CN110252408A - A kind of MOF-808 (Zr) assemble nanometer metallic catalyst, preparation and application with CUS - Google Patents
A kind of MOF-808 (Zr) assemble nanometer metallic catalyst, preparation and application with CUS Download PDFInfo
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
A kind of MOF-808 (Zr) assemble nanometer metallic catalyst, preparation and application with CUS belongs to nano metal catalysis and technical field of fine.The present invention synthesizes MOF-808 (Zr) material with CUS using simple room temperature crystallization method first, then respectively by the catalytic active components such as single component metal Au, Ru, Pd, Pt and two-component metal Au-Ru, Au-Pd, Au-Pt, Ru-Pd, Ru-Pt, Pd-Pt, it is assembled in MOF-808 (Zr) under ultrasonic wave effect, prepares the multifunction catalyst of MOF-808 (Zr) assemble nanometer metal with CUS.Applied to CO2N- formylated and N- methylation catalytic reaction, have well selectivity.
Description
Technical field
MOF-808 (Zr) the material assemble nanometer metallic catalyst that the present invention relates to a kind of with CUS prepares and is applied to
CO2N- formylated and N- methylation catalytic reaction, belong to nano metal catalysis and technical field of fine.
Background technique
With the development of modern industry, a large amount of CO that Fossil fuel consumption generates2It has been discharged into atmosphere, has seriously affected
The environment of atmosphere.Therefore, by CO2The research for being converted into high valuable chemicals has great importance.Research in recent years
Show in the case where effective catalyst acts on, CO2With amine/H2N- formylated and N- methylation reaction may be implemented, by CO2It is converted into N-
The high valuable chemicals such as formamide, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine.Due in CO2With amine/H2N-
It is related to CO in formylated and N- methylation reaction2, amine, H2Etc. the activation and conversion of multiple molecules, it is therefore desirable to construct multi-functional
Catalyst.
Metal-organic framework (MOFs) material is to develop a very fast polyporous materials in recent years, since it has
Specific secondary structure unit and unique binding property, gas be selectively adsorbing and separating and catalysis in terms of show
Excellent performance.MOFs material with the unsaturated position (Coordinatively Unsaturated Sites, CUS) of coordination,
The Coordinate micro environment of its CUS is to absorption, activation and catalyzed conversion CO2Have with good performance, such as Dengke Wang report
CO can be made by having MIL-101 (Fe) catalyst of CUS2Photocatalytic conversion be formic acid (Dengke Wang, Renkun Huang,
Wenjun Liu,Dengrong Sun,and Zhaohui Li.Fe-Based MOFs for Photocatalytic
CO2Reduction:Role of Coordination Unsaturated Sites and Dual Excitation
Pathways.ACS Catal.2014,4,4254-4260).The reports such as Junlei Yan are catalyzed with the MIL-53 (Al) of CUS
Agent is formd in Friedel-Crafts acylation reaction to advantageous coordination intermediary is reacted, and TOF is more traditional than some
Much higher (Junlei Yan, Sai Jiang, Shengfu Ji, Da Shi, the Hefei Cheng.Metal- of complex catalyst
organic framework MIL-53(Al):synthesis,catalytic performance for the Friedel-
Crafts acylation,and reaction mechanism.Sci China Chem,2015,58,1544-1552).Closely
Come studies have shown that the catalyst containing Au, Ru, Pd, Pt isoreactivity component for CO2With amine/H2N- formylated and N- methyl
Changing reaction has good catalytic performance, in CO2And H2Volume ratio when being 1:1, mainly N- formylation reaction；In CO2And H2
Volume ratio when being 1:3, mainly N- methylation reaction.If Cu-BTC assemble nanometer metallic catalyst is to CO2With amine/H2First
Acylation reaction has a kind of good performance (Cu-BTC assemble nanometer metal of Ji Shengfu, Liu Jianfang, Mu Jincheng, Sun Rui, Xu Yue
Catalyst, preparation and be used for CO2Formylation reaction number of patent application: 201810136462.4).The reports such as Gao Tang
Au/γ-Al2O3Catalyst has good CO2With amine/H2N- methylation reaction performance (Gao Tang, Hong-Liang
Bao,Chan Jin,Xin-Hua Zhong and Xian-Long Du.Direct methylation of N-
methylaniline with CO2/H2catalyzed by gold nanoparticles supported on
alumina.RSC Adv.,2015,5,99678-99687)。
If being assembled in nano metal catalytic active component in the MOFs with CUS, since CUS is to CO2, amine have it is suitable
Suitable coordination environment, therefore the multifunction catalyst constructed can activate and convert at the same time CO2, amine and highly selective
Generating N- formamide, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine etc. will be with certain advantage.
