CN107321386A - 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 PDF

Info

Publication number
CN107321386A
CN107321386A CN201710573034.3A CN201710573034A CN107321386A CN 107321386 A CN107321386 A CN 107321386A CN 201710573034 A CN201710573034 A CN 201710573034A CN 107321386 A CN107321386 A CN 107321386A
Authority
CN
China
Prior art keywords
cubdc
organic framework
metal organic
reactant
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710573034.3A
Other languages
Chinese (zh)
Other versions
CN107321386B (en
Inventor
付昱
陈丹
白晓觉
李雨浓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University China
Original Assignee
Northeastern University China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeastern University China filed Critical Northeastern University China
Priority to CN201710573034.3A priority Critical patent/CN107321386B/en
Publication of CN107321386A publication Critical patent/CN107321386A/en
Application granted granted Critical
Publication of CN107321386B publication Critical patent/CN107321386B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J31/02—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
    • 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]
    • 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
    • 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
    • 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
    • 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
    • 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 field, a kind of continuous catalytic method of in-situ reducing metal organic framework film is disclosed.CuBDC composite membranes are clipped on peristaltic pump filter, reactant is drawn by peristaltic pump and sodium borohydride mixed solution successively passes through CuBDC composite membranes, inorganic site Cu (II) moments in CuBDC films are reduced to the Cu bases nano-particle 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 inventive method can carry out continuous catalysis, and the catalyst service life of preparation is long, and reaction speed is fast, and efficiency high, product is easily collected, and does not introduce new impurity.

