CN103949286A - MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof - Google Patents
MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a MOFs (Metal-Organic Frameworks)@noble metal@MOFs catalyst applicable to selective hydrogenation reaction, as well as a preparation method and an application of the catalyst. The preparation method of the catalyst comprises the following steps: (1) dispersing MOFs in a solvent, then adding noble metal nanoparticles into the solvent, stirring at the room temperature and centrifuging to obtain a supported catalyst-MOFs@noble metal; and (2) washing the catalyst obtained in the step (1) by using the solvent, then adding a stabilizer and the solvent, dispersing uniformly and then adding metal slat and ligands, reacting under solvothermal conditions to obtain a MOFs@noble metal@MOFs catalyst which has a core-shell structure and is applicable to the selective hydrogenation reaction. The catalyst prepared by adopting the preparation method is good in dispersion, high in product selectivity, good in catalytic activity, convenient to recycle and applicable to the selective catalytic hydrogenation reaction.
Description
Technical field
The present invention relates to a kind of MOFs@noble metal@MOFs catalyst, preparation method and its usage for selective hydrogenation, wherein, be specifically related to a kind of MOFs@Pt@MOFs catalyst with nucleocapsid structure.
Background technology
Metallic organic framework (Metal Organic Frameworks, MOFs) is a kind of crystallinity porous material being assembled by metal or metal cluster and multiple tooth organic ligand.Because such material has great specific area, the pore structure of high-sequential, and composition, hole size is simply adjustable, and 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 nanoparticles of load obtain multiphase load type catalyst, and such heterogeneous catalyst can be realized and reusing easily.CN103418239A discloses one and has removed nitrogen oxide taking metal-organic framework materials as catalyst selectivity catalytic reduction.CN103191778A discloses a kind of preparation method of the platinum based catalyst with metallic organic framework load, adopt microwave technology and gentle reducing agent that catalytic active component is dispersed in to catalyst surface uniformly, the catalyst granules obtaining of the method is little, is evenly distributed, and electro-chemical activity is high.CN103008012A discloses a kind of preparation method and application of metallic organic framework structural material load platinum catalyst, by the loaded catalyst of dipping and sodium formate reduction preparation high degree of dispersion.
Active, selective and stability is the topmost performance indications of catalyst, and the performance of catalyst is common and its structure is closely related.Noble metal nano particles, because size is little, has very high surface energy, even if load on carrier, is easy to occur migration and reunites in catalytic reaction process, causes catalytic activity to reduce.Covering property catalyst with core-casing structure is due to the protective effect of shell, and noble metal nano patent is not easy to reunite, good stability, and catalytic activity is high.Simultaneously, due to selective effect and the unique steric effect of seeing through of shell, reactant molecule must first see through shell with particular space configuration just can reach catalytic active center, and therefore the restriction of this uniqueness of Shell Materials has played the effect that improves catalytic selectivity.Adopt metallic organic framework catalyst with core-casing structure to realize in high selectivity catalytic reaction document and have no report.
Summary of the invention
For the problem of prior art, one of object of the present invention is to provide a kind of preparation method of the MOF@Pt@MOF catalyst with nucleocapsid structure, and this catalyst can be used for the reaction that cinnamyl alcohol is prepared in cinnamic acid selective hydrogenation.This catalyst has selective height, active good, the feature that stability is high.
In order to achieve the above object, the present invention has adopted following technical scheme:
For a preparation method for the MOFs@noble metal@MOFs catalyst of selective hydrogenation, described method comprises the steps:
(1) metallic organic framework MOFs is scattered in solvent, then adds wherein noble metal nano particles, stirring at room temperature, centrifugal, obtain loaded catalyst MOFs@noble metal;
(2) catalyst step (1) being obtained utilizes solvent wash, then add stabilizing agent and solvent, after being uniformly dispersed, add trivalent metal salt and part, under solvent heat condition, react, obtain having the MOFs@noble metal@MOFs catalyst for selective hydrogenation of 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 that contains stabilizing agent, adds reducing agent;
(b) add hot reflux, obtain noble metal nano particles; Wherein, described solvent is that ethanol is or/and water.
