CN108355716A - A kind of Cu-BTC assemble nanometers metallic catalyst prepares and is used for CO2Formylation reaction - Google Patents
A kind of Cu-BTC assemble nanometers metallic catalyst prepares and is used for CO2Formylation reaction Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Abstract
A kind of Cu BTC assemble nanometers metallic catalyst prepares and is used for CO2Formylation reaction, belong to nano metal catalysis and technical field of fine.Ultrasonic technology is used first, quickly prepares Cu BTC materials；Then the catalytic active components such as single component metal Ru, Au, Pd and two-component metal Ru Au, Ru Pd, Au Pd are assembled in Cu BTC under ul-trasonic irradiation, then after being filtered, washed, being dried in vacuo, are prepared to CO respectively2With amine/H2Being catalytically conveted to N benzamide compounds has the Cu BTC assemble nanometer metal solid catalyst of fine catalytic performance.
Description
Technical field
The present invention relates to a kind of Cu-BTC materials assemble nanometer metallic catalyst, prepare and be used for CO2Formylated catalysis
Reaction belongs to nano metal catalysis and technical field of fine.
Background technology
With the development of modern industry, a large amount of CO that Fossil fuel consumption generates2It has been discharged into air, has seriously affected
The environment of air.Therefore, by CO2The research for being converted into high valuable chemicals has great importance.Research in recent years
Show under the action of catalyst, CO2With amine/H2The high valuable chemicals such as N- formamides can be generated.Such as Lei Zhang reports
Road uses Ru- complex compound homogeneous catalysts, makes CO2In H2In the presence of realize various amine N- formylation reactions (Lei Zhang,
Zhaobin Han,Xiaoyu Zhao,Zheng Wang,and Kuiling Ding.Highly Efficient
Ruthenium-Catalyzed N-Formylation of Amines with H2and
CO2.Angew.Chem.Int.Ed.2015,54:6186-6189).But homogeneous catalyst is after the reaction compared with the separation of product
Difficulty, if preparing some novel solid heterogeneous catalysts, the separation of post catalyst reaction and product is just easier.
Metal-organic framework (MOFs) material has the regular pore passage structure of nano level matrix type, big specific surface area
And the features such as porosity, being widely used in catalysis, absorption, separation etc., (Li Qingyuan, Ji Shengfu, Hao Zhi seek metals-
Organic framework material and its application chemical progress in catalysis is reacted, 2012,24 (8):1506-1518).Our research
It was found that the Cu-BTC in MOFs materials is since it is with three-dimensional open-framework and abundant active site, in Pechmann
Good catalytic performance (Qingyuan Li, Sai Jiang, Shengfu Ji, Da Shi, Junlei are shown in reaction
Yan,Yanxia Huo,Qingmin Zhang.Magnetically recyclable Cu-BTC@SiO2@
Fe3O4catalysts and their catalytic performance for Pechmann
reaction.Industrial&Engineering Chemistry Research,2014,53(39):14948-14955)。
If by CO2With amine/H2The catalytic active components such as good Ru, Au, Pd of N- formylation reactions catalytic performance, be assembled in Cu-BTC
In, the solid heterogeneous catalyst of Cu-BTC assemble nanometer metals is prepared, then the unique pore passage structures of Cu-BTC can be effectively
Inhibit the reunion of metal active constituent particle in catalytic reaction process, meanwhile, post catalyst reaction is compared with the separation just of product
It is easy, the separating technology of catalyst and product is fairly simple.
Recently, we use ultrasonic technology, in the γ-Al with meso-hole structure2O3@Fe3O4Pd catalysis is assembled in material
Active component has prepared the equally distributed Pd/ γ-Al of nano Pd particle particle2O3@Fe3O4Catalyst (Hao Yang, Da Shi,
Sheng-Fu Ji,Dan-Ni Zhang,Xue-Fei Liu.Nanosized Pd assembled on
superparamagnetic core-shell microspheres:Synthesis,characterization and
recyclable catalytic properties for the Heck reaction.Chinese Chemical
Letters,2014,25:1265-1270).Based on these research work basis, the present invention uses ultrasonic technology quick first
Cu-BTC materials are prepared, then respectively by single component metal Ru, Au, Pd and two-component metal Ru-Au, Ru-Pd, Au-Pd etc.
