CN103949286B - A kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage - Google Patents
A kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage Download PDFInfo
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Abstract
The invention discloses a kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage. The preparation method of this catalyst comprises the steps: that metallic organic framework MOFs is scattered in solvent by (1), is then added thereto to noble metal nano particles, is stirred at room temperature, centrifugal, obtains loaded catalyst MOFs noble metal; (2) catalyst that step (1) obtains is utilized solvent wash, it is subsequently adding stabilizer and solvent, add slaine and part after being uniformly dispersed, react when solvent thermal, obtain the MOFs noble metal MOFs catalyst for selective hydrogenation with nucleocapsid structure. Catalyst dispersity prepared by the present invention is good, and selectivity of product is high, and catalysis activity is good, and can recycle easily, it is adaptable to selective catalytic hydrogenation reacts.
Description
Technical field
The present invention relates to a kind of for the MOFs noble metal MOFs catalyst of selective hydrogenation, preparation method and its usage, wherein, be specifically related to a kind of MOFsPtMOFs catalyst with nucleocapsid structure.
Background technology
Metallic organic framework (MetalOrganicFrameworks, MOFs), is a kind of crystallinity porous material assembled by metal or metal cluster and multiple tooth organic ligand. Owing to such material has great specific surface area, the pore structure of high-sequential, and form, hole size is simply adjustable, MOFs material causes broad interest at catalytic field in recent years. Existing bibliographical information (Chem.Soc.Rev., 2012,41,5262��5284) is using MOF as catalyst carrier, and the various metal nanoparticle of load obtains multiphase load type catalyst, and such heterogeneous catalyst can realize reusing easily. CN103418239A discloses a kind of with metal-organic framework materials for catalyst selectivity catalysis reduction elimination nitrogen oxides. The preparation method that CN103191778A discloses a kind of platinum based catalyst with metallic organic framework load, adopt microwave technology and gentle reducing agent that catalytic active component is uniformly dispersed in catalyst surface, the catalyst granules obtained of the method is little, is evenly distributed, and electro-chemical activity is high. CN103008012A discloses preparation method and the application of a kind of metallo-organic framework material loading platinum catalyst, by impregnating and the loaded catalyst of sodium formate reduction preparation high degree of dispersion.
Activity, selectivity and stability are the topmost performance indications of catalyst, and the performance of catalyst is usual and its structure is closely related. Noble metal nano particles is little due to size, has significantly high surface energy, even if load is on carrier, is easy to occur to migrate reunite, causes that catalysis activity reduces in catalytic reaction process. Covering property catalyst with core-casing structure is due to the protective effect of shell, and noble metal nano patent is less likely to occur to reunite, good stability, and catalysis activity is high. Simultaneously, owing to the selectivity of shell passes through the steric effect of effect and uniqueness, reactant molecule first must can be only achieved catalytic active center with particular space configuration through shell, and therefore the restriction effect of this uniqueness of Shell Materials serves the effect improving catalytic selectivity. Metallic organic framework catalyst with core-casing structure is adopted to realize high selective catalysis reaction document has no report.
Summary of the invention
For the problem of prior art, an object of the present invention is in that the preparation method providing a kind of MOFPtMOF catalyst with nucleocapsid structure, and this catalyst can be used for cinnamic aldehyde selective hydrogenation and prepares the reaction of cinnamyl alcohol. This catalyst has selectivity height, and activity is good, the feature that stability is high.
In order to achieve the above object, present invention employs following technical scheme:
The preparation method of a kind of MOFs noble metal MOFs catalyst for selective hydrogenation, described method comprises the steps:
(1) metallic organic framework MOFs is scattered in solvent, is then added thereto to noble metal nano particles, is stirred at room temperature, centrifugal, obtain loaded catalyst MOFs noble metal;
(2) catalyst that step (1) obtains is utilized solvent wash, it is subsequently adding stabilizer and solvent, add trivalent metal salt and part after being uniformly dispersed, react when solvent thermal, obtain the MOFs noble metal MOFs catalyst for selective hydrogenation with nucleocapsid structure.