Preferably, in step (a), noble metal is Pt, and noble metal precursor body is selected from H
2ptCl
4, H
2ptCl
6, K
2ptCl
6, Na
2ptCl
6, K
2ptCl
4or Na
2ptCl
4in the mixture of any one or at least two kinds.Such as H of described mixture
2ptCl
4and H
2ptCl
6mixture, K
2ptCl
6and Na
2ptCl
6mixture, K
2ptCl
4and Na
2ptCl
4mixture, H
2ptCl
4and H
2ptCl
6mixture, K
2ptCl
6, Na
2ptCl
6, K
2ptCl
4and Na
2ptCl
4mixture.
Preferably, stabilizing agent described in step (a) is the mixture of any one or at least two kinds in PVP, PEG, PVA or PAA.The mixture of for example PVP of described mixture and PEG, the mixture of PEG, PVA and PAA, the mixture of PVP, PEG, PVA and PAA.
Preferably, described in step (a), the mol ratio of stabilizing agent and noble metal precursor body is 100:1～5:1, for example 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, described in step (a), solvent is second alcohol and water, and the volume ratio that described ethanol accounts for solvent is 0～100% and does not comprise 0 and 100%.The volume ratio of described ethanol is as being 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 separately ethanol, can be also separately water, can be also the mixture of ethanol and water, and wherein, when solvent is the mixture of second alcohol and water, the volume ratio that ethanol accounts for solvent is 0～100% and does not comprise 0 and 100%.
Preferably, reducing agent described in step (a) can be the mixture of any one or at least two kinds in methyl alcohol, ethanol, propyl alcohol, sodium borohydride or ascorbic acid.The mixture of for example methyl alcohol of described mixture and ethanol, the mixture of propyl alcohol, sodium borohydride and ascorbic acid, the mixture of methyl alcohol, ethanol, propyl alcohol, sodium borohydride and ascorbic acid.
Preferably, the time that adds hot reflux described in step (a) is 3～24h, for example 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, obtain mixed solution;
(d) mixed solution obtaining is reacted and obtains metallic organic framework MOFs under solvent heat condition.
Preferably, the ratio of the described slaine of step (c) and part is 3:1～1:3, for example 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 described solvent of step (c) is selected from the mixture of any one or at least two kinds in DMF, methyl alcohol, ethanol or water.
Preferably, the reaction temperature of the described solvent heat condition of step (d) is 110～220 DEG C, and the reaction time is 8～24h.
The reaction temperature of described solvent thermal reaction is for example 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 reaction time of described solvent thermal reaction is for example 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 the described solvent of step (2) are independently selected from the mixture of any one or at least two kinds in DMF, methyl alcohol, ethanol or water.
Preferably, the described stabilizing agent of step (2) is the mixture of any one or at least two kinds in PVP, PEG, PVA or PAA.The mixture of for example PVP of described mixture and PEG, the mixture of PEG, PVA and PAA, the mixture of PVP, PEG, PVA and PAA.
Preferably, described in step (2), the mol ratio of stabilizing agent and MOFs is 10:1～1:1, for example 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) are all MCl independently
xor/and M (NO
3)
x, x=2 or 3.
Preferably, described M is selected from the combination of any one or at least two kinds in Fe, Co, Ni, Cu, Cr, Al, V, Ga or In.
Preferably, step (2) and the described part of step (c) all independently selected from unsubstituted terephthalic acid (TPA), be substituted the mixture of any one or at least two kinds in terephthalic acid (TPA) or the biphenyl dicarboxylic acid that base replaces.Described substituting group is selected from the combination of any one or at least two kinds in amino, carboxyl, sulfonic group, hydroxyl, alkyl, halogen or sulfydryl.
Preferably, the mol ratio of the described slaine of step (2) and part is 3:1～1:3, for example 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 heat condition of step (2) is 110～220 DEG C, and the reaction time is 8～24h.
The reaction temperature of described solvent thermal reaction is for example 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 reaction time of described solvent thermal reaction is for example 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.
Two of object of the present invention is to provide a kind of MOFs@noble metal@MOFs catalyst, and it is prepared by method described above.
Three of object of the present invention is to provide a kind of purposes of MOFs@noble metal@MOFs catalyst as above, and it prepares the reaction of cinnamyl alcohol for cinnamic acid selective hydrogenation.
The performance evaluation of above-mentioned catalyst is carried out in magnetically-actuated autoclave (Foochow kreis test equipment Co., Ltd) evaluating apparatus, etoh solvent 50mL, cinnamic acid 2mL, reacting gas is hydrogen (2MPa), rotating speed 200rpm, 25～80 DEG C of reaction temperatures, reaction time 1～24h.
