CN107321386B - A kind of continuous catalytic method of in-situ reducing metal organic framework film - Google Patents
A kind of continuous catalytic method of in-situ reducing metal organic framework film Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
The present invention relates to catalysis technical fields, disclose a kind of continuous catalytic method of in-situ reducing metal organic framework film.CuBDC composite membrane is clipped on peristaltic pump filter, reactant is drawn by peristaltic pump and sodium borohydride mixed solution successively passes through CuBDC composite membrane, inorganic site Cu (II) moment in CuBDC film is reduced to the Cu base nanoparticle of lower valency to form metal nano-particle thin films, meanwhile the metal nano-particle thin films of formation carry out continuous catalytic reaction to reactant.The method of the present invention can carry out continuous catalysis, and the catalyst long service life of preparation, reaction speed is fast, high-efficient, and product is easy to collect, and does not introduce new impurity.
Description
Technical field
It is related to catalysis technical field, and in particular to a kind of continuous catalytic method of in-situ reducing metal organic framework film.
Background technique
Metal organic framework (MOF) is a kind of novel nano-pore crystalline material, and structure is by metal ion or metal
Cluster combines diversified organic ligand to be constituted in the form of strong coordinate bond.Metal-organic framework materials have the gold of ultra high density
Belong to active site, therefore it has biggish application potential in catalytic field as different-phase catalyst.Currently, MOF base catalyst
Being directly used in catalysis reaction, there are many reports, but the matter brittleness of MOF material itself and rigidity often limit it into one
The processing of step and extensive use.MOF is usually that directly investment is reacted, by pyrocarbon in solid form as catalyst at present
Reactant is put into the form of the metal/metal oxide of porous charcoal support after change or MOF is loaded into other substrate upslides
Enter reaction, the catalyst of these types is past in practical applications since its active site utilization rate is inefficient mostly not satisfactory
It is difficult very much recycling greatly toward loss to realize reuse, and continuous catalysis difficult to realize.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of continuous catalysis of in-situ reducing metal organic framework film
Method, realizes reactant molecule and reducing agent sodium borohydride continues through metal organic framework film, and metal organic framework is thin
Film umklappen is metal nano-particle thin films, and it is anti-that the metal nano-particle thin films being formed simultaneously carry out continuous catalysis to reactant
It answers.
Specific technical solution is as follows:
CuBDC composite membrane is clipped in peristaltic pump filter by a kind of continuous catalytic method of in-situ reducing metal organic framework film
On heads, reactant and sodium borohydride mixed solution are drawn using peristaltic pump, it is made to pass through CuBDC composite membrane with certain rate,
The Cu base nanoparticle that inorganic site Cu (II) sodium borohydride moment in CuBDC composite membrane is reduced to lower valency forms metal
The metal nano-particle thin films of nanoparticulate thin films, formation carry out continuous catalytic reaction to reactant, comprising the following steps:
(1) it the preparation of CuBDC composite membrane: weighs a certain amount of copper acetate and is dissolved in N,N-dimethylformamide and acetonitrile volume
Than the mixed solvent for 1:2, weighs a certain amount of terephthalic acid (TPA) and be dissolved in n,N-Dimethylformamide and acetonitrile volume ratio for 2:1
In the mixed solvent；One layer of porous membrane is placed in the culture dish bottom for containing terephthalic acid solution in advance, then passes through ultrasound
Spraying device will be uniformly sprayed on the liquid level of terephthalic acid solution after copper acetate solution atomization, form one layer of self-supporting
CuBDC metal organic framework film, along culture dish edge, is sucked out extra molten after CuBDC metal organic framework film is formed
Liquid falls in CuBDC metal organic framework film on filter membrane, forms CuBDC composite membrane；
(2) CuBDC composite membrane the continuous catalysis of in-situ reducing metal organic framework film: is clipped in detachable filter
It is interior, filter is connected at the outlet of peristaltic pump, draws reactant and sodium borohydride mixed solution continuously not using peristaltic pump
Disconnectedly by CuBDC composite membrane, CuBDC composite membrane is converted into metal nanoparticle laminated film catalyst, and the metal of formation is received
Nanoparticle thin film carries out continuous catalytic reaction to reactant；
(3) real-time monitoring: in the exit collecting reaction product solution of peristaltic pump, and reaction product solution is carried out real-time
Monitoring, judges whether metal nano-particle thin films reach the service life according to monitoring data, replaces in time.
