invention the specific embodiment of the asymmetric catalytic hydrogenation of ethyl pyruvate reaction in the glacial acetic acid solvent with 5.0wt.%Pt/MIL-101 metal-organic framework materials loaded platinum catalyst, and its concrete steps are as follows:
A, took by weighing in the hydrogen atmosphere of 0.05g 5.0wt.%Pt/MIL-101 catalyst under the 493K temperature preliminary treatment 2 hours;
B, above-mentioned pretreated catalyst and 10mg cinchonidine, 20mL glacial acetic acid, 1.0mL ethyl pyruvate are passed into the pure hydrogen that pressure is 4.0 MPas in reactor, at room temperature electromagnetic agitation is carried out asymmetric catalytic hydrogenation reaction 30 minutes;
After finishing, c, hydrogenation with after its product and the catalyst separation, with gas-chromatography its product is analyzed.
The basic operation process is substantially the same manner as Example 4, and the catalyst of the present embodiment is 0.5wt.%Pt/MIL-101.
Embodiment 6
The basic operation process is substantially the same manner as Example 4, and the catalyst of the present embodiment is 10wt.%Pt/MIL-101.
Embodiment 7
The basic operation process is substantially the same manner as Example 4, and the solvent of the present embodiment is 20mL ethanol.
The basic operation process is substantially the same manner as Example 4, and the solvent of the present embodiment is the 20mL deionized water.
The basic operation process is substantially the same manner as Example 4, and the solvent of the present embodiment is 7.5mL glacial acetic acid and 12.5mL alcohol mixed solution, is designated as glacial acetic acid-ethanol-1.
The basic operation process is substantially the same manner as Example 4, and the solvent of the present embodiment is 10mL glacial acetic acid and 10ml deionized water mixed solution, is designated as glacial acetic acid-deionized water-1.
Embodiment 11
The basic operation process is substantially the same manner as Example 4, and the substrate of the present embodiment is 1.0mL 2-oxygen-4-phenylbutyrate ethyl ester (EOPB).
Embodiment 12
The basic operation process is substantially the same manner as Example 11, and the solvent of the present embodiment is 20mL ethanol.
Embodiment 13
The basic operation process is substantially the same manner as Example 11, and the solvent of the present embodiment is 12.5mL glacial acetic acid and 7.5mL alcohol mixed solution, is designated as glacial acetic acid-ethanol-2.
Embodiment 14
The basic operation process is substantially the same manner as Example 11, and the solvent of the present embodiment is 16mL glacial acetic acid and 4mL deionized water mixed solution, is designated as glacial acetic acid-deionized water-2.
Embodiment 15
The basic operation process is substantially the same manner as Example 11, and the solvent of the present embodiment is 20mL toluene.
Above embodiment 4-15 prepared catalyst the results are shown in Table 1 for catalytic reaction.
Show 1:Pt/MIL-101 catalyst asymmetric hydrogenation result to alpha-keto ester in different solvents.
| Embodiment | Substrate | Solvent | Conversion ratio | Optical selective |
| 4 | Ethyl pyruvate | Glacial acetic acid | 86.2 | 74.3 |
| 5 | Ethyl pyruvate | Glacial acetic acid | 75.6 | 71.8 |
| 6 | Ethyl pyruvate | Glacial acetic acid 20ml | 91.3 | 76.5 |
| 7 | Ethyl pyruvate | Ethanol | 93.3 | 53.3 |
| 8 | Ethyl pyruvate | Deionized water | 98.5 | 44.4 |
| 9 | Ethyl pyruvate | Glacial acetic acid-ethanol-1 | 92.3 | 71.3 |
| 10 | Ethyl pyruvate | Glacial acetic acid-deionized water-1 | 98.8 | 68.7 |
| 11 | 2-oxygen-4-phenylbutyrate ethyl ester | Glacial acetic acid | 96.6 | 53.7 |
| 12 | 2-oxygen-4-phenylbutyrate ethyl ester | Ethanol | 54.3 | 20.0 |
| 13 | 2-oxygen-4 phenylbutyrate | Glacial acetic acid-ethanol-2 | 96.8 | 60.7 |
| 14 | 2-oxygen-4-phenylbutyrate ethyl ester | Glacial acetic acid-deionized water-2 | 96.2 | 47.5 |
| 15 | 2-oxygen-4-phenylbutyrate ethyl ester | Toluene | 14.7 | 38.8 |
Embodiment 16
In the present embodiment the test in glacial acetic acid-ethanol-1 5.0wt.%Pt/MIL-101 to the stability experiment of ETPY asymmetric catalytic hydrogenation.Concrete steps are as follows:
A, took by weighing in the hydrogen atmosphere of 0.05g 5.0wt.%Pt/MIL-101 catalyst under the 493K temperature preliminary treatment 2 hours;
B, above-mentioned pretreated catalyst and 10mg cinchonidine, 20ml glacial acetic acid, 10mmol ethyl pyruvate are passed into the pure hydrogen that pressure is 4.0 MPas in reactor, at room temperature electromagnetic agitation is carried out asymmetric catalytic hydrogenation reaction 30 minutes.