Description

A kind of continuous catalytic method of in-situ reducing metal organic framework film
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 technology
Metal organic framework (MOF) is a kind of novel nano-pore crystalline material, and its structure is by metal ion or metal Cluster is constituted in strong coordinate bond form with reference to diversified organic ligand.Metal-organic framework materials have the gold of VHD Belong to avtive spot, therefore it has larger application potential as different-phase catalyst in catalytic field.At present, MOF bases catalyst Being directly used in catalytic reaction has had many reports, but the matter fragility of MOF materials in itself and rigidity often limit it and enter one The processing of step and widely use.Current MOF is usually that directly input is reacted, by pyrocarbon in solid form as catalyst Reactant is put into the form of the metal/metal oxide that porous charcoal is supported or MOF is loaded into other substrate upslides after change Enter reaction, the catalyst of these types is inefficient mostly not ideal due to its avtive spot utilization rate, past in actual applications Very it is difficult to reclaim to realize reuse, and continuous catalysis difficult to realize greatly toward loss.
The content of the invention
In order to solve the above technical problems, the 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, while the metal nano-particle thin films formed are anti-to reactant progress continuous catalysis Should.
Concrete technical scheme is as follows：
A kind of continuous catalytic method of in-situ reducing metal organic framework film, peristaltic pump filter is clipped in by CuBDC composite membranes On heads, reactant and sodium borohydride mixed solution are drawn using peristaltic pump, makes it with certain speed by CuBDC composite membranes, Inorganic site Cu (II) sodium borohydride moment in CuBDC composite membranes is reduced to the Cu bases nano-particle formation metal of lower valency Nanoparticulate thin films, the metal nano-particle thin films of formation carry out continuous catalytic reaction to reactant, comprise the following steps：
(1) preparation of CuBDC composite membranes：Weigh a certain amount of copper acetate and be dissolved in N,N-dimethylformamide and acetonitrile volume Than for 1:2 mixed solvent, it is 2 to weigh a certain amount of terephthalic acid (TPA) to be dissolved in DMF with acetonitrile volume ratio: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 Sprayer unit will be uniformly sprayed onto on the liquid level of terephthalic acid solution after copper acetate solution atomization, one layer of self-supporting of formation CuBDC metal organic framework films, after CuBDC metal organic framework films are formed, along culture dish edge, are suctioned out unnecessary molten Liquid, makes CuBDC metal organic framework films fall on filter membrane, forms CuBDC composite membranes；
(2) continuous catalysis of in-situ reducing metal organic framework film：CuBDC composite membranes are clipped in detachable filter It is interior, filter is connected at the outlet of peristaltic pump, reactant is drawn using peristaltic pump and sodium borohydride mixed solution is continuous not Disconnected ground is by CuBDC composite membranes, and CuBDC composite membranes are 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) monitoring in real time：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 life-span according to Monitoring Data, changes in time.
The mol ratio of the copper acetate and terephthalic acid (TPA) is 3:1~1:3.
The molar concentration of the sodium borohydride solution is more than 50 times 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 rotating speed control is 10~150rpm/min.
This method have the advantage that：
(1) CuBDC composite membranes of the present invention are clipped in filter, make reactant and reducing agent sodium borohydride logical by vermiculator The laminated film is crossed, because reducing agent sodium borohydride has the inorganic site Cu (II) in strong reproducibility, CuBDC films by wink Between be reduced to the Cu nano-particles and cuprous nano particle membrane of lower valency, so as to form metal nano-particle thin films, use It is recyclable afterwards to recycle；The metal nano-particle thin films have a three-dimensional porous structure, thus with good permeability and compared with High specific surface area so that it can allow reactant to pass through and fully contact, surpasses in addition, nano level Cu basal granules has High catalytic activity so that the catalytic reaction can be quickly smoothed out.Reaction speed is fast, and efficiency high, product is easily collected, and New impurity is not introduced.
(2) the in-situ reducing metal organic framework film that the present invention is used produces porous metals nanoparticulate thin films catalyst Method, sodium borohydride is the reducing agent needed for structure catalyst in reactant.Because in-situ reducing metal organic framework is thin Reduced during film it is simple and quick, porous metals nanoparticulate thin films be easy to because ingress of air inactivation.Whole process of the present invention exists 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, it is to avoid contact of the metal nanoparticle with air, so as to avoid catalyst caused by the oxygen in air Rapid deactivation, so as to improve the service life of catalyst
(3) because two films in metal nano-particle thin films are all the porous membranes with nano-pore, the present invention is removed Outside can be with continuous catalysis reduction nitro compound, it can also tentatively filter out the granule foreign thing in reactant, play just The function of micron order impurity in step filtering reactant.Both reactant continuously can be largely handled, can tentatively be filtered out again molten Large granular impurity in liquid.
(4) continuous catalytic method for this in-situ reducing metal organic framework film that the present invention is provided, through many experiments Obvious decay did not occurred after 3 hours for checking, the transformation efficiency of its continuous catalysis, and effect persistence is good, simple to operate, just In control and industrialized production.
Brief description of the drawings
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 the exit solution of embodiment 1；
Fig. 4 is that the reaction-ure conversion-age of embodiment 1 changes over time relation；
Fig. 5 is the XRD of CuBDC composite membranes before embodiment 1 is catalyzed；
Fig. 6 is the XRD of metallic nanoparticle composite membrane after embodiment 1 is catalyzed；
Fig. 7 is the SEM figures of CuBDC composite membranes before embodiment 1 is catalyzed；
Fig. 8 is the SEM figures of metallic nanoparticle composite membrane after embodiment 1 is catalyzed.
In Fig. 1,1-reactant and sodium borohydride mixed solution；2-peristaltic pump；3-filter；4-CuBDC composite membranes； 5-reaction mixture.
Embodiment
With reference to specific embodiment, the present invention is described in detail, but protection scope of the present invention is not by embodiment institute Limit.
Embodiment 1：
Reactant is p-nitrophenyl phenol solution, and molar concentration is 0.000067mol/L, the molar concentration of sodium borohydride solution For 0.01mol/L
