CN103908976A - Method for preparing selectivity-adjustable efficient supported precious-metal core-shell catalyst coated with metal-organic framework ZIF-8 membrane - Google Patents
Method for preparing selectivity-adjustable efficient supported precious-metal core-shell catalyst coated with metal-organic framework ZIF-8 membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing a selectivity-adjustable efficient supported precious-metal core-shell catalyst coated with a metal-organic framework ZIF-8 membrane, and belongs to the technical field of new materials. The method comprises the following steps: coating a pre-prepared supported precious-metal catalyst with a ZIF-8 membrane selective-separation layer, repairing the defect of the membrane layer through polyelectrolyte, adjusting and controlling the membrane forming times to obtain continuous ZIF-8 membranes with different compactnesses, and thereby the catalyst has the adjustable high selectivity. Compared with the same kind of catalyst, the selectivity-adjustable efficient supported precious-metal core-shell catalyst has the advantages of simple preparation process, mild conditions and easiness in large-scale amplification. The selectivity-adjustable efficient supported precious-metal core-shell catalyst solves the problem that a multiphase supported precious-metal catalyst has the low selectivity to reactants and products, and simultaneously is beneficial to relieve the fact that active components of the multiphase supported precious-metal catalyst are easily lost and poisoned.
Description
Technical field
The present invention has prepared the coated efficient nucleocapsid catalyst of carried noble metal of a kind of selective adjustable metallic organic framework ZIF-8 film.Mainly be to there is molecule screening function ZIF-8 film and give the high selectivity of loaded noble metal catalyst to reactant and product by outer cladding is a kind of; Also contribute to solve the easily loss, poisoning in reaction of active component of heterogeneous catalyst, cause the problem of activity decreased simultaneously.
Background technology
Nano-noble metal (Pd, Pt, Au etc.) catalyst is at catalytic hydrogenation, and selective oxidation has high catalytic activity in the industrial reaction process that carbon monoxide transforms and carbon-to-carbon coupling etc. is important.Early stage research focuses on homogeneous system, although homogeneous catalyst can provide desirable activity, it has restricted its application in industrial production in the problem aspect recovery separation.Comparatively speaking, heterogeneous catalyst, in keeping more satisfactory activity, has again efficient separation recyclability.Loaded nano noble metal catalyst passes through active constituent loading in multiple prop carrier (organic polymer carrier, charcoal carrier, molecular sieve, SiO
2, Al
2o
3, TiO
2, Fe
3o
4deng) on realize heterogeneousization of homogeneous catalyst.But the active component of such catalyst easily runs off in course of reaction, poisoning, easy-sintering under high temperature, and then affect stability and the life-span of catalyst.For addressing this problem, carry out the active force [Crudden C M, et al., J.Am.Chem.Soc., 2005,127:10045-10050] between enhanced particles and carrier by introducing specific function group; Thereby particle is incorporated into and in the duct of molecular sieve, fixes nano particle and alleviate its run off [Wang H, et al., ChemCatChem, 2010,2:1303-1311].But above method does not relate to the selective problems of catalyst to reaction and product.
Metallic organic framework (metal organic frameworks, MOFs) is a kind of porous crystalline material of using covalency or the self assembly of ion-covalent effect to form by metal ion or metal cluster and organic ligand.The outstanding advantages such as it has high-specific surface area, porous, skeleton structure is adjustable, atmosphere storage with separate, there is great application potential in the aspect such as heterogeneous catalysis, molecular recognition and sensing.Zeolitic imidazolate framework material (Zeolitic imidazolate frameworks, ZIFs) as a kind of MOFs of broad research, compared with the metallic organic framework of other types, there is larger specific area and pore volume and high thermal stability and chemical resistance.The topological structure of ZIF-8 similar to Si-Al zeolite molecular sieve (SOD): the oxygen atom of sial tetrahedron and bridging is replaced by metal ion and imidazoles respectively, and its macropore is of a size of
can allow kinetic diameter to be less than
molecule is is freely come in and gone out, thereby has the feature of molecule screening.Therefore, using ZIF-8 as load or the matrix of coated noble metal nano particles, can effectively improve the selective of catalyst, meanwhile, also can alleviate the loss of active component, poisoning.