The present invention synthesizes MOF-808 (Zr) material with CUS using simple room temperature crystallization method first, then divides
Single component metal Au, Ru, Pd, Pt and two-component metal Au-Ru, Au-Pd, Au-Pt, Ru-Pd, Ru-Pt, Pd-Pt etc. are not urged
Change active component, is assembled in MOF-808 (Zr) under ultrasonic wave effect, prepares MOF-808 (Zr) group with CUS and accommodate
The multifunction catalyst of rice metal.
Due to synthesizing MOF-808 (Zr) material using simple room temperature crystallization method in the present invention, and in MOF-808
(Zr) catalysis such as nanometer Au, Ru, Pd, Pt, Au-Ru, Au-Pd, Au-Pt, Ru-Pd, Ru-Pt, Pd-Pt of assembling high dispersive are living in
Property component.Therefore, MOF-808 (Zr) assemble nanometer metallic catalyst is to CO2With amine/H2N- formylated and N- methylation reaction
Generating the high valuable chemicals such as N- formamide, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine has catalysis well
Performance.In addition, preparation MOF-808 (Zr) material assemble nanometer metal solid heterogeneous catalyst, after the reaction with product point
From being easier, the separating technology of catalyst and product is fairly simple.
MOF-808 (Zr) material assemble nanometer metal solid heterogeneous catalyst of the method for the present invention preparation, can make CO2With
Amine/H2It is catalytically conveted to N- formamide, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine chemical combination object, and is catalyzed reaction
Separating technology process is simple, easy to operate, therefore has important industrial application value.
Summary of the invention
The purpose of the present invention is to provide a kind of by CO2With amine/H2Be catalytically conveted to N- benzamide type, N- methyl nitrosourea class,
N- methyl amine and N, the catalyst and preparation method and application of N- dimethyl aminated compounds.Wherein amine is aromatic amine and fat
Amine, N- benzamide type, N- methyl nitrosourea class, N- methyl amine and N, N- dimethyl aminated compounds are respectively aromatic radical N- formyl
Amine, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine and fat-based N- formamide, N- methyl nitrosourea, N- methyl amine and N,
N- dimethyl amine.
The present invention synthesizes MOF-808 (Zr) material with CUS using simple room temperature crystallization method first, then divides
Not by catalytic active components such as nanometer Au, Ru, Pd, Pt, Au-Ru, Au-Pd, Au-Pt, Ru-Pd, Ru-Pt, Pd-Pt, in ultrasound
It is assembled in MOF-808 (Zr) under wave effect, after being then filtered, washed, being dried in vacuo, prepares to CO2With amine/H2Catalysis
It is converted into aromatic radical N- formamide, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine and fat-based N- formamide, N- methyl
Amide, N- methyl amine and N, N- dimethyl amine chemical combination object have MOF-808 (Zr) the assemble nanometer metal of fine catalytic performance solid
Body catalyst.The mass content of the preferred Au of metal catalytic activity component in MOF-808 (Zr) assemble nanometer metal solid catalyst
For 2.95wt%~4.53wt%；The mass content of Ru is 1.92wt%~4.65wt%；The mass content of Pd is 2.98wt%
~4.89wt%；The mass content of Pt is 2.73wt%~4.88wt%.It is preferred that the content of metal catalytic activity component is not less than
4wt%.
Above-mentioned MOF-808 (Zr) the assemble nanometer metallic catalyst of the present invention, prepares using including following method:
(1) prepared by MOF-808 (Zr) material: weighing a certain amount of zirconium oxychloride (ZrOCl2.8H2O) be dissolved in deionized water and
In the mixed solution of ethyl alcohol (preferred mass ratio be 1:1), be made zirconyl chloride solution (preferred mass concentration is 10.7%~
14.3%)；Weigh a certain amount of trimesic acid (H3BTC) it is dissolved in N, N-dimethylformamide (DMF) and ethyl alcohol (preferred mass
Than H is made in the mixed solution for 1:1)3BTC solution (preferred mass concentration is 12.6%~16.8%)；By oxygen chlorine under stirring
Change zirconium solution and H3BTC solution is added drop-wise in reactor, wherein the metal ion and H of zirconium oxychloride3The molar ratio of BTC is 1:1,
It is sufficiently stirred, under 150W~200W ultrasonic power, ultrasonic 40min~60min, then crystallization 48 hours at room temperature, centrifugation
Separation, with deionized water and ethanol washing, is dried in vacuo 12 hours at 150 DEG C, can be prepared by powder MOF-808 (Zr) material
Material.