Catalytic active component is assembled under ul-trasonic irradiation in Cu-BTC, prepares the solid heterogeneous of Cu-BTC assemble nanometer metals
Catalyst.
As a result of unique ultrasonic technology in the present invention, therefore Cu-BTC materials can be quickly prepared, and
The catalytic active components such as nanometer Ru, Au, Pd, Ru-Au, Ru-Pd, Au-Pd of high dispersive can be assembled in Cu-BTC.Therefore,
Cu-BTC assemble nanometer metallic catalysts are to CO2With amine/H2N- formylation reactions have good catalytic performance.In addition, preparing
Cu-BTC material assemble nanometer metal solid heterogeneous catalysts, be easier after the reaction with the separation of product, catalyst with
The separating technology of product is fairly simple.
Cu-BTC material assemble nanometer metal solid heterogeneous catalysts prepared by the method for the present invention, can make CO2With amine/H2
N- benzamide compounds are catalytically conveted to, and it is simple to be catalyzed Reaction Separation technological process, it is easy to operate, therefore with important
Industrial application value.
Invention content
The purpose of the present invention is to provide a kind of by CO2With amine/H2Be catalytically conveted to N- benzamide compounds catalyst and
Preparation method and application.Wherein amine is aniline, and N- benzamide compounds are formanilide.
The present invention uses ultrasonic technology first, quickly prepares Cu-BTC materials；Then respectively by single component metal Ru,
The catalytic active components such as Au, Pd and two-component metal Ru-Au, Ru-Pd, Au-Pd, Cu-BTC is assembled under ul-trasonic irradiation
In, then after being filtered, washed, being dried in vacuo, prepare to CO2With amine/H2Being catalytically conveted to N- benzamide compounds has very
The Cu-BTC assemble nanometer metal solid catalyst of good catalytic performance.
The above-mentioned Cu-BTC assemble nanometers metallic catalyst of the present invention, prepares using including following method：
(1) Cu-BTC material preparations：It weighs a certain amount of copper nitrate or copper acetate is dissolved in deionized water, copper nitrate is made
Or acetic acid copper solution (a concentration of 8%~15%) of preferred mass；Weigh a certain amount of trimesic acid (H3BTC) it is dissolved in N, N bis-
(preferred mass ratio is 1 for methylformamide (DMF) and ethyl alcohol:1) in mixed solution, trimesic acid solution (preferably matter is made
Measure a concentration of 8%~15%)；Copper nitrate or acetic acid copper solution and trimesic acid solution are added drop-wise in reactor under stirring,
Wherein the molar ratio of the metal ion of copper nitrate or copper acetate and trimesic acid is 3：2, be sufficiently stirred, then 100W~
Ultrasound 30min~50min, is then centrifuged for detaching, be washed with deionized water and ethyl alcohol under 150W ultrasonic powers, and vacuum drying is (such as
It is dried in vacuo 12 hours at 60 DEG C), you can blue powder Cu-BTC materials are made；
(2) prepared by Cu-BTC assemble nanometers metallic catalyst：A certain amount of Cu-BTC materials are weighed, are disperseed in ethanol,
Cu-BTC dispersion liquids are made, and (a concentration of 20%~25%) of preferred mass, is denoted as A liquid；Weigh a certain amount of ruthenic chloride, gold chloride,
One or both of palladium bichloride is dissolved in the mixed solution of alcohol-water, and metal front liquid solution (preferred mass percentage is made
Specific concentration 1%~2%), it is denoted as B liquid；Under stirring, B drops are added in A liquid, are sufficiently stirred, then in 50W~100W ultrasounds
Under power, ultrasonic 50min~60min, during which metal ion can mildly be restored by ethyl alcohol, and is completed group in Cu-BTC and accommodated
The process of rice metal.Then it filters, washed with deionized water and ethyl alcohol, vacuum drying (it is small to be dried in vacuo 12 such as at 60 DEG C
When), Cu-BTC assemble nanometer metal solid catalyst as obtained.
Different metal and its different metal content can be adjusted in catalyst, to obtain with monometallic or double gold
Belong to the Cu-BTC assemble nanometer metal solid catalyst of catalytic active component.