Compared with the prior art, the present invention has following beneficial effect:
Compared with existing loaded catalyst preparation method, to cinnamic acid, selective hydrogenation has very high selective, activity and stability to nucleocapsid structure MOFs@noble metal@MOFs nanocatalyst prepared by the present invention under temperate condition, and cinnamyl alcohol is selectively up to 95%.The present invention combines material science, nanometer technology, Catalyat Engideering, has proposed the new approaches of Kaolinite Preparation of Catalyst, has important using value.
Brief description of the drawings
Fig. 1 is the TEM electromicroscopic photograph of the nano platinum particle that obtains in the embodiment of the present invention 1.
Fig. 2 is the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFs@Pt@MOFs that obtains in the embodiment of the present invention 2.
Fig. 3 is the TEM electromicroscopic photograph of the catalyst with core-casing structure MOFs@Pt@MOFs that obtains 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 examples are only the preferred embodiments of the present invention, so that understand better the present invention, thereby should not be considered as limiting scope of the present 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 (XiangYi H-1650) in following examples; TEM transmission electron microscope photo adopts Tecnai G2F20S-TWIN transmission electron microscope to obtain.
Embodiment 1:
By the H of 0.5mmol PVP and 0.1mmol
2ptCl
6be dissolved in 95mL ethanol and 5mL water, after fully dissolving, this solution be heated to back flow reaction 3h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 3mmol FeCl
3be dissolved in 30mL DMF with the amino terephthalic acid (TPA) of 1mmol2-, then this solution be transferred in polytetrafluoroethyllining lining, under 110 DEG C of solvent heat conditions, react 24h and obtain MOFs.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 10mL DMF, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PVP, 0.9mmol FeCl
3, the amino terephthalic acid (TPA) of 0.3mmol2-and 10mL DMF react 10h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 110 DEG C of solvent heat conditions.
The cinnamic acid selective hydrogenation performance test of catalyst: carry out the performance test of cinnamic acid selective hydrogenation in magnetically-actuated autoclave, catalyst amount 1.0%mol, 25 DEG C of reaction temperatures, reaction pressure 2MPa, mixing speed 200rpm, reaction time 3h.
The cinnamic acid 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 MOFs@Pt@MOFs obtaining in the embodiment of the present invention 1.
Embodiment 2:
By the K of 0.5mmol PEG and 0.1mmol
2ptCl
6be dissolved in 5mL methyl alcohol and 95mL water, after fully dissolving, this solution be heated to back flow reaction 24h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 1mmol FeCl
2and 0.4mmol2,5-dihydric para-phthalic acid is dissolved in 30mL DMF-3mL methyl alcohol, then this solution is transferred in polytetrafluoroethyllining lining, reacts 20h and obtain MOFs under 120 DEG C of solvent heat conditions.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 30mLDMF, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PEG, 0.3mmol Co (NO
3)
2and 0.1mmol2,5-dihydric para-phthalic acid is dissolved in 8mL DMF-1mL methyl alcohol, reacts 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 110 DEG C of solvent heat conditions.
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid 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 MOFs@Pt@MOFs that obtains in the embodiment of the present invention 3.
Embodiment 3:
By the H of 10mmol PVP and 0.1mmol
2ptCl
6be dissolved in 95mL propyl alcohol and 5mL water, after fully dissolving, this solution be heated to back flow reaction 3h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 1mmol Cr (NO
3)
3be dissolved in 10mL water with 1mmol terephthalic acid (TPA), then this solution be transferred in polytetrafluoroethyllining lining, under 220 DEG C of solvent heat conditions, react 10h and obtain MOFs.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 10mL water, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PVP, 0.5mmol Cr (NO
3)
3, 0.5mmol terephthalic acid (TPA) and 5mL water react 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 200 DEG C of solvent heat conditions
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid 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 MOFs@Pt@MOFs that obtains in the embodiment of the present invention 3.