(2) prepared by MOF-808 (Zr) assemble nanometer metallic catalyst: weighing the dispersion of a certain amount of MOF-808 (Zr) material
In ethanol, MOF-808 (Zr) dispersion liquid (preferred mass concentration is 18.6%~19.1%) is made, is denoted as A liquid；It weighs certain
The presoma (preferably chloride) of the catalytic active component metal of amount is dissolved in the mixture of alcohol-water, and the forerunner of metal is made
Liquid solution such as weighs one of gold chloride, ruthenic chloride, palladium chloride, chloroplatinic acid or two kinds any, is dissolved in the mixing of alcohol-water
In solution, the precursor solution of metal is made；Further preferably weigh the mixed solution that a certain amount of gold chloride is dissolved in alcohol-water
In, the precursor solution (preferred mass percent concentration 2%~5%) of metal is made, is denoted as B liquid；Weigh a certain amount of chlorination
One of ruthenium, palladium chloride, chloroplatinic acid, are dissolved in the mixed solution of alcohol-water, and precursor solution (the preferably matter of metal is made
Measure percent concentration 1%~5%), it is denoted as C liquid；Under stirring, the precursor solution of metal is added drop-wise in A liquid, is sufficiently stirred,
Then under 50W~100W ultrasonic power, ultrasonic 50min~60min, during which metal ion can mildly be restored by ethyl alcohol, and
And complete the process of assemble nanometer metal in MOF-808 (Zr).Then filtering, with deionized water and ethanol washing, at 150 DEG C
Vacuum drying 12 hours, MOF-808 (Zr) assemble nanometer metal solid catalyst as obtained.
Different metal and its different metal content can be adjusted in catalyst, to obtain living with bimetallic catalytic
MOF-808 (Zr) assemble nanometer metal solid catalyst of property component.
The present invention is applied to CO using MOF-808 (Zr) assemble nanometer metal solid catalyst of preparation2With amine/H2N-
Formylated and the reaction of N- methylation catalytic, by CO2With amine/H2One step carries out N- formylated and N- methylation reaction synthesizes N- formyl
The compounds such as amine, N- methyl nitrosourea, N- methyl amine and N, N- dimethyl amine.Catalysis reaction carries out in autoclave high-pressure reactor,
It is firstly added MOF-808 (Zr) assemble nanometer metal solid catalyst of liquid amine and activation, is then charged with CO2And H2Gaseous mixture
Body (preferably pressure is 2.5-3.5MPa), is reacted under 80-210 DEG C of reaction temperature, finally obtains N- formamide, N- methyl
Amide, N- methyl amine, N, the compounds such as N- dimethyl amine.The result shows that MOF-808 (Zr) assemble nanometer metal catalytic of preparation
Agent has good catalytic performance and N- formamide, N- methyl nitrosourea, N- methyl amine, N, the selection of the compounds such as N- dimethyl amine
Property (selectivity be not less than 98%), and the catalyst after reacting can be readily separated and recycle, and have and repeat to follow well
Ring service performance.
In CO2And H2Volume ratio when being 1:1, mainly N- formylation reaction；In CO2And H2Volume ratio be 1:3 when,
Mainly N- methylation reaction.
MOF-808 (Zr) assemble nanometer metallic catalyst prepared by the present invention has following remarkable advantage:
(1) in the preparation process of MOF-808 (Zr) assemble nanometer metallic catalyst, due to using unique ultrasonic wave
Technology and the mild restoring method of ethyl alcohol, so that being assembled in Au, Ru, Pd, Pt, Au-Ru, Au-Pd, Au- in MOF-808 (Zr)
The catalytic active components such as Pt, Ru-Pd, Ru-Pt, Pd-Pt, form the nano particle of high dispersive, this not only increases catalyst
Activity, and can to avoid the aggregation and loss of catalytic active component in reaction process, greatly improve catalyst activity and
Stability.
(2) solid heterogeneous catalyst of MOF-808 (Zr) the material assemble nanometer metal prepared, in CO2With amine/H2N-
Formamide, N- methyl nitrosourea, N- methyl amine, N, after the reaction such as N- dimethyl amine, catalyst is simple compared with the separating technology of product
It is single, therefore there is important industrial application value.
Specific embodiment
The present invention will be further described with reference to the examples below, but the present invention is not limited thereto.
Embodiment 1
(1) ZrOCl of 19.3g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 80.7g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 10.7% is made；Weigh 12.6g trimesic acid (H3BTC) it is dissolved in 87.4g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 12.6%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 150W ultrasonic power
60min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 1.