In Cu-BTC assemble nanometer metal solid catalyst no matter monometallic or the preferred Ru of bimetallic catalytic active component
Mass content is 2.38wt%~4.85wt%；The mass content of Au is 3.13wt%~5.87wt%；The mass content of Pd is
3.61wt%~5.17wt%.
The present invention is applied to CO using the Cu-BTC assemble nanometer metal solid catalyst prepared2With amine/H2It is catalytically conveted to
The reaction of N- benzamide compounds, by CO2With amine/H2One-step synthesis N- benzamide compounds.Catalysis reaction is in autoclave reaction under high pressure
It is carried out in device, is firstly added the Cu-BTC assemble nanometer metal solid catalyst of liquid amine and activation, is then charged with CO2And H2It is (excellent
It is 1 to select volume ratio:1) mixed gas, (preferably 100-160 DEG C) is reacted under certain reaction temperature, finally obtains N- formyls
Amine compounds.The result shows that the Cu-BTC assemble nanometer metallic catalysts prepared have good catalytic performance and N- formamides
The selectivity (selectivity is not less than 96%) of object is closed, and the catalyst after reaction can be readily separated and recycle, and have very
Good repetitive cycling performance.
Cu-BTC assemble nanometer metallic catalysts prepared by the present invention have following remarkable advantage：
(1) in the preparation process of Cu-BTC assemble nanometer metallic catalysts, as a result of unique ultrasonic technology
With the mild restoring method of ethyl alcohol so that be assembled in the catalytic activity group such as Ru, Au, Pd, Ru-Au, Ru-Pd, Au-Pd in Cu-BTC
Point, the nano particle of high dispersive is formd, this not only increases the activity of catalyst, and can be to avoid being catalyzed in reaction process
The aggregation and loss of active component greatly improve the activity and stability of catalyst.
(2) solid heterogeneous catalyst of the Cu-BTC material assemble nanometer metals prepared, in CO2With amine/H2N- formylateds
After reaction, the separating technology of catalyst and product is fairly simple, therefore has important industrial application value.
Specific implementation mode
With reference to embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1
(1) Cu (NO of 14.5g are weighed3)2.3H2O (0.06mol) is dissolved in 85.5g deionized waters, and nitric acid copper mass is made
A concentration of 11.3% solution；It weighs trimesic acid 8.4g (0.04mol) and is dissolved in 91.6g ethyl alcohol and N, N-dimethylformamide
(DMF) (mass ratio 1:1) in mixed solution, the solution that trimesic acid mass concentration is 8.4% is made.It, will under stirring
Copper nitrate solution and trimesic acid solution are added drop-wise in reactor, and the wherein metal ion of copper nitrate and trimesic acid rubs
You are than being 3：2.It is sufficiently stirred, then the ultrasound 40min under 100W ultrasonic powers, is then centrifuged for detaching, with deionized water and second
Alcohol washs, and is dried in vacuo 12 hours at 60 DEG C, you can blue powder Cu-BTC materials are made, are denoted as Cu-BTC1.
(2) Cu-BTC1 for weighing 20.0g is dissolved in 80.0g ethyl alcohol, and point that Cu-BTC mass concentrations are 20.0% is made
Dispersion liquid is denoted as A1 liquid.Weigh the RuCl of 2.1g3It is dissolved in the mixed liquor (mass ratio 1 of the alcohol-water of 98.0g:1) Ru matter, is made
The metal front liquid solution for measuring a concentration of 1.02%, is denoted as B1 liquid.Under stirring, B1 drops are added in A1 liquid, are sufficiently stirred, so
Afterwards under 50W ultrasonic powers, ultrasonic 60min, during which metal ion gradually can mildly be restored by ethyl alcohol, and complete Cu-BTC
The process of middle assemble nanometer metal.It after filtering, is washed with deionized water and ethyl alcohol, is dried in vacuo 12 hours at 60 DEG C, as
4.85wt%Ru/Cu-BTC solid catalysts obtained.
(3) in 100mL autoclave high-pressure reactors, 5mL aniline is added, the 4.85wt%Ru/Cu- of preparation is then added
BTC solid catalyst 0.002g, are then charged with the CO of 2.5MPa2And H2(volume ratio 1:1) mixed gas, then at 150 DEG C
Reaction 18 hours.It after the completion of reaction, is determined by chromatography, the conversion ratio of aniline is 56.6%, the selection of formanilide
Property is 97.2%.