Embodiment 4:
By the Na of 2mmol PVA and 0.1mmol
2ptCl
6be dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution be heated to back flow reaction 5h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 2mmol Cr (NO
3)
3be dissolved in 10mL water with 1mmol terephthalic acid (TPA), then this solution be transferred in polytetrafluoroethyllining lining, under 200 DEG C of solvent heat conditions, react 20h and obtain MOFs.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 10mL water, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 0.3mmol PVP, 0.3mmol Cr (NO
3)
3, 0.3mmol terephthalic acid (TPA) and 5mL water react 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 180 DEG C of solvent heat conditions
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid selective hydrogenation results of property of catalyst is in table 1.
Embodiment 5:
By the K of 1mmol PVP and 0.1mmol
2ptCl
4be dissolved in 90mL methyl alcohol and 10mL water, after fully dissolving, this solution be heated to back flow reaction 5h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 1mmol AlCl
3be dissolved in 30mL DMF with the amino terephthalic acid (TPA) of 2mmol2-, then this solution be transferred in polytetrafluoroethyllining lining, under 130 DEG C of solvent heat conditions, react 24h and obtain MOFs.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 30mLDMF, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PVP, 0.2mmol AlCl
3, the amino terephthalic acid (TPA) of 0.4mmol2-is dissolved in 10mL DMF, reacts 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 130 DEG C of solvent heat conditions.
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid selective hydrogenation results of property of catalyst is in table 1.
Embodiment 6:
By the H of 1mmol PAA and 0.1mmol
2ptCl
6be dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution be heated to back flow reaction 3h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 1mmol GaCl
3be dissolved in 30mL DMF with the amino terephthalic acid (TPA) of 1mmol2-, then this solution be transferred in polytetrafluoroethyllining lining, under 150 DEG C of solvent heat conditions, react 24h and obtain MOFs.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 30mLDMF, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PAA, 0.2mmol GaCl
3, the amino terephthalic acid (TPA) of 0.4mmol2-is dissolved in 10mL DMF, reacts 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 130 DEG C of solvent heat conditions.
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid selective hydrogenation results of property of catalyst is in table 1.
Embodiment 7:
By the H of 1mmol PVP and 0.1mmol
2ptCl
6be dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution be heated to back flow reaction 5h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 1mmol Co (NO
3)
2and 0.5mmol2,5-dihydric para-phthalic acid is dissolved in 10mLDMF-10mL ethanol-10mL water, then this solution is transferred in polytetrafluoroethyllining lining, reacts 24h and obtain MOFs under 110 DEG C of solvent heat conditions.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 30mLDMF, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PVP, 0.4mmol Co (NO
3)
2and 0.2mmol2,5-dihydric para-phthalic acid is dissolved in 5mL DMF-5mL ethanol-5mL water, reacts 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 110 DEG C of solvent heat conditions.
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid selective hydrogenation results of property of catalyst is in table 1.
Embodiment 8:
By the H of 1mmol PVP and 0.1mmol
2ptCl
6be dissolved in 90mL ethanol and 10mL water, after fully dissolving, this solution be heated to back flow reaction 5h, obtain nano platinum particle.This solution is gone out to desolventizing by rotary evaporation, be re-dispersed in DMF or water, for subsequent use.
By 1mmol Ni (NO
3)
2and 0.5mmol2,5-dihydric para-phthalic acid is dissolved in 10mLDMF-10mL ethanol-10mL water, then this solution is transferred in polytetrafluoroethyllining lining, reacts 24h and obtain MOFs under 110 DEG C of solvent heat conditions.By centrifugal this MOFs5000rpm 8min, be re-dispersed in 30mLDMF, then in this solution, add Pt nano particle, stirring at room temperature 3h, the centrifugal 8min of 5000rpm, obtains loaded catalyst MOFs@Pt.Then add 1mmol PVP, 0.4mmol Ni (NO
3)
2and 0.2mmol2,5-dihydric para-phthalic acid is dissolved in 5mL DMF-5mL ethanol-5mL water, reacts 8h and obtain nucleocapsid structure MOFs@Pt@MOFs catalyst under 110 DEG C of solvent heat conditions.
The cinnamic acid selective hydrogenation performance test of catalyst is with embodiment 1.
The cinnamic acid selective hydrogenation results of property of catalyst is in table 1.