At present, prepare this kind of catalyst and mainly have two kinds of methods, the first will obtain metal@ZIF-8 type nucleocapsid catalyst by noble metal nano particles being embedded in ZIF-8 duct or at nano particle outer cladding ZIF-8 film.As people such as Jiang, by by ZIF-8 and (CH
3)
2two kinds of solids mixings of Au (acac) also grind, at process H
2the method of reduction obtains Au@ZIF-8 catalyst, and for CO oxidation [Jiang H L, et al., J.Am.Chem.Soc., 2009,131:11302-11303]; The method that the people such as Li reduce by continuous sedimentation by Au, Ag nanometer particle load in the surface and duct of ZIF-8, obtain bimetallic catalyst, catalyzing N aBH4 reduction p-nitrophenol is produced 4-amino phenols [Li Z, et al., Chem.Mater., 2013,25:1761-1768] people such as .Lu puts into PVP-Pt in the synthetic liquid of ZIF-8, completes coated [Lu G, et al. by adsorb PVP-Pt in ZIF-8 building-up process, Nat.Chem.2012,4:310-316]; The synthetic ZIF-8 film of the Pd nanocrystal surface of the people such as Kuo in 80nm left and right, obtains eggshell type Pd@ZIF-8 catalyst [Kuo C H, et al., J.Am.Chem.Soc., 2012,134:14345-14348]; The people such as Yang utilize the stabilization of two N atom pair noble metal nano particles in glyoxal ethyline, first make 2-mIM-Pt, synthetic [the Yang Q H as organic ligand induction ZIF-8 monocrystalline by 2-miM again, et al., Chem Common, 2013,49:3330-3332]. above catalyst type all belongs to the homogeneous phase noble metal nano particles of ZIF-8 particle parcel non-loading type, being selectively single and being difficult for modulation of this catalyst.
Summary of the invention
The technical problem to be solved in the present invention is the drawback existing for the preparation of current heterogeneous catalyst and the coated heterogeneous carried noble metal microballoon of a kind of novel ZIF-8 film proposing and the nucleocapsid catalyst that obtains.At pre-synthesis Pd/SiO
2loaded catalyst superficial growth forms the ZIF-8 rete of continuous uniform, obtains Pd/SiO
2@ZIF-8 film nucleocapsid catalyst, by regulation and control Pd/SiO
2the number of times of loaded catalyst outer surface growth ZIF-8 film, changes the thickness of ZIF-8 film and compactness and gives catalyst adjustable selective; Also contribute to solve the problems such as the easy loss of catalyst active center, and be verified in hydrogenation reaction simultaneously.
Technical scheme of the present invention is as follows:
A preparation method for the coated efficient nucleocapsid catalyst of carried noble metal of selective adjustable metallic organic framework ZIF-8 film is pre-synthesis SiO
2microsphere supported and Pd nano particle, then by mix and blend by Pd nanometer particle load to SiO
2upper formation loading type Pd/SiO
2catalyst, then selects layer to the coated ZIF-8 film of pre-synthesis loaded noble metal catalyst; In the time of diauxic growth ZIF-8, by repairing and the thickness regulation and control of rete defect, obtain fine and close continuous ZIF-8 film, catalyst is had selectively adjustable.
In the time of pre-synthesis loaded noble metal catalyst, used carrier is the solid SiO after activation
2microballoon, activation method is 95 DEG C, hydrothermal treatment consists 8h.Noble metal used is the Pd nano particle that PVP is stable, in the time of diauxic growth ZIF-8 film, adopts ionic high molecular polymer polystyrene sodium sulfate salt to repair rete defect.
Concrete steps are as follows:
(1) preparation of Pd nano particle
First prepare 2mM H
2pdCl
4the aqueous solution, then with PVP, H
2o, HCl are heated to boiling after mixing, add ethanol, backflow 3h at once;
(2) SiO
2the preparation of carrier
According to stober method, adopting TEOS is silicon source, NH
4oH is catalyst, under ethanol/water mixed system, and ordinary-temp hydrolysis 1h;
(3) SiO that Pd nano particle method (1) being made and method (2) obtain
2normal temperature mixing 24h, obtains Pd/SiO
2catalyst;
(4) Pd/SiO method (3) being obtained
2the aqueous solution and PDDA aqueous solution, normal temperature leaves standstill 30min, and deionized water eccentric cleaning is repeatedly; Leave standstill 30min with PSS aqueous solution normal temperature again, deionized water methyl alcohol difference eccentric cleaning repeatedly;
(5) modification method (4) being obtained the Pd/SiO of PDDA and PSS
2put in the synthetic liquid of ZIF-8 ice bath 2h, normal temperature 1h; That synthesizes liquid consists of zinc nitrate, glyoxal ethyline (2meIM), methyl alcohol as film forming liquid raw material, and a mole proportioning for synthetic liquid is about: 2-mIM:Zn (NO
3)
26H
2o:CH
3oH=10:1:810.