Embodiment 2
(1) Cu (NO of 10.9g are weighed3)2.3H2O (0.045mol) is dissolved in 89.1g deionized waters, and it is copper that nitric acid is made
Measure a concentration of 8.5% solution；It weighs trimesic acid 6.3g (0.03mol) and is dissolved in 43.7g ethyl alcohol and N, N-dimethylformamide
(DMF) (mass ratio 1:1) in mixed solution, the solution that trimesic acid mass concentration is 12.6% is made.It, will under stirring
Copper nitrate solution and trimesic acid solution are added drop-wise in reactor, and the wherein metal ion of copper nitrate and trimesic acid rubs
You are than being 3：2.It is sufficiently stirred, then the ultrasound 30min under 150W ultrasonic powers, is then centrifuged for detaching, with deionized water and second
Alcohol washs, and is dried in vacuo 12 hours at 60 DEG C, you can blue powder Cu-BTC materials are made, are denoted as Cu-BTC2.
(2) Cu-BTC2 for weighing 25.0g is dissolved in dispersion 75.0g ethyl alcohol, Cu-BTC mass concentrations 25.0% is made
Dispersion liquid is denoted as A2 liquid.Weigh the HAuCl of 2.7g4It is dissolved in the mixed liquor (mass ratio 1 of 96.6g alcohol-waters:1) Au, is made
Mass content is the metal front liquid solution of 1.56wt%, is denoted as B2 liquid.Under stirring, B2 drops are added in A2 liquid, are fully stirred
It mixes, then under 80W ultrasonic powers, ultrasonic 55min, during which metal ion gradually can mildly be restored by ethyl alcohol, and be completed
The process of assemble nanometer metal in Cu-BTC.It after filtering, is washed with deionized water and ethyl alcohol, it is small that 12 is dried in vacuo at 60 DEG C
When, 5.87wt%Au/Cu-BTC solid catalysts as obtained.
(3) in 100mL autoclave high-pressure reactors, 5mL aniline is added, the 5.87wt%Au/Cu- of preparation is then added
BTC solid catalyst 0.003g, are then charged with the CO of 3.5MPa2And H2(volume ratio 1:1) mixed gas, then at 140 DEG C
Reaction 16 hours.It after the completion of reaction, is determined by chromatography, the conversion ratio of aniline is 58.2%, the selection of formanilide
Property is 98.5%.
Embodiment 3
(1) Cu (NO of 18.1g are weighed3)2.3H2O (0.075mol) is dissolved in 81.9g deionized waters, and it is copper that nitric acid is made
Measure a concentration of 14.1% solution；It weighs trimesic acid 10.5g (0.05mol) and is dissolved in 89.5g ethyl alcohol and N, N dimethyl formyl
Amine (DMF) (mass ratio 1:1) in mixed solution, the solution that trimesic acid mass concentration is 10.5% is made.Under stirring,
Copper nitrate solution and trimesic acid solution are added drop-wise in reactor, wherein the metal ion of copper nitrate and trimesic acid
Molar ratio is 3：2.Be sufficiently stirred, then the ultrasound 50min under 120W ultrasonic powers, is then centrifuged for detaching, with deionized water and
Ethyl alcohol washs, and is dried in vacuo 12 hours at 60 DEG C, you can blue powder Cu-BTC materials are made, are denoted as Cu-BTC3.
(2) Cu-BTC3 for weighing 22.0g is dissolved in dispersion 78.0g ethyl alcohol, and it is 22.0% that Cu-BTC mass concentrations, which are made,
Dispersion liquid, be denoted as A3 liquid.Weigh the PdCl of 2.0g2It is dissolved in the mixed liquor (mass ratio 1 of 98.0g alcohol-waters:1) Pd, is made
Mass content is the metal front liquid solution of 1.20wt%, is denoted as B3 liquid.Under stirring, B3 drops are added in A3 liquid, are fully stirred
It mixes, then under 60W ultrasonic powers, ultrasonic 60min, during which metal ion gradually can mildly be restored by ethyl alcohol, and be completed
The process of assemble nanometer metal in Cu-BTC.It after filtering, is washed with deionized water and ethyl alcohol, it is small that 12 is dried in vacuo at 60 DEG C
When, 5.17wt%Pd/Cu-BTC solid catalysts as obtained.