The cinnamic acid selective hydrogenation results of property of table 1 catalyst
| Embodiment | Cinnamic acid conversion ratio (%) | Cinnamyl alcohol selective (%) | Cinnamyl alcohol productive rate (%) |
| 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 acid selective hydrogenation.Compared with conventional load type method for preparing catalyst, to cinnamic acid, selective hydrogenation has very high selective, activity and stability to nucleocapsid structure MOFs@noble metal@MOFs nanocatalyst prepared by the present invention under temperate condition.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. for a preparation method for the MOFs noble metal MOFs catalyst of selective hydrogenation, it is characterized in that, described method comprises the steps:
(1) metallic organic framework MOFs is scattered in solvent, then adds wherein noble metal nano particles, stirring at room temperature, centrifugal, obtain loaded catalyst MOFs@noble metal;
(2) catalyst step (1) being obtained utilizes solvent wash, then add stabilizing agent and solvent, after being uniformly dispersed, add slaine and part, under solvent heat condition, react, obtain the MOFs@noble metal@MOFs catalyst for selective hydrogenation.
2. the method for claim 1, is characterized in that, described noble metal is selected from Pt.
3. method as claimed in claim 1 or 2, is characterized in that, the preparation method of described noble metal nano particles comprises the steps:
(a) noble metal precursor body is dissolved in the solvent that contains stabilizing agent, adds reducing agent;
(b) add hot reflux, obtain noble metal nano particles; Wherein, described solvent is that ethanol is or/and water.
4. method as claimed in claim 3, is characterized in that, in step (a), noble metal is Pt, and noble metal precursor body is selected from H
2ptCl
4, H
2ptCl
6, K
2ptCl
6, Na
2ptCl
6, K
2ptCl
4or Na
2ptCl
4in the mixture of any one or at least two kinds;
Preferably, described in step (a), solvent is second alcohol and water, and the volume ratio that described ethanol accounts for solvent is 0～100% and does not comprise 0 and 100%;
Preferably, described in step (a), the mol ratio of stabilizing agent and noble metal precursor body is 100:1～5:1;
Preferably, reducing agent described in step (a) is selected from the mixture of any one or at least two kinds in methyl alcohol, ethanol, propyl alcohol, sodium borohydride or ascorbic acid;
Preferably, the time that adds hot reflux described in step (a) is 3～24h.
5. the method as described in one of claim 1-4, is characterized in that, the preparation method of described metallic organic framework MOFs comprises the steps:
(c) slaine and part are dissolved in solvent, obtain mixed solution;
(d) mixed solution obtaining is reacted and obtains metallic organic framework MOFs under solvent heat condition.
6. method as claimed in claim 5, is characterized in that, the mol ratio of the described slaine of step (c) and part is 3:1～1:3;
Preferably, the described solvent of step (c) is selected from the mixture of any one or at least two kinds in DMF, methyl alcohol, ethanol or water;
Preferably, the reaction temperature of the described solvent heat condition of step (d) is 110～220 DEG C, and the reaction time is 8～24h.
7. the method as described in one of claim 1-6, is characterized in that, step (1) and the described solvent of step (2) are independently selected from the mixture of any one or at least two kinds in DMF, methyl alcohol, ethanol or water.
8. the method as described in one of claim 1-7, is characterized in that, described stabilizing agent is the mixture of any one or at least two kinds in PVP, PEG, PVA or PAA;
Preferably, described in step (2), the mol ratio of stabilizing agent and MOFs is 10:1～1:1;
Preferably, described slaine is MCl
xor/and M (NO
3)
x, x=2 or 3;
Preferably, described M is selected from the combination of any one or at least two kinds in Fe, Co, Ni, Cu, Cr, Al, V, Ga or In;
Preferably, described part is selected from unsubstituted terephthalic acid (TPA), be substituted the mixture of any one or at least two kinds in terephthalic acid (TPA) or the biphenyl dicarboxylic acid that base replaces, and described substituting group is selected from the combination of any one or at least two kinds in amino, carboxyl, sulfonic group, hydroxyl, alkyl, halogen or sulfydryl;
Preferably, the mol ratio of the described slaine of step (2) and part is 3:1～1:3;
Preferably, the reaction temperature of the described solvent heat condition of step (2) is 110～220 DEG C, and the reaction time is 8～24h.
9. for a MOFs noble metal MOFs catalyst for selective hydrogenation, it is characterized in that, it is prepared by method as described in one of claim 1-8.
10. a purposes for a kind of MOFs noble metal MOFs catalyst for selective hydrogenation as claimed in claim 9, is characterized in that, it prepares the reaction of cinnamyl alcohol for cinnamic acid selective hydrogenation.
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