(1) preparation of CuBDC composite membranes：Two kinds of reaction solutions are prepared, the first is acetic acid copper solution, and solute is anhydrous vinegar Sour copper, solvent is that volume ratio is 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is that terephthalic acid (TPA) is molten Liquid, solute is terephthalic acid (TPA), and solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Anhydrous vinegar Sour copper is 3 with terephthalic acid (TPA) mol ratio: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 onto on the liquid level of terephthalic acid solution after copper acetate solution atomization, and two kinds of materials are accepting the liquid level of liquid The CuBDC metal organic framework films of one layer of self-supporting, after CuBDC metal organic framework films are formed, edge are formed after contact Culture dish edge, suctions out redundant solution, CuBDC metal organic framework films is fallen on filter membrane, forms CuBDC composite membranes.
(2) continuous catalysis of in-situ reducing metal organic framework film：CuBDC composite membranes are 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 rotating speed is 150rpm, and flow velocity is 6mL/min.
(3) monitoring in real time：Exit solution is collected, a uv-visible absorption spectra is measured every 10min, works as reaction When the conversion ratio of thing drops to 80%, CuBDC composite membranes are changed in time.
Reactant p-nitrophenol is light yellow, is added after reducing agent sodium borohydride, because pH increase solution is changed into bright Yellow；Peristaltic pump draws reactant and is passed to metal nano-particle thin films, and the liquid in exit is changed into Transparent color, shows reaction Thing p-nitrophenol is changed completely；After repeatedly continuous circulation catalysis, composite membrane, film in careful taking-up filter Black is changed into by previous blueness, illustrates that initial CuBDC metal organic framework membrane structures have discovered that transformation.
Embodiment 2：
Reactant is p-nitrophenyl phenol solution, and molar concentration is 0.0001mol/L, and the molar concentration of sodium borohydride solution is 0.005mol/L。
(1) preparation of CuBDC composite membranes：Two kinds of reaction solutions are prepared, the first is acetic acid copper solution, and solute is anhydrous vinegar Sour copper, solvent is that volume ratio is 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is that terephthalic acid (TPA) is molten Liquid, solute is terephthalic acid (TPA), and solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Anhydrous vinegar Sour copper is 3 with terephthalic acid (TPA) mol ratio: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 onto on the liquid level of terephthalic acid solution after copper acetate solution atomization, and two kinds of materials are accepting the liquid level of liquid The CuBDC metal organic framework films of one layer of self-supporting, after CuBDC metal organic framework films are formed, edge are formed after contact Culture dish edge, suctions out redundant solution, CuBDC metal organic framework films is fallen on filter membrane, forms CuBDC composite membranes.
(2) continuous catalysis of in-situ reducing metal organic framework film：CuBDC composite membranes are 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 rotating speed is 75rpm, and flow velocity is 6mL/min.
(3) monitoring in real time：Exit solution is collected, a uv-visible absorption spectra is measured every 10min, works as reaction When the conversion ratio of thing drops to 80%, CuBDC composite membranes are changed in time.
Embodiment 3：
Reactant is p-nitrophenyl phenol solution, and molar concentration is 0.0002mol/L, and the molar concentration of sodium borohydride solution is 0.04mol/L。
(1) preparation of CuBDC composite membranes：Two kinds of reaction solutions are prepared, the first is acetic acid copper solution, and solute is anhydrous vinegar Sour copper, solvent is that volume ratio is 1:2 N,N-dimethylformamide and acetonitrile mixed solvent；Second is that terephthalic acid (TPA) is molten Liquid, solute is terephthalic acid (TPA), and solvent is that volume ratio is 2:1 N,N-dimethylformamide and acetonitrile mixed solvent；Anhydrous vinegar Sour copper is 1 with terephthalic acid (TPA) mol ratio: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 onto on the liquid level of terephthalic acid solution after copper acetate solution atomization, and two kinds of materials are accepting the liquid level of liquid The CuBDC metal organic framework films of one layer of self-supporting, after CuBDC metal organic framework films are formed, edge are formed after contact Culture dish edge, suctions out redundant solution, CuBDC metal organic framework films is fallen on filter membrane, forms CuBDC composite membranes.
(2) continuous catalysis of in-situ reducing metal organic framework film：CuBDC composite membranes are 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 rotating speed is 20rpm, and flow velocity is 6mL/min.
(3) monitoring in real time：Exit solution is collected, a uv-visible absorption spectra is measured every 10min, works as reaction When the conversion ratio of thing drops to 80%, CuBDC composite membranes are changed in time.
Fig. 2 is the uv-visible absorption spectroscopy figure that p-nitrophenyl phenol solution is added before and after sodium borohydride, as illustrated, P-nitrophenyl phenol solution has feature ultraviolet absorption peak at 317nm, and after sodium borohydride is added, the absworption peak occurs obvious Red shift is reached 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, i.e., with the addition of sodium borohydride, the basicity increase of solution causes the phenolic hydroxyl group of p-nitrophenol Generation proton abstraction, causes the red shift of absworption peak.As shown in Fig. 2 in the presence of no catalyst, the solution is steady Fixed does not occur obvious change, and obvious change does not occur in 10h yet for the peak position and photon absorbing intensity of its ultraviolet absorption peak.
P-nitrophenol is continued through CuBDC composite membranes using peristaltic-type pump arrangement, collect the liquid in peristaltic pump exit, Every 10min uv-visible absorption spectroscopies, Fig. 3 is the ultra-violet absorption spectrum of the exit solution of embodiment 1, as illustrated, right Nitrophenol solution is passed through after film, and its absworption peak at 400nm is almost wholly absent, and shows the p-nitrophenol in solution Almost react complete, shown that metal nano-particle thin films have the catalytic performance of superelevation.
Fig. 4 is that the reaction-ure conversion-age of embodiment 1 changes over time relation, as illustrated, after 3h, p-nitrophenol leads to Obvious decay still will not occur for the conversion ratio crossed after CuBDC composite membranes, and be maintained at more than 90%.The experimental result table Bright, the thinking that the place of catalyst and catalytic reaction is served as using CuBDC composite membranes is practicable, and it can the company of playing The effect of continuous catalytic solution reactant.
Fig. 5 is the XRD of CuBDC composite membranes before embodiment 1 is catalyzed, and Fig. 6 is that metal nanoparticle is answered after embodiment 1 is catalyzed The XRD of film is closed, as illustrated, its structure also changes, Cu and Cu are changed into by initial CuBDC structures2O nano-particles are answered Close structure.
Fig. 7 is the SEM figures of CuBDC composite membranes before embodiment 1 is catalyzed, and Fig. 8 is that metal nanoparticle is answered after embodiment 1 is catalyzed The SEM figures of film are closed, as illustrated, the film of sheet accumulation is changed into the porous membrane of nano-particle composition, i.e. metal organic framework Film serves as the precursor of catalyst, by the nano-particle that sodium borohydride reduction is metal/metal oxide, made from this method Metal nano-particle thin films have the advantages that permeability is good, avtive spot is more and stability is high.