(3) in 100ml autoclave high-pressure reactors, 5mL aniline is added, the 5.17wt%Pd/Cu- of preparation is then added
BTC solid catalyst 0.003g, are then charged with the CO of 3.0MPa2And H2(volume ratio 1:1) mixed gas, then at 160 DEG C
Reaction 18 hours.It after the completion of reaction, is determined by chromatography, the conversion ratio of aniline is 52.9%, the selection of formanilide
Property is 96.8%.
Embodiment 4
(1) Cu (CH of 12.0g are weighed3COO)2.H2O (0.06mol) is dissolved in 88.0g deionized waters, and it is copper that acetic acid is made
Measure a concentration of 10.9% solution；It weighs trimesic acid 4.2g (0.02mol) and is dissolved in 45.8g ethyl alcohol and N, N dimethyl formyl
Amine (DMF) (mass ratio 1:1) in mixed solution, the solution that trimesic acid mass concentration is 8.4% is made.Under stirring,
Under stirring, acetic acid copper solution and trimesic acid solution are added drop-wise in reactor, wherein the metal ion of copper acetate and equal benzene
The molar ratio of tricarboxylic acid is 3：2.It is sufficiently stirred, then the ultrasound 40min under 150W ultrasonic powers, is then centrifuged for detaching, spend
Ionized water and ethyl alcohol washing, are dried in vacuo 12 hours, you can blue powder Cu-BTC materials are made, are denoted as Cu- at 60 DEG C
BTC4。
(2) the Cu-BTC4 materials for weighing 20.0g, are dissolved in 80.0g ethyl alcohol, and it is 20.0% that Cu-BTC mass concentrations, which are made,
Dispersion liquid, be denoted as A4 liquid；Weigh the RuCl of 1.5g3It is dissolved in the mixed liquor (mass ratio 1 of the alcohol-water of 48.5g:1) it, is made
The metal front liquid solution that Ru mass concentrations are 1.46%, is denoted as B4 liquid；Weigh the HAuCl of 1.2g4It is dissolved in 48.8g alcohol-waters
Mixed liquor (mass ratio 1:1) the metal front liquid solution that Au mass contents are 1.39wt%, is made, is denoted as B4 ' liquid.Stirring
Under, B4 liquid and B4 ' drops are added in A4 liquid, are sufficiently stirred, then under 100W ultrasonic powers, ultrasonic 55min, during which metal
Ion gradually can mildly be restored by ethyl alcohol, and complete the process of assemble nanometer metal in Cu-BTC.After filtering, deionization is used
Water and ethyl alcohol washing are dried in vacuo 12 hours at 60 DEG C, and 3.41wt%Ru-3.25wt%Au/Cu-BTC as obtained is solid
Body catalyst.
(3) in 100ml autoclave high-pressure reactors, 5mL aniline is added, the 3.41wt%Ru- of preparation is then added
3.25wt%Au/Cu-BTC solid catalyst 0.002g, are then charged with the CO of 4.5MPa2And H2(volume ratio 1:1) gaseous mixture
Then body reacts 16 hours at 150 DEG C.After the completion of reaction, being determined by chromatography, the conversion ratio of aniline is 60.5%,
The selectivity of formanilide is 98.3%.
Embodiment 5
(1) Cu (CH of 9.0g are weighed3COO)2.H2O (0.045mol) is dissolved in 91.0g deionized waters, and it is copper that acetic acid is made
Measure a concentration of 8.2% solution；It weighs trimesic acid 6.3g (0.03mol) and is dissolved in 43.7g ethyl alcohol and N, N-dimethylformamide
(DMF) (mass ratio 1:1) in mixed solution, the solution that trimesic acid mass concentration is 12.6% is made.It, will under stirring
Acetic acid copper solution and trimesic acid solution are added drop-wise in reactor, and the wherein metal ion of copper acetate and trimesic acid rubs
You are than being 3：2.It is sufficiently stirred, then the ultrasound 50min under 100W ultrasonic powers, is then centrifuged for detaching, with deionized water and second
Alcohol washs, and is dried in vacuo 12 hours at 60 DEG C, you can blue powder Cu-BTC materials are made, are denoted as Cu-BTC5.