(2) MOF-808 (Zr) 1 for weighing 19.1g, is dissolved in 80.9g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
19.1% dispersion liquid is denoted as A1 liquid.Weigh the HAuCl of 7.8g4Be dissolved in 92.2g alcohol-water mixed liquor (mass ratio 1:
1) the metal front liquid solution that Au mass content is 4.53wt%, is made, is denoted as B1 liquid.Under stirring, the B1 drop of 20g is added to
It in A1 liquid, is sufficiently stirred, then under 50W ultrasonic power, ultrasonic 60min, during which metal ion can be gradually mild by ethyl alcohol
Reduction, and complete the process of assemble nanometer metal in MOF-808 (Zr).After filtering, with deionized water and ethanol washing,
It is dried in vacuo at 150 DEG C 12 hours, 4.53wt%Au/MOF-808 (Zr) solid catalyst as obtained.
(3) in 100mL autoclave high-pressure reactor, 5mL aniline is added, the 4.53wt%Au/MOF- of preparation is then added
808 (Zr) solid catalyst 0.0025g, are then charged with the CO of 3.0MPa2And H2(volume ratio 1:1) mixed gas, then exists
It is reacted 8 hours at 190 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of aniline is 60.16%, formanilide
Selectivity be 98.62%.
Embodiment 2
(1) ZrOCl of 22.6g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 77.4g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 12.5% is made；Weigh 14.7g trimesic acid (H3BTC) it is dissolved in 85.3g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 14.7%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 180W ultrasonic power
50min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 2.
(2) MOF-808 (Zr) 2 for weighing 19.1g, is dissolved in 80.9g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
19.1% dispersion liquid is denoted as A2 liquid.Weigh the RuCl of 9.5g3It is dissolved in the mixed liquor (mass ratio 1:1) of 90.5g alcohol-water,
The metal front liquid solution that Ru mass content is 4.65wt% is made, is denoted as B2 liquid.Under stirring, the B2 drop of 20g is added to A2
It in liquid, is sufficiently stirred, then under 80W ultrasonic power, ultrasonic 55min, during which metal ion gradually can mildly be gone back by ethyl alcohol
Original, and complete the process of assemble nanometer metal in MOF-808 (Zr).After filtering, with deionized water and ethanol washing, 150
It is dried in vacuo at DEG C 12 hours, 4.65wt%Ru/MOF-808 (Zr) solid catalyst as obtained.
(3) in 100mL autoclave high-pressure reactor, the methylphenylamine of 5mL is added, the 4.65wt% of preparation is then added
Ru/MOF-808 (Zr) solid catalyst 0.0022g, is then charged with the CO of 3.2MPa2And H2(volume ratio 1:1) mixed gas,
Then it is reacted 8 hours at 200 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of aniline is 68.25%, N- first
The selectivity of base formanilide is 98.31%.
Embodiment 3
(1) ZrOCl of 25.8g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 74.2g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 14.3% is made；Weigh 16.8g trimesic acid (H3BTC) it is dissolved in 83.2g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 16.8%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 200W ultrasonic power
40min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 3.
(2) MOF-808 (Zr) 3 for weighing 19.0g, is dissolved in 81.0g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
19.0% dispersion liquid is denoted as A3 liquid.Weigh the PdCl of 8.2g2It is dissolved in the mixed liquor (mass ratio 1:1) of 91.8g alcohol-water,
The metal front liquid solution that Pd mass content is 4.89wt% is made, is denoted as B3 liquid.Under stirring, the B3 drop of 20g is added to A3
It in liquid, is sufficiently stirred, then under 100W ultrasonic power, ultrasonic 50min, during which metal ion gradually can mildly be gone back by ethyl alcohol
Original, and complete the process of assemble nanometer metal in MOF-808 (Zr).After filtering, with deionized water and ethanol washing, 150
It is dried in vacuo at DEG C 12 hours, 4.89wt%Pd/MOF-808 (Zr) solid catalyst as obtained.
(3) in 100mL autoclave high-pressure reactor, 5mL cyclohexylamine is added, the 4.89wt%Pd/ of preparation is then added
MOF-808 (Zr) solid catalyst 0.0021g, is then charged with the CO of 3.1MPa2And H2(volume ratio 1:1) mixed gas, then
It is reacted 10 hours at 140 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of cyclohexylamine is 66.37%, N- first
The selectivity of acyl cyclohexylamine is 98.75%.
Embodiment 4
(1) ZrOCl of 20.6g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 79.4g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 11.4% is made；Weigh 13.4g trimesic acid (H3BTC) it is dissolved in 86.6g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 13.4%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 180W ultrasonic power
55min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 4.