The invention solves the activated centre that traditional heterogeneous catalyst faces easily run off, poisoning, the problem of high temperature easy-sintering, and obtain the thickness rete different with compactness by the grow number of times of ZIF-8 film of adjustment, and then the molecule of different sizes is sieved, give catalyst with adjustable selective, be with a wide range of applications.
Brief description of the drawings
Fig. 1 a is SiO
2carrier TEM figure.
Fig. 1 b is Pd/SiO
2the TEM figure of loaded catalyst.
Fig. 1 c is the TEM figure of one-pass film-forming rear catalyst.
Fig. 1 d is the TEM figure of two-step film forming rear catalyst.
Fig. 2 a is the SEM figure of one-pass film-forming rear catalyst.
Fig. 2 b is the SEM figure of two-step film forming rear catalyst.
Fig. 3 is the XRD spectra of different samples.
Fig. 4 is the active temporal evolution curve of different catalysts.
Fig. 5 is that different thickness catalyst are to the big or small olefine selective block diagram of difference.
Detailed description of the invention
Describe the specific embodiment of the present invention in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
(1) preparation of Pd nano particle
First prepare 2mM H
2pdCl
4the aqueous solution, then with PVP, H
2o, HCl are heated to boiling after mixing, add ethanol, backflow 3h at once;
(2) SiO
2the preparation of carrier
According to stober method, adopting TEOS is silicon source, NH
4oH is catalyst, under ethanol/water mixed system, and ordinary-temp hydrolysis 1h;
(3) SiO that Pd nano particle method (1) being made and method (2) obtain
2normal temperature mixing 24h, obtains Pd/SiO
2catalyst;
(4) Pd/SiO method (3) being obtained
2the aqueous solution and PDDA aqueous solution, normal temperature leaves standstill 30min, and deionized water eccentric cleaning is repeatedly; Leave standstill 30min with PSS aqueous solution normal temperature again, deionized water methyl alcohol difference eccentric cleaning repeatedly;
(5) modification method (4) being obtained the Pd/SiO of PDDA and PSS
2put in the synthetic liquid of ZIF-8 ice bath 2h, normal temperature 1h; That synthesizes liquid consists of zinc nitrate, glyoxal ethyline (2meIM), methyl alcohol as film forming liquid raw material, and a mole proportioning for synthetic liquid is about: 2-mIM:Zn (NO
3)
26H
2o:CH
3oH=10:1:810;
(6) say that 80 DEG C of vacuum drying of catalyst that method (5) obtains spend the night, be placed in drier to be tested.
Embodiment 2
(1) preparation of Pd nano particle
First prepare 2mM H
2pdCl
4the aqueous solution, then with PVP, H
2o, HCl are heated to boiling after mixing, add ethanol, backflow 3h at once;
(2) SiO
2the preparation of carrier
According to stober method, adopting TEOS is silicon source, NH
4oH is catalyst, under ethanol/water mixed system, and ordinary-temp hydrolysis 1h;
(3) SiO that Pd nano particle method (1) being made and method (2) obtain
2normal temperature mixing 24h, obtains Pd/SiO
2catalyst;
(4) say that 80 DEG C of vacuum drying of catalyst that method (3) obtains spend the night, be placed in drier to be tested.