After finishing, c, hydrogenation with after its product and the catalyst separation, with gas-chromatography its product is analyzed.
Above step a-c reacted as the first round, reclaimed thereafter the first round and reacted used catalyst, repeatedly washed with absolute ethyl alcohol, then was directly used in the catalytic reaction of next time, repeated above-mentioned steps b and c.The reaction result that catalyst circulation is used is seen Fig. 4.As seen from Figure 4, catalyst of the present invention still keeps stable activity and optical selective in reusing process, uses still to have higher activity and optical selective 5 times.
Embodiment 17
The 5.0wt.%Pt/MIL-101 catalyst of embodiment 2 preparations is used in the catalytic hydrogenation of deionized water to benzaldehyde and derivative (halogenated benzaldehyde and methoxy substitution benzaldehyde) thereof, and concrete reaction result sees Table 2.The below is described in further detail application of the present invention with 5.0wt.%Pt/MIL-101 metal-organic framework materials loaded platinum catalyst embodiment to the catalytic hydrogenation of benzaldehyde in deionized water, and its concrete steps are as follows:
A, took by weighing in the hydrogen atmosphere of 0.05g 5.0wt.%Pt/MIL-101 catalyst under the 493K temperature preliminary treatment 2 hours;
B, with above-mentioned pretreated catalyst and 21mmol benzaldehyde, the 20ml deionized water is mixed, and passes into the pure hydrogen that pressure is 4.0 MPas in reactor, at room temperature electromagnetic agitation was carried out catalytic hydrogenation 1 hour;
After finishing, c, hydrogenation with after its product and the catalyst separation, with gas-chromatography its product is analyzed.
Embodiment 18
The 5.0wt.%Pt/MIL-101 catalyst of embodiment 2 preparation is used for catalytic hydrogenation at deionized water p-nitrophenyl and derivative (comprising nitrotoleune, halogenated nitrobenzene, Nitroanisole) thereof, and concrete reaction result sees Table 3.The below is described in further detail application of the present invention with the embodiment of 5.0wt.%Pt/MIL-101 metal-organic framework materials loaded platinum catalyst catalytic hydrogenation of p-nitrophenyl in deionized water, and its concrete steps are as follows:
A, took by weighing in the hydrogen atmosphere of 0.05g 5.0wt.%Pt/MIL-101 catalyst under the 493K temperature preliminary treatment 2 hours;
B, with above-mentioned pretreated catalyst and 21mmol nitrobenzene, the 20ml deionized water is mixed, and passes into the pure hydrogen that pressure is 4.0 MPas in reactor, at room temperature electromagnetic agitation was carried out catalytic hydrogenation 30 minutes;
After finishing, c, hydrogenation with after its product and the catalyst separation, with gas-chromatography its product is analyzed.
Table 2:Pt/MIL-101 catalyst is to the catalytic hydrogenation of benzaldehyde and derivative thereof.
The catalytic reduction reaction of table 3:Pt/MIL-101 catalyst p-nitrophenyl and derivative thereof
Catalytic hydrogenation result to benzaldehyde and derivative thereof finds out from Pt/MIL-101 catalyst shown in the above table 2, and major part has the reaction conversion ratio of substituent benzaldehyde than the height of benzaldehyde.Fluorobenzene formaldehyde not only have very high conversion ratio also have simultaneously 100% selective.The 2-chlorobenzaldehyde has been obtained the selective of higher activity and 100% in the Chlorobenzaldehyde, and the conversion ratio of 3-chlorobenzaldehyde (74.5%) and selective (77.0%) are relatively low.The catalytic hydrogenation conversion ratio (94.1%) of Benzaldehyde,2-methoxy and selective (97.5%) are higher in the benzaldehyde of methoxy substitution, and the conversion ratio of 4-methoxybenzaldehyde only has 49.9%.