(2) Cu-BTC5 for weighing 25.0g is dissolved in dispersion 75.0g ethyl alcohol, Cu-BTC mass concentrations 25.0% is made
Dispersion liquid is denoted as A5 liquid；Weigh the RuCl of 1.3g3It is dissolved in the mixed liquor (mass ratio 1 of 48.7g alcohol-waters:1) Ru matter, is made
The metal front liquid solution for measuring a concentration of 1.26%, is denoted as B5 liquid；Weigh the PdCl of 1.6g2It is dissolved in the mixing of 48.4g alcohol-waters
Liquid (mass ratio 1:1) the metal front liquid solution of Pd mass contents 1.92wt%, is made, is denoted as B5 ' liquid.Under stirring, by B5
Liquid and B5 ' are added drop-wise in A5 liquid, are sufficiently stirred, and then under 80W ultrasonic powers, ultrasonic 60min, during which metal ion can be by
Ethyl alcohol gradually mildly restores, and completes the process of assemble nanometer metal in Cu-BTC.After filtering, washed with deionized water and ethyl alcohol
It washs, is dried in vacuo at 60 DEG C 12 hours, 2.38wt%Ru-3.61wt%Pd/Cu-BTC solid catalysts as obtained.
(3) in 100ml autoclave high-pressure reactors, 5mL aniline is added, the 2.38wt%Ru- of preparation is then added
3.61wt%Pd/Cu-BTC solid catalyst 0.002g, are then charged with the CO of 4.0MPa2And H2(volume ratio 1:1) gaseous mixture
Then body reacts 17 hours at 160 DEG C.After the completion of reaction, being determined by chromatography, the conversion ratio of aniline is 59.2%,
The selectivity of formanilide is 98.6%.
Embodiment 6
(1) Cu (CH of 15.0g are weighed3COO)2.H2O (0.075mol) is dissolved in 85.0g deionized waters, and copper acetate is made
The solution that mass concentration is 13.6%；It weighs trimesic acid 10.5g (0.05mol) and is dissolved in 89.5g ethyl alcohol and N, N dimethyl first
Amide (DMF) (mass ratio 1:1) in mixed solution, the solution that trimesic acid mass concentration is 10.5% is made.Stirring
Under, copper nitrate solution and trimesic acid solution are added drop-wise in reactor, the wherein metal ion of copper nitrate and equal benzene front three
The molar ratio of acid is 3：2.It is sufficiently stirred, then the ultrasound 50min under 120W ultrasonic powers, is then centrifuged for detaching, uses deionization
Water and ethyl alcohol washing, are dried in vacuo 12 hours, you can blue powder Cu-BTC materials are made, are denoted as Cu-BTC6 at 60 DEG C.
(2) Cu-BTC6 for weighing 22.0g is dissolved in dispersion 78.0g ethyl alcohol, Cu-BTC mass concentrations 22.0% is made
The dispersion liquid of (20%~25%) is denoted as A6 liquid；Weigh the HAuCl of 1.1g4It is dissolved in the mixed liquor (mass ratio of 48.9g alcohol-waters
It is 1:1) the metal front liquid solution that Au mass contents are 1.27wt%, is made, is denoted as B6 liquid；Weigh the PdCl of 1.5g2It is dissolved in
Mixed liquor (the mass ratio 1 of 48.3g alcohol-waters:1) the metal front liquid solution of Pd mass contents 1.80wt%, is made, is denoted as
B6 ' liquid.Under stirring, B6 liquid and B6 ' are added drop-wise in A6 liquid, are sufficiently stirred, then under 100W ultrasonic powers, ultrasonic 60min,
Period metal ion gradually can mildly be restored by ethyl alcohol, and complete the process of assemble nanometer metal in Cu-BTC.After filtering,
It is washed, is dried in vacuo at 60 DEG C 12 hours with deionized water and ethyl alcohol, 3.13wt%Au-3.82wt%Pd/ as obtained
Cu-BTC solid catalysts.