Embodiment 3
(1) preparation of Pd nano particle
First prepare 2mM H
2pdCl
4the aqueous solution, then with PVP, H
2o, HCl are heated to boiling after mixing, add ethanol, backflow 3h at once;
(2) SiO
2the preparation of carrier
According to stober method, adopting TEOS is silicon source, NH
4oH is catalyst, under ethanol/water mixed system, and ordinary-temp hydrolysis 1h;
(3) SiO that Pd nano particle method (1) being made and method (2) obtain
2normal temperature mixing 24h, obtains Pd/SiO
2catalyst;
(4) Pd/SiO method (3) being obtained
2the aqueous solution and PDDA aqueous solution, normal temperature leaves standstill 30min, and deionized water eccentric cleaning is repeatedly; Leave standstill 30min with PSS aqueous solution normal temperature again, deionized water methyl alcohol difference eccentric cleaning repeatedly;
(5) modification method (4) being obtained the Pd/SiO of PDDA and PSS
2put in the synthetic liquid of ZIF-8 ice bath 2h, normal temperature 1h; That synthesizes liquid consists of zinc nitrate, glyoxal ethyline (2meIM), methyl alcohol as film forming liquid raw material, and a mole proportioning for synthetic liquid is about: 2-mIM:Zn (NO
3)
26H
2o:CH
3oH=10:1:810;
(6) film forming method (5) being obtained catalyst and PSS aqueous solution normal temperature once leaves standstill 30min, and deionized water methyl alcohol respectively eccentric cleaning is repeatedly put in the synthetic liquid of ZIF-8 afterwards, ice bath 2h, normal temperature 1h; That synthesizes liquid consists of zinc nitrate, glyoxal ethyline (2meIM), methyl alcohol as film forming liquid raw material, and a mole proportioning for synthetic liquid is about: 2-mIM:Zn (NO
3)
26H
2o:CH
3oH=10:1:810;
(7) the 80 DEG C of vacuum drying of catalyst that method (6) obtained are spent the night, and are placed in drier to be tested.
Embodiment 4
Get 0.1g catalyst and be placed in reaction unit, then add 15nl ethyl acetate, 0.3ml n-hexylene, adopts hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction finishes, by catalyst and feed liquid centrifugation, adopt gas-chromatography (chromatographic column: HP-5; FID) testing result.
Embodiment 5
Get 0.1g catalyst and be placed in reaction unit, then add 15nl ethyl acetate, 0.3ml cyclohexene, adopts hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction finishes, by catalyst and feed liquid centrifugation, adopt gas-chromatography (chromatographic column: HP-5; FID) testing result.
Embodiment 6
Get 0.1g catalyst and be placed in reaction unit, then add 15nl ethyl acetate, 0.3ml cyclo-octene, adopts hydrogen purge reaction unit 3 times, 35 DEG C of reaction 24h.After reaction finishes, by catalyst and feed liquid centrifugation, adopt gas-chromatography (chromatographic column: HP-5; FID) testing result.
Claims (7)
1. a preparation method for the coated efficient nucleocapsid catalyst of carried noble metal of selective adjustable metallic organic framework ZIF-8 film, is characterized in that, the coated ZIF-8 film of pre-synthesis loaded noble metal catalyst is selected to layer; In the time of diauxic growth ZIF-8, by repairing and the thickness regulation and control of rete defect, obtain fine and close continuous ZIF-8 film, catalyst is had selectively adjustable.
2. preparation method according to claim 1, is characterized in that, in the time of synthetic loaded noble metal catalyst, used carrier is the solid SiO after activation
2microballoon; Activation method is 95 DEG C, hydrothermal treatment consists 8h.
3. preparation method according to claim 2, is characterized in that, described noble metal is Pd nano particle.
4. preparation method according to claim 3, is characterized in that, described Pd nano particle is the stable Pd nano particle of PVP.
5. according to the preparation method described in claim 1,2,3 or 4, it is characterized in that, in the time of diauxic growth ZIF-8 film, adopt ionic high molecular polymer to repair rete defect.
6. preparation method according to claim 5, is characterized in that, described ionic high molecular polymer is anionic high molecular polymer.
7. preparation method according to claim 6, is characterized in that, described anionic high molecular polymer is polystyrene sodium sulfate salt.