(2) MOF-808 (Zr) 4 for weighing 19.0g, is dissolved in 81.0g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
19.0% dispersion liquid is denoted as A3 liquid.Weigh the H of 10.2g2PtCl6Be dissolved in 89.8g alcohol-water mixed liquor (mass ratio 1:
1) the metal front liquid solution that Pt mass content is 4.88wt%, is made, is denoted as B4 liquid.Under stirring, the B4 drop of 20g is added to
It in A4 liquid, is sufficiently stirred, then under 90W ultrasonic power, ultrasonic 55min, during which metal ion can be gradually mild by ethyl alcohol
Reduction, and complete the process of assemble nanometer metal in MOF-808 (Zr).After filtering, with deionized water and ethanol washing,
It is dried in vacuo at 150 DEG C 12 hours, 4.88wt%Pt/MOF-808 (Zr) solid catalyst as obtained.
(3) in 100mL autoclave high-pressure reactor, the N-methylcyclohexylamine of 5mL is added, preparation is then added
4.88wt%Pt/MOF-808 (Zr) solid catalyst 0.0022g, is then charged with the CO of 3.3MPa2And H2(volume ratio 1:1) is mixed
Gas is closed, is then reacted 10 hours at 140 DEG C.After the reaction was completed, it is determined by chromatography, the conversion of N-methylcyclohexylamine
Rate is that 62.07%, N- methyl N-formyl cyclohexylamine selectivity is 98.85%.
Embodiment 5
(1) ZrOCl of 24.5g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 75.5g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 13.5% is made；Weigh 16.0g trimesic acid (H3BTC) it is dissolved in 84.0g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 16.0%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 190W ultrasonic power
45min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 5.
(2) MOF-808 (Zr) 5 for weighing 19.0g, is dissolved in 81.0g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
19.0% dispersion liquid is denoted as A5 liquid.Weigh the HAuCl of 5.4g4Be dissolved in 94.6g alcohol-water mixed liquor (mass ratio 1:
1) the metal front liquid solution that Au mass content is 3.15wt%, is made, is denoted as B5 liquid.Weigh the RuCl of 3.9g3It is dissolved in 96.1g
Alcohol-water mixed liquor (mass ratio 1:1), be made Ru mass concentration be 1.92% metal front liquid solution, be denoted as C5
Liquid.Under stirring, the C5 drop of the B5 liquid of 20g and 20g is added in A5 liquid, is sufficiently stirred, then under 80W ultrasonic power, surpassed
Sound 55min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete assemble nanometer metal in MOF-808 (Zr)
Process.After filtering, with deionized water and ethanol washing, it is dried in vacuo at 150 DEG C 12 hours, 3.15wt% as obtained
Au-1.92wt%Ru//MOF-808 (Zr) solid catalyst.
(3) in 100mL autoclave high-pressure reactor, the butylamine of 5mL is added, the 3.15wt%Au- of preparation is then added
1.92wt%Ru//MOF-808 (Zr) solid catalyst 0.002g, is then charged with the CO of 3.0MPa2And H2(volume ratio 1:1) is mixed
Gas is closed, is then reacted 10 hours at 80 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of butylamine is
The selectivity of 65.10%, N- formyl butylamine is 98.75%.
Embodiment 6
(1) ZrOCl of 21.9g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 78.1g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 12.1% is made；Weigh 14.3g trimesic acid (H3BTC) it is dissolved in 85.7g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 14.3%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 180W ultrasonic power
55min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 6.
(2) MOF-808 (Zr) 6 for weighing 18.8g, is dissolved in 81.2g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
18.8% dispersion liquid is denoted as A6 liquid.Weigh the HAuCl of 5.1g4Be dissolved in 94.9g alcohol-water mixed liquor (mass ratio 1:
1) the metal front liquid solution that Au mass content is 2.95wt%, is made, is denoted as B6 liquid.Weigh the PdCl of 5.3g2It is dissolved in 94.7g
Alcohol-water mixed liquor (mass ratio 1:1), be made Pd mass concentration be 3.19% metal front liquid solution, be denoted as C6
Liquid.Under stirring, the C6 drop of the B6 liquid of 20g and 20g is added in A6 liquid, is sufficiently stirred, then under 90W ultrasonic power, surpassed
Sound 50min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete assemble nanometer metal in MOF-808 (Zr)
Process.After filtering, with deionized water and ethanol washing, it is dried in vacuo at 150 DEG C 12 hours, 2.95wt% as obtained
Au-3.19wt%Pd/MOF-808 (Zr) solid catalyst.
(3) in 100mL autoclave high-pressure reactor, the N- methylbutylamine of 5mL is added, the 2.95wt% of preparation is then added
Au-3.19wt%Pd/MOF-808 (Zr) solid catalyst 0.0021g, is then charged with the CO of 3.0MPa2And H2(volume ratio 1:
1) then mixed gas is reacted 10 hours at 80 DEG C.After the reaction was completed, it is determined by chromatography, N- methylbutylamine turns
Rate is that 71.36%, N- methyl N-formyl butylamine selectivity is 98.78%.