Preferably, described noble metal is selected from Pt.
Preferably, the preparation method of described noble metal nano particles comprises the steps:
A noble metal precursor body is dissolved in the solvent containing stabilizer by (), add reducing agent;
B () is heated to reflux, obtain noble metal nano particles; Wherein, described solvent is ethanol or/and water.
Preferably, in step (a), noble metal is Pt, and noble metal precursor body is selected from H2PtCl4��H2PtCl6��K2PtCl6��Na2PtCl6��K2PtCl4Or Na2PtCl4In the mixture of any one or at least two. Described mixture such as H2PtCl4And H2PtCl6Mixture, K2PtCl6And Na2PtCl6Mixture, K2PtCl4And Na2PtCl4Mixture, H2PtCl4And H2PtCl6Mixture, K2PtCl6��Na2PtCl6��K2PtCl4And Na2PtCl4Mixture.
Preferably, stabilizer described in step (a) is the mixture of any one or at least two in PVP, PEG, PVA or PAA. The mixture of described mixture such as PVP and PEG, PEG, PVA and PAA mixture, PVP, PEG, PVA and PAA mixture.
Preferably, the mol ratio of stabilizer described in step (a) and noble metal precursor body is 100:1��5:1, for instance 95:1,90:1,85:1,80:1,75:1,70:1,65:1,60:1,55:1,50:1,45:1,40:1,35:1,30:1,25:1,20:1,15:1 or 10:1.
Preferably, solvent described in step (a) is second alcohol and water, and described ethanol accounts for the volume ratio of solvent and is 0��100% and do not include 0 and 100%. The volume ratio of described ethanol is as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%.
That is, described solvent can be individually for ethanol, it is also possible to is individually for water, it is also possible to for the mixture of second alcohol and water, wherein, when solvent is the mixture of second alcohol and water, ethanol accounts for the volume ratio of solvent and is 0��100% and do not include 0 and 100%.
Preferably, reducing agent described in step (a) can be the mixture of any one or at least two in methanol, ethanol, propanol, sodium borohydride or ascorbic acid. The mixture of described mixture such as methanol and ethanol, the mixture of propanol, sodium borohydride and ascorbic acid, the mixture of methanol, ethanol, propanol, sodium borohydride and ascorbic acid.
Preferably, the time being heated to reflux described in step (a) is 3��24h, for instance 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h.
Preferably, the preparation method of described metallic organic framework MOFs comprises the steps:
C slaine and part are dissolved in solvent by (), obtain mixed solution;
D the mixed solution obtained is obtained by reacting metallic organic framework MOFs by () when solvent thermal.
Preferably, the ratio of the described slaine of step (c) and part is 3:1��1:3, for instance 2.7:1,2.4:1,2.1:1,1.8:1,1.5:1,1.2:1,0.9:1,0.6:1,0.3:1,1:1,1:0.3,1:0.6,1:0.9,1:1.2,1:1.5,1:1.8,1:2.1,1:2.4 or 1:2.7.
Preferably, the mixture of the described solvent of step (c) any one or at least two in DMF, methanol, ethanol or water.
Preferably, the reaction temperature of the described solvent thermal condition of step (d) is 110��220 DEG C, and the response time is 8��24h.
The reaction temperature of described solvent thermal reaction is such as 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C or 215 DEG C.
The response time of described solvent thermal reaction is such as 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h or 23.5h.
Preferably, step (1) and step (2) described solvent are independently selected from the mixture of any one in DMF, methanol, ethanol or water or at least two.
Preferably, step (2) described stabilizer is the mixture of any one or at least two in PVP, PEG, PVA or PAA. The mixture of described mixture such as PVP and PEG, PEG, PVA and PAA mixture, PVP, PEG, PVA and PAA mixture.