The molar ratio of the copper acetate and terephthalic acid (TPA) is 3:1~1:3.
The molar concentration of the sodium borohydride solution is 50 times or more of reactant molar concentration.
The reactant is aromatic nitro class compound.
The porous membrane is arbitrary solid porous film.
The outlet bore of the peristaltic pump is 1mm~5mm, and revolving speed control is 10~150r/min.
This method have the advantage that:
(1) CuBDC composite membrane of the present invention is clipped in filter, keeps reactant and reducing agent sodium borohydride logical by vermiculator
The laminated film is crossed, since reducing agent sodium borohydride has strong reproducibility, the inorganic site Cu (II) in CuBDC film is by wink
Between be reduced to the Cu nanoparticle and cuprous nano particle membrane of lower valency, to form metal nano-particle thin films, use
It can be recycled and recycle afterwards；The metal nano-particle thin films have three-dimensional porous structure, therefore have good permeability and compared with
High specific surface area makes it possible to and reactant is allowed to pass through and come into full contact with, and surpasses in addition, nanoscale Cu basal granule has
High catalytic activity, so that catalysis reaction can quickly be gone on smoothly.Reaction speed is fast, high-efficient, and product is easy to collect, and
New impurity is not introduced.
(2) the in-situ reducing metal organic framework film that the present invention uses generates porous metals nanoparticulate thin films catalyst
Method, sodium borohydride is reducing agent needed for structure catalyst in reactant.Since in-situ reducing metal organic framework is thin
Restored when film it is simple and quick, porous metals nanoparticulate thin films be easy to because ingress of air inactivate.Whole process of the present invention exists
It is carried out in liquid phase, for the continuous catalysis to reactant while moment in-situ reducing changes in the solution, air can be completely cut off.Behaviour
Make simple and convenient, contact of the metal nanoparticle with air is avoided, so as to avoid catalyst caused by the oxygen in air
Rapid deactivation, to improve the service life of catalyst
(3) since two films in metal nano-particle thin films are all the porous membranes with nano-pore, the present invention is removed
It can be restored outside nitro compound with continuous catalysis, can fall the granule foreign object in reactant with primary filtration, played just
The function of micron order impurity in step filtering reactant.Not only reactant continuously can be largely handled, but also can be fallen with primary filtration molten
Large granular impurity in liquid.
(4) continuous catalytic method of this in-situ reducing metal organic framework film provided by the invention, through many experiments
Verifying, the transformation efficiency of continuous catalysis did not occurred significantly to decay after 3 hours, and effect persistence is good, easy to operate, just
In control and industrialized production.
Detailed description of the invention
Fig. 1 is continuous catalysis schematic device of the present invention；
Fig. 2 is the uv-visible absorption spectroscopy figure that p-nitrophenyl phenol solution is added before and after sodium borohydride；
Fig. 3 is the ultra-violet absorption spectrum of 1 exit solution of embodiment；
Fig. 4 is that 1 reaction-ure conversion-age of embodiment changes over time relationship；
Fig. 5 is the XRD diagram of CuBDC composite membrane before embodiment 1 is catalyzed；
Fig. 6 is the XRD diagram of metallic nanoparticle composite membrane after embodiment 1 is catalyzed；
Fig. 7 is the SEM figure of CuBDC composite membrane before embodiment 1 is catalyzed；
Fig. 8 is the SEM figure of metallic nanoparticle composite membrane after embodiment 1 is catalyzed.
In Fig. 1,1-reactant and sodium borohydride mixed solution；2-peristaltic pumps；3-filters；4-CuBDC composite membranes；
5-reaction mixtures.
Specific embodiment
The present invention is described in detail combined with specific embodiments below, but protection scope of the present invention is not by embodiment institute
Limit.