Embodiment 7
(1) ZrOCl of 23.8g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 76.2g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 13.2% is made；Weigh 15.6g trimesic acid (H3BTC) it is dissolved in 84.4g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 15.6%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 160W ultrasonic power
60min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 7.
(2) MOF-808 (Zr) 7 for weighing 18.6g, is dissolved in 81.4g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
18.6% dispersion liquid is denoted as A7 liquid.Weigh the HAuCl of 5.8g4Be dissolved in 94.2g alcohol-water mixed liquor (mass ratio 1:
1) the metal front liquid solution that Au mass content is 3.35wt%, is made, is denoted as B7 liquid.Weigh the H of 7.4g2PtCl6It is dissolved in
The metal front liquid solution that Pt mass concentration is 3.51% is made in the mixed liquor (mass ratio 1:1) of the alcohol-water of 92.6g, note
For C7 liquid.Under stirring, the C7 drop of the B7 liquid of 20g and 20g is added in A7 liquid, is sufficiently stirred, then in 80W ultrasonic power
Under, ultrasonic 60min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete assemble nanometer in MOF-808 (Zr)
The process of metal.After filtering, with deionized water and ethanol washing, it is dried in vacuo at 150 DEG C 12 hours, it is as obtained
3.35wt%Au-3.51wt%Pt/MOF-808 (Zr) solid catalyst.
(3) in 100mL autoclave high-pressure reactor, 5mL aniline is added, the 3.35wt%Au- of preparation is then added
3.51wt%Pt/MOF-808 (Zr) solid catalyst 0.0022g, is then charged with the CO of 3.5MPa2And H2(volume ratio 1:3) is mixed
Gas is closed, is then reacted 12 hours at 200 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of aniline is
72.59%, the selectivity of methylphenylamine is 75.20%, and the selectivity of n,N-Dimethylaniline is 23.62%, overall selectivity
It is 98.82%.
Embodiment 8
(1) ZrOCl of 21.3g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 78.7g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 11.8% is made；Weigh 13.9g trimesic acid (H3BTC) it is dissolved in 86.1g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 13.9%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 150W ultrasonic power
60min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 8.
(2) MOF-808 (Zr) 8 for weighing 18.7g, is dissolved in 81.3g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
18.7% dispersion liquid is denoted as A8 liquid.Weigh the RuCl of 7.3g3Be dissolved in the alcohol-water of 92.7g mixed liquor (mass ratio 1:
1) the metal front liquid solution that Ru mass concentration is 3.54%, is made, is denoted as B8 liquid.Weigh the PdCl of 5.0g2It is dissolved in 94.7g's
The mixed liquor (mass ratio 1:1) of alcohol-water is made the metal front liquid solution that Pd mass concentration is 2.98%, is denoted as C8 liquid.
Under stirring, the C8 drop of the B8 liquid of 20g and 20g is added in A7 liquid, is sufficiently stirred, then under 60W ultrasonic power, ultrasound
55min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete assemble nanometer metal in MOF-808 (Zr)
Process.After filtering, with deionized water and ethanol washing, it is dried in vacuo at 150 DEG C 12 hours, 3.54wt% as obtained
Ru-2.98wt%Pd/MOF-808 (Zr) solid catalyst.
(3) in 100mL autoclave high-pressure reactor, the open-chain crown ether of 5mL is added, the 3.54wt% of preparation is then added
Ru-2.98wt%Pd/MOF-808 (Zr) solid catalyst 0.0025g, is then charged with the CO of 3.2MPa2And H2(volume ratio 1:
3) then mixed gas is reacted 12 hours at 210 DEG C.After the reaction was completed, it is determined by chromatography, open-chain crown ether turns
Rate is 66.89%, is 78.35% to methyl N-methylaniline selectivity, to methyl N, the selectivity of accelerine
It is 20.26%, overall selectivity 98.61%.
Embodiment 9
(1) ZrOCl of 25.1g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 74.9g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 13.9% is made；Weigh 16.4g trimesic acid (H3BTC) it is dissolved in 83.6g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 16.4%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 170W ultrasonic power
55min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 9.