Preferably, the mol ratio of stabilizer described in step (2) and MOFs is 10:1��1:1, for instance 9.5:1,9:1,8.5:1,8:1,7.5:1,7:1,6.5:1,6:1,5.5:1,5:1,4.5:1,4:1,3.5:1,3:1,2.5:1,2:1 or 1.5:1.
Preferably, step (2) and the described slaine of step (c) all independently be MClxOr/and M (NO3)x, x=2 or 3.
Preferably, the combination of the described M any one or at least two in Fe, Co, Ni, Cu, Cr, Al, V, Ga or In.
Preferably, step (2) and the described part of step (c) are all independently selected from the mixture of any one in unsubstituted p-phthalic acid, the p-phthalic acid being substituted with a substituent or biphenyl dicarboxylic acid or at least two.The combination of the described substituent group any one or at least two in amino, carboxyl, sulfonic group, hydroxyl, alkyl, halogen or sulfydryl.
Preferably, the mol ratio of step (2) described slaine and part is 3:1��1:3, for instance 2.7:1,2.4:1,2.1:1,1.8:1,1.5:1,1.2:1,0.9:1,0.6:1,0.3:1,1:1,1:0.3,1:0.6,1:0.9,1:1.2,1:1.5,1:1.8,1:2.1,1:2.4 or 1:2.7.
Preferably, the reaction temperature of the described solvent thermal condition of step (2) is 110��220 DEG C, and the response time is 8��24h.
The reaction temperature of described solvent thermal reaction is such as 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C or 215 DEG C.
The response time of described solvent thermal reaction is such as 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h or 23.5h.
The two of the purpose of the present invention are in that to provide a kind of MOFs noble metal MOFs catalyst, and it is prepared by method as defined above.
The three of the purpose of the present invention are in that to provide the purposes of a kind of MOFs noble metal MOFs catalyst as above, and it prepares the reaction of cinnamyl alcohol for cinnamic aldehyde selective hydrogenation.
The performance evaluation of above-mentioned catalyst carries out in magnetically-actuated autoclave (Foochow kreis test equipment company limited) evaluating apparatus, etoh solvent 50mL, cinnamic aldehyde 2mL, reacting gas is hydrogen (2MPa), rotating speed 200rpm, reaction temperature 25��80 DEG C, response time 1��24h.
Compared with the prior art, there is advantages that
Compared with existing loaded catalyst preparation method, cinnamic aldehyde selective hydrogenation is had significantly high selectivity, activity and stability by nucleocapsid structure MOFs noble metal MOFs nanocatalyst prepared by the present invention in a mild condition, and cinnamyl alcohol selectivity is up to 95%. Material science, nanotechnology, Catalyat Engideering are combined by the present invention, it is proposed that prepare the new approaches of catalyst, have important using value.
Accompanying drawing explanation
Fig. 1 is the TEM electromicroscopic photograph of the nano platinum particle obtained in the embodiment of the present invention 1.
Fig. 2 is the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFsPtMOFs obtained in the embodiment of the present invention 2.
Fig. 3 is the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFsPtMOFs obtained in the embodiment of the present invention 3.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail. It will be understood to those of skill in the art that following example are only the preferred embodiments of the present invention, in order to be more fully understood that the present invention, thus should not be taken as limiting the scope of the invention.
Experimental technique in following embodiment, if no special instructions, is conventional method; Experiment material used, if no special instructions, is and is purchased available from routine biochemistry chemical reagent work.
Centrifugal employing table model high speed centrifuge (XiangYiH-1650) in following example; TEM transmission electron microscope photo adopts TecnaiG2F20S-TWIN transmission electron microscope to obtain.
Embodiment 1:
By the H of 0.5mmolPVP and 0.1mmol2PtCl6It is dissolved in 95mL ethanol and 5mL water, after fully dissolving, this solution is heated to back flow reaction 3h, obtains nano platinum particle.This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 3mmolFeCl3It is dissolved in 30mLDMF with 1mmol2-amino p-phthalic acid, then this solution is transferred in polytetrafluoroethyllining lining, in 110 DEG C of solvent thermal when, react 24h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 10mLDMF, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPVP, 0.9mmolFeCl3, 0.3mmol2-amino p-phthalic acid and 10mLDMF, react 10h in 110 DEG C of solvent thermal when and obtain nucleocapsid structure MOFsPtMOFs catalyst.