Embodiment 1:
Reactant is p-nitrophenyl phenol solution, molar concentration 0.000067mol/L, the molar concentration of sodium borohydride solution
For 0.01mol/L
(1) preparation of CuBDC composite membrane: preparing two kinds of reaction solutions, the first is acetic acid copper solution, and solute is anhydrous vinegar
Sour copper, solvent are the n,N-Dimethylformamide and acetonitrile mixed solvent that volume ratio is 1:2；Second molten for terephthalic acid (TPA)
Liquid, solute are terephthalic acid (TPA)s, and solvent is the n,N-Dimethylformamide and acetonitrile mixed solvent that volume ratio is 2:1；Anhydrous vinegar
Sour copper and terephthalic acid (TPA) molar ratio are 3:1；
One layer of solid porous film is placed in the culture dish bottom for containing terephthalic acid solution in advance, then passes through ultrasound spray
Mist device will be uniformly sprayed on the liquid level of terephthalic acid solution after copper acetate solution atomization, and two kinds of substances are in the liquid level for accepting liquid
The CuBDC metal organic framework film that one layer of self-supporting is formed after contact, after CuBDC metal organic framework film is formed, edge
Culture dish edge is sucked out redundant solution, falls in CuBDC metal organic framework film on filter membrane, forms CuBDC composite membrane.
(2) CuBDC composite membrane the continuous catalysis of in-situ reducing metal organic framework film: is clipped in detachable filter
It is interior, it is placed at the outlet of peristaltic pump.The reaction solution of above-mentioned preparation is set to accompany composite membrane continually by interior using peristaltic pump
Filter, the outlet bore of peristaltic pump is 2.5mm, and holdings revolving speed is 150rpm, flow velocity 6mL/min.
(3) real-time monitoring: collecting exit solution, measures a uv-visible absorption spectra every 10min, works as reaction
When the conversion ratio of object drops to 80%, CuBDC composite membrane is replaced in time.
Reactant p-nitrophenol be it is light yellow, be added reducing agent sodium borohydride after, since the increase solution of pH becomes bright
Yellow；Peristaltic pump draws reactant and makes it through metal nano-particle thin films, and the liquid in exit becomes Transparent color, shows to react
Object p-nitrophenol is converted completely；After repeatedly continuous circulation catalysis, composite membrane in careful taking-up filter, film
Black is changed by previous blue, illustrates that initial CuBDC metal organic framework membrane structure has discovered that transformation.
Embodiment 2:
Reactant is p-nitrophenyl phenol solution, and the molar concentration of molar concentration 0.0001mol/L, sodium borohydride solution are
0.005mol/L。
(1) preparation of CuBDC composite membrane: preparing two kinds of reaction solutions, the first is acetic acid copper solution, and solute is anhydrous vinegar
Sour copper, solvent are the n,N-Dimethylformamide and acetonitrile mixed solvent that volume ratio is 1:2；Second molten for terephthalic acid (TPA)
Liquid, solute are terephthalic acid (TPA)s, and solvent is the n,N-Dimethylformamide and acetonitrile mixed solvent that volume ratio is 2:1；Anhydrous vinegar
Sour copper and terephthalic acid (TPA) molar ratio are 3:5；
One layer of solid porous film is placed in the culture dish bottom for containing terephthalic acid solution in advance, then passes through ultrasound spray
Mist device will be uniformly sprayed on the liquid level of terephthalic acid solution after copper acetate solution atomization, and two kinds of substances are in the liquid level for accepting liquid
The CuBDC metal organic framework film that one layer of self-supporting is formed after contact, after CuBDC metal organic framework film is formed, edge
Culture dish edge is sucked out redundant solution, falls in CuBDC metal organic framework film on filter membrane, forms CuBDC composite membrane.
(2) CuBDC composite membrane the continuous catalysis of in-situ reducing metal organic framework film: is clipped in detachable filter
It is interior, it is placed at the outlet of peristaltic pump.The reaction solution of above-mentioned preparation is set to accompany composite membrane continually by interior using peristaltic pump
Filter, the outlet bore of peristaltic pump is 2.5mm, and holdings revolving speed is 75rpm, flow velocity 6mL/min.