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Cited By (10)
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|---|---|---|---|---|
| CN104492491A (en) * | 2014-12-12 | 2015-04-08 | 大连理工大学 | ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof |
| CN106317278A (en) * | 2015-07-01 | 2017-01-11 | 中国科学院大连化学物理研究所 | Preparation method for monodisperse core-shell-structured ZIF-8@PDVB-VI composite microspheres |
| CN107537571A (en) * | 2017-10-23 | 2018-01-05 | 南京工程学院 | A kind of multi-walled carbon nanotube noble metal catalyst and preparation method thereof |
| CN108993597A (en) * | 2018-08-01 | 2018-12-14 | 中国科学技术大学 | A kind of catalyst and preparation method thereof for alkynes hydrogenation |
| CN109759140A (en) * | 2019-01-24 | 2019-05-17 | 济南大学 | A method of synthesis MOFs Shell Materials are assisted by technique for atomic layer deposition |
| CN111187421A (en) * | 2020-01-15 | 2020-05-22 | 浙江理工大学 | Nanoparticle/metal-organic framework material and preparation method and application thereof |
| CN113304736A (en) * | 2021-06-07 | 2021-08-27 | 浙江月旭材料科技有限公司 | Water-resistant composite material and preparation method and application thereof |
| CN113413777A (en) * | 2021-07-30 | 2021-09-21 | 南京理工大学 | VZIF-67/ZIF-67-polyimide mixed matrix membrane, preparation method and application thereof |
| CN113624742A (en) * | 2021-08-31 | 2021-11-09 | 重庆大学 | Hydrogen enhanced Raman spectroscopy detection method for sulfhydryl gas in plasmon MOF |
| CN114522733A (en) * | 2022-03-04 | 2022-05-24 | 安徽大学 | Method for preparing nano composite material by using bond breaking strategy and application of nano composite material in CO catalysis2Application in ethynylation reaction |
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| CN104492491A (en) * | 2014-12-12 | 2015-04-08 | 大连理工大学 | ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof |
| CN106317278A (en) * | 2015-07-01 | 2017-01-11 | 中国科学院大连化学物理研究所 | Preparation method for monodisperse core-shell-structured ZIF-8@PDVB-VI composite microspheres |
| CN106317278B (en) * | 2015-07-01 | 2018-08-31 | 中国科学院大连化学物理研究所 | A kind of preparation method of monodisperse nucleocapsid ZIF-8@PDVB-VI complex microspheres |
| CN107537571A (en) * | 2017-10-23 | 2018-01-05 | 南京工程学院 | A kind of multi-walled carbon nanotube noble metal catalyst and preparation method thereof |
| CN107537571B (en) * | 2017-10-23 | 2020-09-18 | 南京工程学院 | Multi-walled carbon nanotube-based noble metal catalyst and preparation method thereof |
| CN108993597A (en) * | 2018-08-01 | 2018-12-14 | 中国科学技术大学 | A kind of catalyst and preparation method thereof for alkynes hydrogenation |
| CN109759140B (en) * | 2019-01-24 | 2021-11-19 | 济南大学 | Method for synthesizing MOFs shell material by aid of atomic layer deposition technology |
| CN109759140A (en) * | 2019-01-24 | 2019-05-17 | 济南大学 | A method of synthesis MOFs Shell Materials are assisted by technique for atomic layer deposition |
| CN111187421B (en) * | 2020-01-15 | 2022-02-22 | 浙江理工大学 | Nanoparticle/metal-organic framework material and preparation method and application thereof |
| CN111187421A (en) * | 2020-01-15 | 2020-05-22 | 浙江理工大学 | Nanoparticle/metal-organic framework material and preparation method and application thereof |
| CN113304736A (en) * | 2021-06-07 | 2021-08-27 | 浙江月旭材料科技有限公司 | Water-resistant composite material and preparation method and application thereof |
| CN113304736B (en) * | 2021-06-07 | 2022-03-04 | 浙江月旭材料科技有限公司 | Water-resistant composite material and preparation method and application thereof |
| CN113413777A (en) * | 2021-07-30 | 2021-09-21 | 南京理工大学 | VZIF-67/ZIF-67-polyimide mixed matrix membrane, preparation method and application thereof |
| CN113624742A (en) * | 2021-08-31 | 2021-11-09 | 重庆大学 | Hydrogen enhanced Raman spectroscopy detection method for sulfhydryl gas in plasmon MOF |
| CN113624742B (en) * | 2021-08-31 | 2022-05-20 | 重庆大学 | Hydrogen enhanced Raman spectroscopy detection method for sulfhydryl gas in plasmon MOF |
| CN114522733A (en) * | 2022-03-04 | 2022-05-24 | 安徽大学 | Method for preparing nano composite material by using bond breaking strategy and application of nano composite material in CO catalysis2Application in ethynylation reaction |
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