The cinnamic aldehyde selective hydrogenation performance test of catalyst: carry out cinnamic aldehyde selective hydrogenation performance test in magnetically-actuated autoclave, catalyst amount 1.0%mol, reaction temperature 25 DEG C, reaction pressure 2MPa, mixing speed 200rpm, response time 3h.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Fig. 1 provides the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFsPtMOFs obtained in the embodiment of the present invention 1.
Embodiment 2:
By the K of 0.5mmolPEG and 0.1mmol2PtCl6It is dissolved in 5mL methanol and 95mL water, after fully dissolving, this solution is heated to back flow reaction 24h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 1mmolFeCl2With 0.4mmol2,5-dihydric para-phthalic acid is dissolved in 30mLDMF-3mL methanol, then this solution is transferred in polytetrafluoroethyllining lining, in 120 DEG C of solvent thermal when, reacts 20h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 30mLDMF, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPEG, 0.3mmolCo (NO3)2With 0.1mmol2,5-dihydric para-phthalic acid is dissolved in 8mLDMF-1mL methanol, in 110 DEG C of solvent thermal when, reacts 8h obtain nucleocapsid structure MOFsPtMOFs catalyst.
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Fig. 2 is the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFsPtMOFs obtained in the embodiment of the present invention 3.
Embodiment 3:
By the H of 10mmolPVP and 0.1mmol2PtCl6It is dissolved in 95mL propanol and 5mL water, after fully dissolving, this solution is heated to back flow reaction 3h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 1mmolCr (NO3)3It is dissolved in 10mL water with 1mmol p-phthalic acid, then this solution is transferred in polytetrafluoroethyllining lining, in 220 DEG C of solvent thermal when, react 10h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 10mL water, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPVP, 0.5mmolCr (NO3)3, 0.5mmol p-phthalic acid and 5mL water, react 8h in 200 DEG C of solvent thermal when and obtain nucleocapsid structure MOFsPtMOFs catalyst
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Fig. 3 is the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFsPtMOFs obtained in the embodiment of the present invention 3.
Embodiment 4:
By the Na of 2mmolPVA and 0.1mmol2PtCl6It is dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution is heated to back flow reaction 5h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 2mmolCr (NO3)3It is dissolved in 10mL water with 1mmol p-phthalic acid, then this solution is transferred in polytetrafluoroethyllining lining, in 200 DEG C of solvent thermal when, react 20h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 10mL water, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 0.3mmolPVP, 0.3mmolCr (NO3)3, 0.3mmol p-phthalic acid and 5mL water, react 8h in 180 DEG C of solvent thermal when and obtain nucleocapsid structure MOFsPtMOFs catalyst
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Embodiment 5:
By the K of 1mmolPVP and 0.1mmol2PtCl4It is dissolved in 90mL methanol and 10mL water, after fully dissolving, this solution is heated to back flow reaction 5h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 1mmolAlCl3It is dissolved in 30mLDMF with 2mmol2-amino p-phthalic acid, then this solution is transferred in polytetrafluoroethyllining lining, in 130 DEG C of solvent thermal when, react 24h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 30mLDMF, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPVP, 0.2mmolAlCl3, 0.4mmol2-amino p-phthalic acid is dissolved in 10mLDMF, reacts 8h and obtain nucleocapsid structure MOFsPtMOFs catalyst in 130 DEG C of solvent thermal when.