(3) real-time monitoring: collecting exit solution, measures a uv-visible absorption spectra every 10min, works as reaction
When the conversion ratio of object drops to 80%, CuBDC composite membrane is replaced in time.
Embodiment 3:
Reactant is p-nitrophenyl phenol solution, and the molar concentration of molar concentration 0.0002mol/L, sodium borohydride solution are
0.04mol/L。
(1) preparation of CuBDC composite membrane: preparing two kinds of reaction solutions, the first is acetic acid copper solution, and solute is anhydrous vinegar
Sour copper, solvent are the n,N-Dimethylformamide and acetonitrile mixed solvent that volume ratio is 1:2；Second molten for terephthalic acid (TPA)
Liquid, solute are terephthalic acid (TPA)s, and solvent is the n,N-Dimethylformamide and acetonitrile mixed solvent that volume ratio is 2:1；Anhydrous vinegar
Sour copper and terephthalic acid (TPA) molar ratio are 1:3；
One layer of solid porous film is placed in the culture dish bottom for containing terephthalic acid solution in advance, then passes through ultrasound spray
Mist device will be uniformly sprayed on the liquid level of terephthalic acid solution after copper acetate solution atomization, and two kinds of substances are in the liquid level for accepting liquid
The CuBDC metal organic framework film that one layer of self-supporting is formed after contact, after CuBDC metal organic framework film is formed, edge
Culture dish edge is sucked out redundant solution, falls in CuBDC metal organic framework film on filter membrane, forms CuBDC composite membrane.
(2) CuBDC composite membrane the continuous catalysis of in-situ reducing metal organic framework film: is clipped in detachable filter
It is interior, it is placed at the outlet of peristaltic pump.The reaction solution of above-mentioned preparation is set to accompany composite membrane continually by interior using peristaltic pump
Filter, the outlet bore of peristaltic pump is 2.5mm, and holdings revolving speed is 20rpm, flow velocity 6mL/min.
(3) real-time monitoring: collecting exit solution, measures a uv-visible absorption spectra every 10min, works as reaction
When the conversion ratio of object drops to 80%, CuBDC composite membrane is replaced in time.
Fig. 2 is the uv-visible absorption spectroscopy figure that p-nitrophenyl phenol solution is added before and after sodium borohydride, as shown,
P-nitrophenyl phenol solution has feature ultraviolet absorption peak at 317nm, and after sodium borohydride is added, which occurs apparent
Red shift reaches at 400nm, and along with from light yellow to the obvious color change of glassy yellow.The phenomenon can be attributed to nitre
The proton abstraction of base phenol leads to the phenolic hydroxyl group of p-nitrophenol that is, as the addition of sodium borohydride, the basicity of solution increase
Proton abstraction occurs, leads to the red shift of absorption peak.As shown in Fig. 2, the solution is steady in the presence of no catalyst
Fixed does not occur significantly to change, and the peak position and photon absorbing intensity of ultraviolet absorption peak do not occur significantly to change in 10h yet.
So that p-nitrophenol is continued through CuBDC composite membrane using peristaltic-type pump arrangement, collect the liquid in peristaltic pump exit,
Every 10min uv-visible absorption spectroscopy, Fig. 3 is the ultra-violet absorption spectrum of 1 exit solution of embodiment, as shown, right
After nitrophenol solution passes through film, the absorption peak at 400nm almost disappears, and shows the p-nitrophenol in solution
Almost fully reacting shows that metal nano-particle thin films have the catalytic performance of superelevation.
Fig. 4 is that 1 reaction-ure conversion-age of embodiment changes over time relationship, as shown, p-nitrophenol is logical after 3h
Conversion ratio after crossing CuBDC composite membrane still will not occur significantly to decay, and be maintained at 90% or more.The experimental result table
It is bright, using CuBDC composite membrane serve as catalyst and catalysis reaction place thinking be it is practicable, it can the company of playing
The effect of continuous catalytic solution reactant.