(2) MOF-808 (Zr) 9 for weighing 18.7g, is dissolved in 81.3g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
18.7% dispersion liquid is denoted as A9 liquid.Weigh the RuCl of 6.0g3Be dissolved in the alcohol-water of 94.0g mixed liquor (mass ratio 1:
1) the metal front liquid solution that Ru mass concentration is 2.93%, is made, is denoted as B9 liquid.Weigh the H of 7.8g2PtCl6It is dissolved in 92.2g
Alcohol-water mixed liquor (mass ratio 1:1), be made Pt mass concentration be 3.71% metal front liquid solution, be denoted as C9
Liquid.Under stirring, the C9 drop of the B9 liquid of 20g and 20g is added in A9 liquid, is sufficiently stirred, then under 70W ultrasonic power, surpassed
Sound 60min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete assemble nanometer metal in MOF-808 (Zr)
Process.After filtering, with deionized water and ethanol washing, it is dried in vacuo at 150 DEG C 12 hours, 2.93wt% as obtained
Ru-3.71wt%Pt/MOF-808 (Zr) solid catalyst.
(3) in 100mL autoclave high-pressure reactor, the cyclohexylamine of 5mL is added, the 2.93wt%Ru- of preparation is then added
3.71wt%Pt/MOF-808 (Zr) solid catalyst 0.0022g, is then charged with the CO of 3.0MPa2And H2(volume ratio 1:3) is mixed
Gas is closed, is then reacted 12 hours at 140 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of cyclohexylamine is
72.58%, the selectivity of N-methylcyclohexylamine is 77.29%, N, and the selectivity of N- dimethyl cyclohexyl amine is 21.08%, total to select
Selecting property is 98.37%.
Embodiment 10
(1) ZrOCl of 23.2g is weighed2.8H2O is dissolved in (mass ratio in the deionized water of 76.8g and the mixed solution of ethyl alcohol
For 1:1), the solution that zirconium oxychloride mass concentration is 12.8% is made；Weigh 15.1g trimesic acid (H3BTC) it is dissolved in 84.9g
In ethyl alcohol and the mixed solution of n,N dimethylformamide (DMF) (preferred mass ratio is 1:1), it is dense that trimesic acid quality is made
The solution that degree is 15.1%.Under stirring, zirconyl chloride solution and trimesic acid solution are added drop-wise in reactor, wherein oxygen chlorine
The molar ratio of the metal ion and trimesic acid of changing zirconium is 1:1.It is sufficiently stirred, it is then ultrasonic under 180W ultrasonic power
50min, then crystallization 48 hours, centrifuge separation with deionized water and ethanol washing, are dried in vacuo at 150 DEG C at room temperature
12 hours, it can be prepared by powder MOF-808 (Zr) material, be denoted as MOF-808 (Zr) 10.
(2) MOF-808 (Zr) 10 for weighing 18.8g, is dissolved in 81.2g ethyl alcohol, and MOF-808 (Zr) mass concentration is made and is
18.8% dispersion liquid is denoted as A10 liquid.Weigh the PdCl of 5.9g2Be dissolved in the alcohol-water of 94.1g mixed liquor (mass ratio 1:
1) the metal front liquid solution that Pd mass concentration is 3.51%, is made, is denoted as B10 liquid.Weigh the H of 5.7g2PtCl6It is dissolved in 94.3g
Alcohol-water mixed liquor (mass ratio 1:1), be made Pt mass concentration be 2.73% metal front liquid solution, be denoted as C10
Liquid.Under stirring, the C10 drop of the B10 liquid of 20g and 20g is added in A10 liquid, is sufficiently stirred, then under 50W ultrasonic power,
Ultrasonic 60min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete assemble nanometer gold in MOF-808 (Zr)
The process of category.After filtering, with deionized water and ethanol washing, it is dried in vacuo at 150 DEG C 12 hours, it is as obtained
3.51wt%Pd-2.73wt%Pt/MOF-808 (Zr) solid catalyst.
(3) in 100mL autoclave high-pressure reactor, the butylamine of 5mL is added, the 3.51wt%Pd- of preparation is then added
2.73wt%Pt/MOF-808 (Zr) solid catalyst 0.002g, is then charged with the CO of 3.2MPa2And H2(volume ratio 1:3) is mixed
Gas is closed, is then reacted 12 hours at 80 DEG C.After the reaction was completed, it is determined by chromatography, the conversion ratio of butylamine is
The selectivity of 73.86%, N- methylbutylamine is 78.86%, N, and the selectivity of N- dimethyl butylamine is 20.01%, overall selectivity
It is 98.87%.
Above-described embodiment catalyst repetitive cycling is not dropped using 20 performances.
Claims (10)
1. a kind of MOF-808 (Zr) assemble nanometer metallic catalyst with CUS, which is characterized in that the MOF-808 with CUS
(Zr) material is assembled in MOF-808 (Zr) under ultrasonic wave effect, prepares with CUS's then by catalytic active component
The multifunction catalyst of MOF-808 (Zr) assemble nanometer metal；Catalytic active component be selected from nanometer Au, Ru, Pd, Pt, Au-Ru,
Au-Pd, Au-Pt, Ru-Pd, Ru-Pt, Pd-Pt catalytic active component.