Can find out from the catalytic hydrogenation result of Pt/MIL-101 catalyst p-nitrophenyl shown in the above table 3 and derivative thereof, the conversion ratio of nitrotoleune and selectively relatively high, the conversion ratio of meta-nitrotoluene and para-nitrotoluene is respectively 69.5%, 76.7%, the conversion ratio 62.9% that is higher than nitrobenzene, and ortho-methylnitrobenzene is lower.The conversion ratio of o-chloronitrobenzene, m-chloro-nitrobenzene and paranitroanisole is well below nitrobenzene, and the catalytic hydrogenation reaction activity of parachloronitrobenzene and ortho-nitroanisole is near the reactivity of nitrobenzene.M-chloro-nitrobenzene and parachloronitrobenzene have a small amount of accessory substance to generate in catalytic hydrogenation.
Protection content of the present invention is not limited to above embodiment.Under the spirit and scope that do not deviate from inventive concept, variation and advantage that those skilled in the art can expect all are included in the present invention, and take appending claims as protection domain.
Claims (10)
1. a metallic organic framework structural material load platinum catalyst is characterized in that, comprises carrier and is carried on active constituent on the carrier; Wherein, described carrier is metallic organic framework structural material MIL-101, and described active constituent is platinum.
2. metallic organic framework structural material load platinum catalyst as claimed in claim 1, it is characterized in that, the loading of described platinum is 0.5-10.0wt.%, and described platinum is 24.2-78.6% at the decentralization of described carrier surface, and the average grain diameter of described platinum is 1.4-4.6nm.
3. the preparation method of metallic organic framework structural material load platinum catalyst as claimed in claim 1, it is characterized in that, take six hydration chloroplatinic acids as the active constituent precursor, described metallic organic framework structural material MIL-101 is carrier, at room temperature stir dipping, solvent evaporated, reduction obtains described metallic organic framework structural material load platinum catalyst under 60-100 ℃ of temperature conditions again.
4. the preparation method of metallic organic framework structural material load platinum catalyst as claimed in claim 4 is characterized in that, may further comprise the steps:
(1) preparation of metallic organic framework structural material MIL-101: with Cr (NO
3)
39H
2O, HF, terephthalic acid (TPA) and deionized water were with 1: 1: 1: 265 mol ratio kept 7-10 hour in 453K-503K constant temperature; Through cooling, filtration, washing, drying, obtain described metallic organic framework structural material MIL-101;
(2) preparation of catalyst: six hydration chloroplatinic acids are dissolved in solvent obtain the active constituent precursor, add described metallic organic framework structural material MIL-101, the loading of control platinum is 0.5-10wt.%, under 15-35 ℃, through stirring dipping and solvent evaporated, obtain described metallic organic framework structural material load platinum catalyst through reduction.
5. the preparation method of metallic organic framework structural material load platinum catalyst as claimed in claim 5 is characterized in that, described solvent is water or ethanol.
6. the preparation method of metallic organic framework structural material load platinum catalyst as claimed in claim 5 is characterized in that, described reduction is as reducing agent with sodium borohydride aqueous solution, hydrazine hydrate, formaldehyde or aqueous sodium formate solution.
7. the as claimed in claim 1 application of metallic organic framework structural material load platinum catalyst, it is characterized in that, be used for the asymmetric catalytic hydrogenation reaction to the chiral carbonyl compounds of diving, described latent chiral carbonyl compounds comprises ethyl pyruvate and 2-oxygen-4-phenylbutyrate ethyl ester.
8. the as claimed in claim 7 application of metallic organic framework structural material load platinum catalyst is characterized in that, preliminary treatment in the hydrogen atmosphere of described metal-organic framework materials load platinum catalyst under the 503K temperature.
9. the as claimed in claim 7 application of metallic organic framework structural material load platinum catalyst, it is characterized in that, described catalytic hydrogenation is to carry out in pressure is the pure hydrogen of 4.0 MPas, and reaction dissolvent is water, acetic acid, ethanol or their mixed solvent, and reaction temperature is room temperature.
10. the as claimed in claim 7 application of metallic organic framework structural material load platinum catalyst is characterized in that, described catalytic hydrogenation refers to the catalytic hydrogenation of aromatic aldehyde and derivative and nitro benzene and its derivative.
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