Fig. 5 is the XRD diagram of CuBDC composite membrane before embodiment 1 is catalyzed, and Fig. 6 is that metal nanoparticle is multiple after embodiment 1 is catalyzed
The XRD diagram for closing film is changed into Cu and Cu by initial CuBDC structure as shown, its structure also changes2O nanoparticle is multiple
Close structure.
Fig. 7 is the SEM figure of CuBDC composite membrane before embodiment 1 is catalyzed, and Fig. 8 is that metal nanoparticle is multiple after embodiment 1 is catalyzed
The SEM figure of film is closed, as shown, the film of sheet accumulation becomes the porous membrane of nanoparticle composition, i.e. metal organic framework
Film serves as the precursor of catalyst, is the nanoparticle of metal/metal oxide by sodium borohydride reduction, made from this method
Metal nano-particle thin films have the advantages that permeability is good, active site is more and stability is high.
Claims (6)
1. a kind of continuous catalytic method of in-situ reducing metal organic framework film, which is characterized in that CuBDC composite membrane to be clipped in
On peristaltic pump filter, reactant and sodium borohydride mixed solution are drawn using peristaltic pump, it is made to pass through CuBDC with certain rate
Composite membrane, inorganic site Cu (II) the sodium borohydride moment in CuBDC composite membrane are reduced to the Cu base nanoparticle of lower valency
Metal nano-particle thin films are formed, the metal nano-particle thin films of formation carry out continuous catalytic reaction to reactant, including following
Step:
(1) it the preparation of CuBDC composite membrane: weighs a certain amount of copper acetate and is dissolved in N,N-dimethylformamide with acetonitrile volume ratio and be
The mixed solvent of 1:2 weighs a certain amount of terephthalic acid (TPA) and is dissolved in n,N-Dimethylformamide and acetonitrile volume ratio for the mixed of 2:1
In bonding solvent；One layer of porous membrane is placed in the culture dish bottom for containing terephthalic acid solution in advance, then passes through ullrasonic spraying
Device will be uniformly sprayed on the liquid level of terephthalic acid solution after copper acetate solution atomization, form the CuBDC gold of one layer of self-supporting
Belong to organic backbone film, after CuBDC metal organic framework film is formed, along culture dish edge, redundant solution is sucked out, makes
CuBDC metal organic framework film is fallen on filter membrane, forms CuBDC composite membrane；
(2) continuous catalysis of in-situ reducing metal organic framework film: CuBDC composite membrane is clipped in detachable filter, will
Filter is connected at the outlet of peristaltic pump, draws reactant using peristaltic pump and sodium borohydride mixed solution continuously leads to
CuBDC composite membrane is crossed, CuBDC composite membrane is converted into metal nanoparticle laminated film catalyst, the metal nanoparticle of formation
Film carries out continuous catalytic reaction to reactant；
(3) real-time monitoring: in the exit collecting reaction product solution of peristaltic pump, and reaction product solution is supervised in real time
It surveys, judges whether metal nano-particle thin films reach the service life according to monitoring data, replace in time.
2. a kind of continuous catalytic method of in-situ reducing metal organic framework film as described in claim 1, it is characterised in that:
The molar ratio of the copper acetate and terephthalic acid (TPA) is 3:1~1:3.
3. a kind of continuous catalytic method of in-situ reducing metal organic framework film as described in claim 1, it is characterised in that:
The molar concentration of the sodium borohydride solution is 50 times or more of reactant molar concentration.
4. a kind of continuous catalytic method of in-situ reducing metal organic framework film as described in claim 1, it is characterised in that:
The reactant is aromatic nitro class compound.
5. a kind of continuous catalytic method of in-situ reducing metal organic framework film as described in claim 1, it is characterised in that:
The porous membrane is arbitrary solid porous film.
6. a kind of continuous catalytic method of in-situ reducing metal organic framework film as described in claim 1, it is characterised in that:
The outlet bore of the peristaltic pump is 1mm~5mm, and revolving speed control is 10~150r/min.
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