2. a kind of MOF-808 (Zr) assemble nanometer metallic catalyst with CUS described in accordance with the claim 1, feature exist
In the mass content of Au is 2.95wt%~4.53wt%；The mass content of Ru is 1.92wt%~4.65wt%；The quality of Pd
Content is 2.98wt%~4.89wt%；The mass content of Pt is 2.73wt%~4.88wt%；It is preferred that metal catalytic activity group
The content divided is not less than 4wt%.
3. the preparation method of catalyst of any of claims 1 or 2, which comprises the following steps:
(1) prepared by MOF-808 (Zr) material: weighing the mixed solution that a certain amount of zirconium oxychloride is dissolved in deionized water and ethyl alcohol
In, zirconyl chloride solution is made；Weigh a certain amount of trimesic acid (H3BTC) it is dissolved in N, N-dimethylformamide (DMF) and second
In the mixed solution of alcohol, H is made3BTC solution；By zirconyl chloride solution and H under stirring3BTC solution is added drop-wise in reactor,
The metal ion and H of middle zirconium oxychloride3The molar ratio of BTC is 1:1, is sufficiently stirred, under 150W~200W ultrasonic power, ultrasound
40min~60min, then crystallization 48 hours, centrifuge separation are true at 150 DEG C with deionized water and ethanol washing at room temperature
Sky is 12 hours dry, can be prepared by powder MOF-808 (Zr) material；
(2) prepared by MOF-808 (Zr) assemble nanometer metallic catalyst: weighing a certain amount of MOF-808 (Zr) material and is dispersed in second
In alcohol, MOF-808 (Zr) dispersion liquid is made, is denoted as A liquid；Weigh the presoma chloride of a certain amount of catalytic active component metal
It is dissolved in the mixture of alcohol-water, the precursor solution of metal is made, under stirring, the precursor solution of metal is added drop-wise to A liquid
In, it is sufficiently stirred, then under 50W~100W ultrasonic power, ultrasonic 50min~60min, during which metal ion can be by ethyl alcohol
Mild reduction, and complete the process of assemble nanometer metal in MOF-808 (Zr)；Then it filters, washed with deionized water and ethyl alcohol
It washs, is dried in vacuo at 150 DEG C, MOF-808 (Zr) assemble nanometer metal solid catalyst as obtained.
4. according to the method for claim 3, which is characterized in that deionized water and ethyl alcohol mass ratio are 1:1 in step (1),
The mass concentration of zirconyl chloride solution is 10.7%~14.3%；The mass ratio of N, N-dimethylformamide (DMF) and ethyl alcohol is 1:
1, H3The mass concentration of BTC solution is 12.6%~16.8%).
5. according to the method for claim 3, which is characterized in that MOF-808 (Zr) dispersion liquid mass concentration is in step (2)
18.6%~19.1%；One of gold chloride, ruthenic chloride, palladium chloride, chloroplatinic acid or two kinds any are weighed, alcohol-water is dissolved in
Mixed solution in, the precursor solution of metal is made.
6. according to the method for claim 5, which is characterized in that weigh the mixing that a certain amount of gold chloride is dissolved in alcohol-water
In solution, the precursor solution of metal is made, mass percent concentration 2%~5% is denoted as B liquid；Weigh a certain amount of chlorination
One of ruthenium, palladium chloride, chloroplatinic acid, are dissolved in the mixed solution of alcohol-water, and the precursor solution of metal, quality hundred is made
Divide specific concentration 1%~5%, is denoted as C liquid；Under stirring, one or more of B liquid and C liquid are added drop-wise in A liquid, are sufficiently stirred.
7. the application of catalyst of any of claims 1 or 2, which is characterized in that be applied to CO2With amine/H2N- formylated and N-
Methylation catalytic reaction.
8. according to the application of claim 7, which is characterized in that catalysis reaction carries out in autoclave high-pressure reactor, is firstly added
Liquid amine and the MOF-808 of activation (Zr) assemble nanometer metal solid catalyst, are then charged with CO2And H2Mixed gas, reaction pressure
Power is 2.5-3.5MPa, is reacted under 80-210 DEG C of reaction temperature.
9. according to the application of claim 7, which is characterized in that N- formamide, N- methyl nitrosourea, N- methyl amine, N are finally obtained,
The compounds such as N- dimethyl amine.
10. according to the application of claim 7, which is characterized in that in CO2And H2Volume ratio be 1:1 when, mainly N- formylated
Reaction；In CO2And H2Volume ratio when being 1:3, mainly N- methylation reaction.
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Application publication date: 20190920 |
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