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Embodiment 6:
By the H of 1mmolPAA and 0.1mmol2PtCl6It is dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution is heated to back flow reaction 3h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 1mmolGaCl3It is dissolved in 30mLDMF with 1mmol2-amino p-phthalic acid, then this solution is transferred in polytetrafluoroethyllining lining, in 150 DEG C of solvent thermal when, react 24h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 30mLDMF, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPAA, 0.2mmolGaCl3, 0.4mmol2-amino p-phthalic acid is dissolved in 10mLDMF, reacts 8h and obtain nucleocapsid structure MOFsPtMOFs catalyst in 130 DEG C of solvent thermal when.
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Embodiment 7:
By the H of 1mmolPVP and 0.1mmol2PtCl6It is dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution is heated to back flow reaction 5h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 1mmolCo (NO3)2With 0.5mmol2,5-dihydric para-phthalic acid is dissolved in 10mLDMF-10mL ethanol-10mL water, then this solution is transferred in polytetrafluoroethyllining lining, in 110 DEG C of solvent thermal when, reacts 24h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 30mLDMF, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPVP, 0.4mmolCo (NO3)2With 0.2mmol2,5-dihydric para-phthalic acid is dissolved in 5mLDMF-5mL ethanol-5mL water, in 110 DEG C of solvent thermal when, reacts 8h obtain nucleocapsid structure MOFsPtMOFs catalyst.
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
Embodiment 8:
By the H of 1mmolPVP and 0.1mmol2PtCl6It is dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution is heated to back flow reaction 5h, obtains nano platinum particle. This solution is gone out solvent by rotary evaporation, is re-dispersed in DMF or water, standby.
By 1mmolNi (NO3)2With 0.5mmol2,5-dihydric para-phthalic acid is dissolved in 10mLDMF-10mL ethanol-10mL water, then this solution is transferred in polytetrafluoroethyllining lining, in 110 DEG C of solvent thermal when, reacts 24h obtain MOFs. By centrifugal for this MOFs5000rpm 8min, it is re-dispersed in 30mLDMF, in this solution, then adds Pt nanoparticle, 3h, 5000rpm centrifugal 8min is stirred at room temperature, obtains loaded catalyst MOFsPt. It is subsequently adding 1mmolPVP, 0.4mmolNi (NO3)2With 0.2mmol2,5-dihydric para-phthalic acid is dissolved in 5mLDMF-5mL ethanol-5mL water, in 110 DEG C of solvent thermal when, reacts 8h obtain nucleocapsid structure MOFsPtMOFs catalyst.
The cinnamic aldehyde selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic aldehyde selective hydrogenation results of property of catalyst is in Table 1.
The cinnamic aldehyde selective hydrogenation results of property of table 1 catalyst
| Embodiment | Cinnamic aldehyde conversion ratio (%) | Cinnamyl alcohol selectivity (%) | Cinnamyl alcohol productivity (%) |
| 1 | 85.5 | 96.4 | 82.4 |
| 2 | 86.1 | 95.0 | 81.8 |
| 3 | 85.7 | 92.6 | 79.4 |
| 4 | 84.9 | 91.5 | 77.7 |
| 5 | 83.6 | 92.0 | 76.9 |
| 6 | 85.8 | 91.7 | 78.7 |
| 7 | 82.7 | 95.6 | 79.1 |
| 8 | 80.3 | 94.2 | 75.6 |
In sum, the invention provides a kind of nucleocapsid structure MOFs noble metal MOFs nanocatalyst for cinnamic aldehyde selective hydrogenation. Compared with traditional supported catalysts preparation method, cinnamic aldehyde selective hydrogenation is had significantly high selectivity, activity and stability by nucleocapsid structure MOFs noble metal MOFs nanocatalyst prepared by the present invention in a mild condition.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, does not namely mean that the present invention has to rely on above-mentioned method detailed and could implement. The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope.