Claims (6)

1. a kind of continuous catalytic method of in-situ reducing metal organic framework film, it is characterised in that be clipped in CuBDC composite membranes On peristaltic pump filter, reactant and sodium borohydride mixed solution are drawn using peristaltic pump, it is passed through CuBDC with certain speed Inorganic site Cu (II) sodium borohydride moment in composite membrane, CuBDC composite membranes is reduced to the Cu base nano-particles 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) preparation of CuBDC composite membranes：Weigh a certain amount of copper acetate and be dissolved in N,N-dimethylformamide and be with acetonitrile volume ratio 1:2 mixed solvent, it is 2 to weigh a certain amount of terephthalic acid (TPA) to be dissolved in DMF with acetonitrile volume ratio:1 it is mixed 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 onto on the liquid level of terephthalic acid solution after copper acetate solution atomization, forms the CuBDC gold of one layer of self-supporting Belong to organic backbone film, after CuBDC metal organic framework films are formed, along culture dish edge, suction out redundant solution, make CuBDC metal organic framework films fall on filter membrane, form CuBDC composite membranes；
(2) continuous catalysis of in-situ reducing metal organic framework film：CuBDC composite membranes are 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 membranes are crossed, CuBDC composite membranes are converted into metal nanoparticle laminated film catalyst, the metal nanoparticle of formation Film carries out continuous catalytic reaction to reactant；
(3) monitoring in real time：In the exit collecting reaction product solution of peristaltic pump, and reaction product solution is supervised in real time Survey, judge whether metal nano-particle thin films reach the life-span according to Monitoring Data, change in time.
2. a kind of continuous catalytic method of in-situ reducing metal organic framework film as claimed in claim 1, it is characterised in that： The mol 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 claimed in claim 1, it is characterised in that： The molar concentration of the sodium borohydride solution is more than 50 times of reactant molar concentration.
4. a kind of continuous catalytic method of in-situ reducing metal organic framework film as claimed 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 claimed 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 claimed in claim 1, it is characterised in that： The outlet bore of the peristaltic pump is 1mm~5mm, and rotating speed control is 10~150rpm/min.
CN201710573034.3A 2017-07-14 2017-07-14 A kind of continuous catalytic method of in-situ reducing metal organic framework film Active CN107321386B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710573034.3A CN107321386B (en) 2017-07-14 2017-07-14 A kind of continuous catalytic method of in-situ reducing metal organic framework film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710573034.3A CN107321386B (en) 2017-07-14 2017-07-14 A kind of continuous catalytic method of in-situ reducing metal organic framework film