(3) in 100ml autoclave high-pressure reactors, 5mL aniline is added, the 3.13wt%Au- of preparation is then added
3.82wt%Pd/Cu-BTC solid catalyst 0.003g, are then charged with the CO of 3.5MPa2And H2(volume ratio 1:1) gaseous mixture
Then body reacts 18 hours at 150 DEG C.After the completion of reaction, being determined by chromatography, the conversion ratio of aniline is 58.8%,
The selectivity of formanilide is 98.2%.
Claims (10)
1. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst, which is characterized in that include the following steps：
(1) Cu-BTC material preparations：It weighs a certain amount of copper nitrate or copper acetate is dissolved in deionized water, copper nitrate or vinegar is made
Sour copper solution；Weigh a certain amount of trimesic acid (H3BTC it) is dissolved in N, the mixing of N-dimethylformamide (DMF) and ethyl alcohol is molten
In liquid, trimesic acid solution is made；Copper nitrate or acetic acid copper solution and trimesic acid solution are added drop-wise to reaction under stirring
In device, wherein the molar ratio of the metal ion of copper nitrate or copper acetate and trimesic acid is 3：2, it is sufficiently stirred, then exists
Ultrasound 30min~50min, is then centrifuged for detaching, be washed with deionized water and ethyl alcohol under 100W~150W ultrasonic powers, and vacuum is dry
It is dry, you can blue powder Cu-BTC materials are made；
(2) prepared by Cu-BTC assemble nanometers metallic catalyst：A certain amount of Cu-BTC materials are weighed, dispersion in ethanol, is made
Cu-BTC dispersion liquids are denoted as A liquid；One or both of a certain amount of ruthenic chloride, gold chloride, palladium bichloride are weighed, ethyl alcohol-is dissolved in
In the mixed solution of water, metal front liquid solution is made, is denoted as B liquid；Under stirring, B drops are added in A liquid, are sufficiently stirred, so
Afterwards under 50W~100W ultrasonic powers, ultrasonic 50min~60min, during which metal ion can mildly be restored by ethyl alcohol, and
Complete the process of assemble nanometer metal in Cu-BTC.Then it filters, washed with deionized water and ethyl alcohol, be dried in vacuo, as make
The Cu-BTC assemble nanometer metal solid catalyst obtained.
2. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst described in accordance with the claim 1, which is characterized in that step
Suddenly (1) copper nitrate or copper acetate concentration of polymer solution are 8%~15%.
3. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst described in accordance with the claim 1, which is characterized in that step
Suddenly N in (1), N-dimethylformamide (DMF) and ethyl alcohol mass ratio are 1:1.
4. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst described in accordance with the claim 1, which is characterized in that step
Suddenly (1) trimesic acid concentration of polymer solution is 8%~15%.
5. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst described in accordance with the claim 1, which is characterized in that step
Suddenly (2) Cu-BTC dispersion liquid mass concentrations are 20%~25%.
6. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst described in accordance with the claim 1, which is characterized in that step
Suddenly (2) metal precursor solution quality percent concentration 1%~2%.
7. a kind of preparation method of Cu-BTC assemble nanometers metallic catalyst described in accordance with the claim 1, which is characterized in that
In Cu-BTC assemble nanometer metal solid catalyst no matter monometallic or bimetallic catalytic active component, the mass content of Ru is
2.38wt%~4.85wt%；The mass content of Au is 3.13wt%~5.87wt%；The mass content of Pd be 3.61wt%~
5.17wt%.
8. the Cu-BTC assemble nanometer metallic catalysts being prepared according to claim 1-7 any one of them preparation methods.
9. the Cu-BTC assemble nanometer metallic catalysts being prepared according to claim 1-7 any one of them preparation methods
Using applied to CO2With amine/H2It is catalytically conveted to the reaction of N- benzamide compounds, by CO2With amine/H2One-step synthesis N- formyls
Amine compounds.
10. according to the application of claim 9, which is characterized in that catalysis reaction carries out in autoclave high-pressure reactor, is firstly added
The Cu-BTC assemble nanometer metal solid catalyst of liquid amine and activation, is then charged with CO2And H2Volume ratio is 1:1 gaseous mixture
Body is reacted at 100-160 DEG C of certain reaction temperature, finally obtains N- benzamide compounds.
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