Claims (20)
1. the purposes for the MOFs noble metal MOFs catalyst of selective hydrogenation, it prepares the reaction of cinnamyl alcohol for cinnamic aldehyde selective hydrogenation, the preparation method of the described MOFs noble metal MOFs catalyst for selective hydrogenation, comprises the steps:
(1) metallic organic framework MOFs is scattered in solvent, is then added thereto to noble metal nano particles, is stirred at room temperature, centrifugal, obtain loaded catalyst MOFs noble metal;
(2) catalyst that step (1) obtains is utilized solvent wash, it is subsequently adding stabilizer and solvent, add slaine and part after being uniformly dispersed, react when solvent thermal, obtain the MOFs noble metal MOFs catalyst for selective hydrogenation.
2. purposes as claimed in claim 1, it is characterised in that described noble metal is selected from Pt.
3. purposes as claimed in claim 1 or 2, it is characterised in that the preparation method of described noble metal nano particles comprises the steps:
A noble metal precursor body is dissolved in the solvent containing stabilizer by (), add reducing agent;
B () is heated to reflux, obtain noble metal nano particles; Wherein, described solvent is ethanol or/and water.
4. purposes as claimed in claim 3, it is characterised in that in step (a), noble metal is Pt, and noble metal precursor body is selected from H2PtCl4��H2PtCl6��K2PtCl6��Na2PtCl6��K2PtCl4Or Na2PtCl4In the mixture of any one or at least two.
5. purposes as claimed in claim 3, it is characterised in that solvent described in step (a) is second alcohol and water, and described ethanol accounts for the volume ratio of solvent and is 0��100% and do not include 0 and 100%.
6. purposes as claimed in claim 3, it is characterised in that the mol ratio of stabilizer described in step (a) and noble metal precursor body is 100:1��5:1.
7. purposes as claimed in claim 3, it is characterised in that the mixture of any one or at least two in methanol, ethanol, propanol, sodium borohydride or ascorbic acid of the reducing agent described in step (a).
8. purposes as claimed in claim 3, it is characterised in that the time being heated to reflux described in step (b) is 3��24h.
9. the purposes as described in one of claim 1-2, it is characterised in that the preparation method of described metallic organic framework MOFs comprises the steps:
C slaine and part are dissolved in solvent by (), obtain mixed solution;
D the mixed solution obtained is obtained by reacting metallic organic framework MOFs by () when solvent thermal.
10. purposes as claimed in claim 9, it is characterised in that the mol ratio of the described slaine of step (c) and part is 3:1��1:3.
11. purposes as claimed in claim 9, it is characterised in that the mixture of the described solvent of step (c) any one or at least two in DMF, methanol, ethanol or water.
12. purposes as claimed in claim 9, it is characterised in that the reaction temperature of the described solvent thermal condition of step (d) is 110��220 DEG C, and the response time is 8��24h.
13. the purposes as described in one of claim 1-2, it is characterised in that step (1) and step (2) described solvent are independently selected from the mixture of any one in DMF, methanol, ethanol or water or at least two.
14. the purposes as described in one of claim 1-2, it is characterised in that described stabilizer is the mixture of any one or at least two in PVP, PEG, PVA or PAA.
15. the purposes as described in one of claim 1-2, it is characterised in that the mol ratio of stabilizer described in step (2) and MOFs is 10:1��1:1.
16. the purposes as described in one of claim 1-2, it is characterised in that described slaine is MClxOr/and M (NO3)x, x=2 or 3.
17. purposes as claimed in claim 16, it is characterised in that the combination of the described M any one or at least two in Fe, Co, Ni, Cu, Cr, Al, V, Ga or In.
18. the purposes as described in one of claim 1-2, it is characterized in that, the mixture of the described part any one or at least two in unsubstituted p-phthalic acid, the p-phthalic acid being substituted with a substituent or biphenyl dicarboxylic acid, the combination of the described substituent group any one or at least two in amino, carboxyl, sulfonic group, hydroxyl, alkyl, halogen or sulfydryl.
19. the purposes as described in one of claim 1-2, it is characterised in that the mol ratio of step (2) described slaine and part is 3:1��1:3.
20. the purposes as described in one of claim 1-2, it is characterised in that the reaction temperature of the described solvent thermal condition of step (2) is 110��220 DEG C, and the response time is 8��24h.
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