Publications (2)

Publication Number Publication Date
CN107321386A true CN107321386A (en) 2017-11-07
CN107321386B CN107321386B (en) 2019-09-27

Family

ID=60226981

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710573034.3A Active CN107321386B (en) 2017-07-14 2017-07-14 A kind of continuous catalytic method of in-situ reducing metal organic framework film

Country Status (1)

Country Link
CN (1) CN107321386B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113578271A (en) * 2021-07-14 2021-11-02 南京工业大学 Preparation method and application of copper metal organic framework composite material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105664944A (en) * 2016-02-19 2016-06-15 中国环境科学研究院 Cu catalyst based on metal organic framework, preparation method and application
CN106478406A (en) * 2016-08-26 2017-03-08 东北大学 A kind of preparation method of nano-grade metal-organic framework materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105664944A (en) * 2016-02-19 2016-06-15 中国环境科学研究院 Cu catalyst based on metal organic framework, preparation method and application
CN106478406A (en) * 2016-08-26 2017-03-08 东北大学 A kind of preparation method of nano-grade metal-organic framework materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YITING WANG ET AL.: "Synthesis of porous Cu2O/CuO cages using Cu-based metal–organic frameworks as templates and their gas-sensing properties", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113578271A (en) * 2021-07-14 2021-11-02 南京工业大学 Preparation method and application of copper metal organic framework composite material

Also Published As

Publication number Publication date
CN107321386B (en) 2019-09-27

Similar Documents

Publication Publication Date Title
CN103272576B (en) Vanadate nanofiber photocatalyst and preparation method thereof
CN103638979B (en) A kind of magnetic class zeolite imidazole ester metal-organic framework materials, preparation and for liquid phase condensations catalytic reaction
CN108355717A (en) A kind of preparation method of cellulose/BiOBr composite photocatalyst materials
CN102921466B (en) Heterogeneous Au/Ze-MOF catalyst and preparation method and application thereof
CN104307514B (en) A kind of titania/silica compound spherical shell parcel nano catalyst and preparation method thereof
CN103551197B (en) One has hole cage pore passage structure magnetic metal organic framework material, preparation and for acylation reaction
CN106732816B (en) A kind of Pd/TiO2/ cotton fiber composite formaldehyde room-temperature oxidation catalyst and preparation method thereof
CN100442982C (en) Method for preparing nano Ag (I)/Ag (III)/TiO2 composite material
CN107353680A (en) A kind of light catalyzed coating and its preparation method and application
CN102698770A (en) Manganese dioxide composite metal oxide catalyst, preparation method and application
CN104258901A (en) Cs supported pure silicon molecular sieve catalyst, preparation method and applications thereof
CN107670680A (en) A kind of immobilized fenton catalyst and preparation method and application
CN107321386A (en) A kind of continuous catalytic method of in-situ reducing metal organic framework film
CN111569875A (en) Copper/porous carbon nanorod material, preparation method and application
CN102764648A (en) Preparation method of palladium catalyst,
CN106807451A (en) A kind of flexible platinum formaldehyde room temperature oxidation catalyst and preparation method thereof
CN205833182U (en) A kind of industrial waste Al2o3bead micropore activation system
CN106391000A (en) Pd(111)/gamma-Al2O3 catalyst for CO dehydrogenation purification reaction and preparation method thereof
CN105709614A (en) Ultrathin layered material, and preparation method thereof
CN209034112U (en) A kind of organic waste gas purifying processing device
CN101559970B (en) Preparation of nano cuprous oxide by two-step method of electron beam irradiation and compressed air oxidation
CN108176390A (en) A kind of mesoporous composite titanium-tin photochemical catalyst and preparation method thereof
CN107469869A (en) A kind of preparation method of photocatalytic fiber net
CN107434434A (en) A kind of photocatalysis stone material and its preparation method and application
CN103272625B (en) Phosphate nanofiber photocatalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant