CN103249738A - Process for coating support surface with porous metal-rganic framework - Google Patents

Process for coating support surface with porous metal-rganic framework Download PDF

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Publication number
CN103249738A
CN103249738A CN2011800586987A CN201180058698A CN103249738A CN 103249738 A CN103249738 A CN 103249738A CN 2011800586987 A CN2011800586987 A CN 2011800586987A CN 201180058698 A CN201180058698 A CN 201180058698A CN 103249738 A CN103249738 A CN 103249738A
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acid
dioctyl phthalate
solution
mof
porous metal
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M·加布
A·韦伯
M·克斯特
U·穆勒
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/147—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing embedded adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3265—Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/02—Magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/04—Calcium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
    • C07F3/06—Zinc compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/02—Metal coatings
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals

Abstract

Provided is a process for coating at least part of a surface of a support with a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion. The process comprises the following steps: (a) spraying the at least one part of the support surface with a first solution comprising the at least one metal ion; (b) spraying the at least one part of the support surface with a second solution comprising the at least one at least bidentate organic compound; wherein step (b) is carried out before, after or simultaneously with step (a), to form a layer of the porous metal-organic framework.

Description

Method with porous metal-organic framework coated carrier surface
The present invention relates to be coated to porous metal-organic framework (" MOF ") method of small part carrier surface.
The method that applies with metallic organic framework is described in the prior art.
WO2009/056184A1 for example described will comprise metallic organic framework suspension spray on material such as non-woven fabrics.
DE102006031311A1 proposes sorbing material such as metallic organic framework are applied on the solid support material by bonding or other fixing means.
Form the MOF layer on the gold surface and be described in people such as S.Hermes by being incorporated into by self-assembled monolayer, J.Am.Chem.Soc.127 (2005), 13744-13745 (also referring to people such as S.Hermes, Chem.Mater.19 (2007), 2168-2173; People such as D.Zacher, J.Mater.Chem.17 (2007), 2785-2792; People such as O.Shekhah, J.Am.Chem.Soc.129 (2007), 15118-15119; People such as A.Schroedel, Angew.Chem.Int.Ed.49 (2010), 7225-7228) in.
MOF layer on the silicone carrier is described in G.Lu, and J.Am.Chem.Soc.132 (2010) is among the 7832-7833.
MOF layer on the polyacrylonitrile carrier is described in people such as A.Centrone, and J.Am.Chem.Soc.132 (2010) is among the 15687-15691.
Copper on the copper film-benzene tricarboxylic acid ester MOF is described in people such as H.Guo, and J.Am.Chem.Soc.131 (2009) is among the 1646-1647.
Produce the MOF layer by dipping and crystal growth at alumina supporter and be described in people such as Y.-S.Li, Angew.Chem.Int.Ed.49 (2010) is among the 548-551.Similarly subject description is in people such as J.Gascon, Microporous and Mesoporous Materials113 (2008), people such as 132-138 and A.Demessence, Chem.Commun.2009, people such as 7149-7151 and P.K ü sgen, Advanced Engineering Materials11 (2009) is among the 93-95.
The galvanic deposit of MOF film is described in people such as A.Dom é nech, and Electrochemistry Communications8 (2006) is among the 1830-1834.
The MOF layer also be used for to apply kapillary (people such as N.Chang, J.Am.Chem.Soc.132 (2010), 13645-13647).
Although the method with porous metal-organic framework coated carrier surface is known by prior art, need improved method.
The purpose of this invention is to provide and improve one's methods.
This purpose is by realizing that with comprising the method that porous metal-organic framework with at least a at least two bidentate organic compounds of at least a metallic ion coordination is coated to the small part carrier surface described method comprises step:
(a) with at least a portion carrier surface first solution spray that comprises at least a metal ion;
(b) with at least a portion carrier surface second solution spray that comprises at least a at least two bidentate organic compounds,
Wherein step (b) is before step (a), carry out forming the porous metal-organic framework layer later on or simultaneously.
Found to cause on carrier surface metallic organic framework with the spontaneous formation of the form of layer first and second solution sprays.Herein, particularly advantageous is to obtain homogeneous layer.Spraying can be given the preparation method who carries out sooner than dipping method.Adhesion can improve, and makes to save tackiness agent.
Step (a) can be carried out before step (b).Step (a) also can be carried out after step (b).Step (a) and step (b) also can be carried out simultaneously.
Can be preferably with gained porous metal-organic framework layer drying.If step (a) and (b) do not carry out simultaneously then also can be carried out drying step between two steps.
The drying of gained porous metal-organic framework layer can be carried out by heating and/or by the pressure that reduces especially.Heating is for example carried out under 120-300 ℃ temperature.Preferably that described layer is dry down at least 150 ℃.
Spraying can be undertaken by known spray technique.Preferably in the spraying drum, carry out with first, second or with first and second solution sprays.
Solution can be under different temperature or identical temperature.This can for more than the room temperature or below.Be equally applicable to carrier surface.First solution or second solution or first and second solution are preferably under room temperature (22 ℃).
First and second solution can comprise identical or different solvent.The preferred same solvent of using.Possible solvent is the known solvent of prior art.First solution or second solution or first and second solution are preferably the aqueous solution.
Carrier surface can be metal or nonmetal, optional modified surface.Optimum fiber or foam surface.
The sheet fabric structure that especially preferably comprises or formed by natural fiber and/or synthon (man-made fiber), wherein natural fiber is selected from wool fiber, cotton fibre (CO) and particularly Mierocrystalline cellulose especially, and/or synthon are selected from polyester (PES) especially; Polyolefine, particularly polyethylene (PE) and/or polypropylene (PP); Polyvinyl chloride (CLF); Polyvinylidene dichloride (CLF); Acetic ester (CA); Triacetate (CTA); Polyacrylic (PAN); Polyamide (PA), particularly aromatics, preferred anti-retardant polyamide; Polyvinyl alcohol (PVAL); Urethane; Polyvinyl ester; (methyl) acrylate; Poly(lactic acid) (PLA); Gac; And composition thereof.
The foam that is particularly preferred for sealing and insulate, acoustic foam, the rigid foam that is used for packing and the flame-resistant foam of being formed by following component: urethane, polystyrene, polyethylene, polypropylene, PVC, viscose glue, spongy rubber and composition thereof.The foam of being formed by melamine resin (Basotect) very particularly preferably.
Specially suitable solid support material is filtering material (comprising finishing material, cotton, cigarette filter, filter paper, as for example can commercial acquisition being used for the laboratory purposes).
First solution comprises at least a metal ion.This can be used as metal-salt and uses.Second solution comprises at least a at least two bidentate organic compounds.This can be preferably the solution of its salt.
At least a metal ion directly contacts with form layers on carrier surface by two kinds of solution with at least a two bidentate organic compounds form porous metal-organic framework at least.The metallic organic framework that can produce like this is well known in the prior art.
This metalloid organic backbone (MOF) for example is described in people such as US5,648,508, EP-A-0790253, M.O'Keeffe, J.Sol.State Chem., 152(2000), 3-20 page or leaf, people such as H.Li, Nature402, (1999), the 276th page, people such as M.Eddaoudi, Topics in Catalysis 9, (1999), 105-111 page or leaf, people such as B.Chen, Science 291, (2001), the 1021-1023 page or leaf, DE-A-10111230, DE-A102005053430, WO-A2007/054581 is among WO-A2005/049892 and the WO-A2007/023134.
As one group of concrete these metallic organic framework, " limited " skeleton has been described in the document recently, wherein owing to the concrete selection of organic compound, skeleton can not infinitely prolong, but forms polyhedron.People such as A.C.Sudik, J.Am.Chem.Soc.127 (2005), 7110-7118 have described the concrete skeleton of this class.Yet they are described to metal-organic polyhedra (MOP) to distinguish them.
Another is organized concrete porous metal-organic framework and comprises wherein as the organic compound of part for derived from the heterocycle of at least a pyrroles of being selected from, α-pyridone and DB3 ketone and have those of monocycle, dicyclo or polycyclic system of at least two ring nitrogen.The electrochemical preparation of this class skeleton is described among the WO-A2007/131955.
Usually the metallic organic framework that is suitable for absorbing gas and liquid for example is described among WO-A2005/003622 and the EP-A1702925.
These concrete groups are particularly suitable for purpose of the present invention.
Metallic organic framework of the present invention comprises the hole, particularly micropore and/or mesopore.It is 2nm or littler hole that micropore is defined as diameter, and mesopore is by the definition of the diameter of 2-50nm, under every kind of situation according to Pure﹠amp; Applied Chem.57 (1983), 603-619, the particularly definition that provides on the 606th page.The existence of micropore and/or mesopore can be measured by absorption and be checked, it measures MOF absorptive capacity to nitrogen under 77K according to DIN66131 and/or DIN66134.
The specific surface area of the MOF that calculates according to Langmuir's model (DIN66131,66134) is preferably greater than 10m 2/ g is more preferably greater than 20m 2/ g is more preferably greater than 50m 2/ g.Depend on MOF, also can realize greater than 100m 2/ g is more preferably greater than 150m 2/ g is preferably greater than 200m especially 2/ g.
Metal component in the skeleton of the present invention is preferably selected from Ia, IIa, IIIa, IVa-VIIIa and Ib-VIb family.Preferred especially Mg, Ca, Sr, Ba, Sc, Y, Ln, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ro, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, wherein Ln is lanthanon.
Lanthanon is La, Ce, Pr, Nd, Pm, Sm, En, Gd, Tb, Dy, Ho, Er, Tm, Yb.
About the ion of these elements, can mention Mg especially 2+, Ca 2+, Sr 2+, Ba 2+, Sc 3+, Y 3+, Ln 3+, Ti 4+, Zr 4+, Hf 4+, V 4+, V 3+, V 2+, Nb 3+, Ta 3+, Cr 3+, Mo 3+, W 3+, Mn 3+, Mn 2+, Re 3+, Re 2+, Fe 3+, Fe 2+, Ru 3+, Ru 2+, Os 3+, Os 2+, Co 3+, Co 2+, Rh 2+, Rh +, Ir 2+, Ir +, Ni 2+, Ni +, Pd 2+, Pd +, Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+, Ga 3+, In 3+, Tl 3+, Si 4+, Si 2+, Ge 4+, Ge 2+, Sn 4+, Sn 2+, Pb 4+, Pb 2+, As 5+, As 3+, As +, Sb 5+, Sb 3+, Sb +, Bi 5+, Bi 3+And Bi +
Very particularly preferably Mg, Ca, Al, Y, Sc, Zr, Ti, V, Cr, Mo, Fe, Co, Cu, Ni, Zn, Ln.More preferably Mg, Ca, Al, Mo, Y, Sc, Mg, Fe, Cu and Zn.Preferred especially Mg, Ca, Sc, Al, Cu and Zn.Can mention Mg, Ca, Al and Zn, particularly Al very especially herein.
Statement " at least two bidentate organic compounds " refer to comprise at least one can with given metal ion form at least two coordinate bonds and/or and two or more, each forms the organic compound of the functional group of a coordinate bond in preferred two atoms metals.
Functional group as forming above-mentioned coordinate bond can mention for example following functional group :-CO especially 2H ,-CS 2H ,-NO 2,-B (OH) 2,-SO 3H ,-Si (OH) 3,-Ge (OH) 3,-Sn (OH) 3,-Si (SH) 4,-Ge (SH) 4,-Sn (SH) 3,-PO 3H ,-AsO 3H ,-AsO 4H ,-P (SH) 3,-As (SH) 3,-CH (RSH) 2,-C (RSH) 3,-CH (RNH 2) 2,-C (RNH 2) 3,-CH (ROH) 2,-C (ROH) 3,-CH (RCN) 2,-C (RCN) 3, wherein R for example is preferably the alkylidene group with 1,2,3,4 or 5 carbon atom, for example methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, isobutylene, uncle's butylidene or positive pentylidene, or comprise one or two aromatic ring as two C 6The aryl of ring, its can choose wantonly condense and every kind of situation under can suitably be replaced by at least one substituting group independently of each other and/or every kind of situation under can comprise at least one heteroatoms such as N, O and/or S independently of each other.In same embodiment preferred, can mention the functional group that does not wherein have above-mentioned radicals R.Just in this point, can especially mention-CH (SH) 2,-C (SH) 3,-CH (NH 2) 2,-C (NH 2) 3,-CH (OH) 2,-C (OH) 3,-CH (CN) 2Or-C (CN) 3
Yet functional group also can be the heteroatoms of heterocycle.Here can mention nitrogen-atoms especially.
Described at least two functional groups are bonding on any suitable organic compound in principle, and condition is that it guarantees that the organic compound that has these functional groups can form coordinate bond and can produce skeleton.
Comprise the organic compound of at least two functional groups preferably derived from saturated or unsaturated lipid compounds of group or aromatic substance or aliphatic series and aromatic substance.
The aliphatic series of aliphatic cpd or aliphatic series and aromatic substance partly can be for linearity and/or branching and/or ring-type, and wherein to have a plurality of rings also be possible to each compound.The aliphatic series part of aliphatic cpd or aliphatic series and aromatic substance more preferably comprises 1-15, and more preferably 1-14, more preferably 1-13, more preferably 1-12, more preferably 1-11, preferred especially 1-10 carbon atom, for example 1,2,3,4,5,6,7,8,9 or 10 carbon atom.Special optimization methane, diamantane, acetylene, ethene or divinyl herein.
The aromatics of aromatic substance or aromatics and aliphatic cpd part can have one or more rings, 2,3,4 or 5 rings for example, and wherein ring can exist and/or two rings can exist with the form of condensing independently of each other at least.The aromatics part of aromatic substance or aliphatic series and aromatic substance especially preferably has 1,2 or 3 ring, and one of them or two rings are particularly preferred.In addition, each ring of described compound can comprise at least one heteroatoms such as N, O, S, B, P, Si, Al independently, preferred N, O and/or S.The aromatics part of aromatic substance or aromatics and aliphatic cpd more preferably comprises one or two C 6Ring, wherein two rings exist independently of each other or with the form of condensing.Can mention benzene, naphthalene and/or biphenyl and/or dipyridyl and/or pyridine especially as aromatic substance.
At least two bidentate organic compounds more preferably have 1-18, and preferred 1-10,6 carbon atoms and only also have 2,3 or 4 carboxyls as the aliphatic series of functional group or aromatics, acyclic or cyclic hydrocarbon particularly.
At least a at least two bidentate organic compounds are preferably derived from dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid.
For example; at least two bidentate organic compounds are derived from dicarboxylic acid; oxalic acid for example; succsinic acid; tartrate; 1; 4-butane dioctyl phthalate; 1; 4-butylene dioctyl phthalate; 4-oxo pyrans-2; the 6-dioctyl phthalate; 1; the 6-hexmae dicarboxylic acid; the decane dioctyl phthalate; 1; 8-heptadecane dioctyl phthalate; 1; 9-heptadecane dioctyl phthalate; the heptadecane dioctyl phthalate; the acetylene dioctyl phthalate; 1; the 2-phthalic acid; 1; the 3-phthalic acid; 2; the 3-dinicotinic acid; pyridine-2; the 3-dioctyl phthalate; 1; 3-divinyl-1; the 4-dioctyl phthalate; 1; the 4-phthalic acid; right-phthalic acid; imidazoles-2; the 4-dioctyl phthalate; 2-toluquinoline-3, the 4-dioctyl phthalate; quinoline-2, the 4-dioctyl phthalate; quinoxaline-2; the 3-dioctyl phthalate; 6-chloro-quinoxaline-2; the 3-dioctyl phthalate; 4,4'-tetramethyl triaminotriphenyl methane NH2-3, the 3'-dioctyl phthalate; quinoline-3; the 4-dioctyl phthalate; 7-chloro-4-hydroxyquinoline-2; the 8-dioctyl phthalate; the imide dioctyl phthalate; pyridine-2, the 6-dioctyl phthalate; glyoxal ethyline-4, the 5-dioctyl phthalate; thiophene-3; the 4-dioctyl phthalate; 2 isopropyl imidazole-4; the 5-dioctyl phthalate; tetrahydropyrans-4, the 4-dioctyl phthalate; perylene-3, the 9-dioctyl phthalate; the perylene dioctyl phthalate; Pluriol E200-dioctyl phthalate; 3; 6-two oxa-octane dicarboxylic acids; 3; 5-cyclohexadiene-1, the 2-dioctyl phthalate; octane dicarboxylic acid; pentane-3, the 3-dioctyl phthalate; 4; the 4'-diaminostilbene; 1'-biphenyl-3, the 3'-dioctyl phthalate; 4,4'-benzidine-3; the 3'-dioctyl phthalate; p-diaminodiphenyl-3; the 3'-dioctyl phthalate; two (phenyl amino) benzene-2 of 1,4-, the 5-dioctyl phthalate; 1; the 1'-binaphthyl dicarboxylic acid; 7-chloro-8-toluquinoline-2; the 3-dioctyl phthalate; 1-anilino anthraquinone-2, the 4'-dioctyl phthalate; polytetrahydrofuran 250-dioctyl phthalate; two (carboxymethyl) piperazines-2 of 1,4-; the 3-dioctyl phthalate; 7-chloroquinoline-3; the 8-dioctyl phthalate; 1-(4-carboxyl) phenyl-3-(4-chlorine) phenylpyrrazolin-4, the 5-dioctyl phthalate; 1,4; 5; 6,7,7-chlordene-5-norbornylene-2; the 3-dioctyl phthalate; the phenyl indan dioctyl phthalate; 1; 3-dibenzyl-2-oxoimidazolinium-4, the 5-dioctyl phthalate; 1,4 cyclohexanedicarboxylic acid; naphthalene-1; the 8-dioctyl phthalate; 2-Benzoylbenzene-1; the 3-dioctyl phthalate; 1,3-dibenzyl-2-oxoimidazolinium-4,5-is suitable-dioctyl phthalate; 2; 2'-diquinolyl-4; the 4'-dioctyl phthalate; pyridine-3, the 4-dioctyl phthalate; 3,6; 9-trioxa undecane dioctyl phthalate; the hydroxy benzophenone keto-dibasic acid; Pluriol E300-dioctyl phthalate; Pluriol E400-dioctyl phthalate; Pluriol E600-dioctyl phthalate; pyrazoles-3; the 4-dioctyl phthalate; 2,3-pyrazine dioctyl phthalate; 5,6-dimethyl-2; 3-pyrazine dioctyl phthalate; 4; 4'-diamino (phenyl ether) imide dioctyl phthalate; 4,4'-diaminodiphenyl-methane imide dioctyl phthalate; 4,4'-diamino (sulfobenzide) imide dioctyl phthalate; 1; the 4-naphthalic acid; 2; the 6-naphthalic acid; 1,3-adamantane acid; 1,8-naphthalic acid; 2; the 3-naphthalic acid; 8-methoxyl group-2; the 3-naphthalic acid; 8-nitro-2, the 3-naphthalic acid; 8-sulfo group-2, the 3-naphthalic acid; anthracene-2; the 3-dioctyl phthalate; 2'; 3'-phenylbenzene-right-terphenyl-4,4 " dioctyl phthalate; (phenyl ether)-4,4'-dioctyl phthalate; imidazoles-4; 5-dioctyl phthalate; 4 (1H)-oxo thiochromes-2; 8-dioctyl phthalate; the 5-tertiary butyl-1, the 3-phthalic acid; 7,8-quinoline dioctyl phthalate; 4; 5-imidazoles dioctyl phthalate; 4-tetrahydrobenzene-1; the 2-dioctyl phthalate; the hexatriacontane dioctyl phthalate; tetradecane dioctyl phthalate; 1,7-heptane dioctyl phthalate; 5-hydroxyl-1, the 3-phthalic acid; 2; 5-dihydroxyl-1; the 4-dioctyl phthalate; pyrazine-2, the 3-dioctyl phthalate; furans-2, the 5-dioctyl phthalate; 1-nonene-6; the 9-dioctyl phthalate; eicosene dicarboxylic acid; 4; 4'-dihydroxyl ditan-3, the 3'-dioctyl phthalate; 1-amino-4-methyl-9,10-dioxo-9; 10-dihydroanthracene-2; the 3-dioctyl phthalate; 2,5-dinicotinic acid; tetrahydrobenzene-2, the 3-dioctyl phthalate; 2; 9-dichloro fluorubin-4; the 11-dioctyl phthalate; 7-chloro-3-toluquinoline-6, the 8-dioctyl phthalate; 2,4-dichloro benzophenone-2 '; 5 '-dioctyl phthalate; 1; the 3-phthalic acid; 2,6-dinicotinic acid; 1-methylpyrrole-3, the 4-dioctyl phthalate; 1-benzyl-1H-pyrroles-3; the 4-dioctyl phthalate; anthraquinone-1; the 5-dioctyl phthalate; 3,5-pyrazoles dioctyl phthalate; 2-oil of mirbane-1, the 4-dioctyl phthalate; heptane-1; the 7-dioctyl phthalate; tetramethylene-1; 1-dioctyl phthalate 1,14-tetradecane dioctyl phthalate; 5,6-dehydrogenation norcamphane-2; the 3-dioctyl phthalate; 5-ethyl-2,3-dinicotinic acid or camphor dioctyl phthalate.
In addition, a kind of in the dicarboxylic acid more preferably mentioned by above example like this of at least two bidentate organic compounds.
At least two bidentate organic compounds can be for example derived from tricarboxylic acid, for example:
2-hydroxyl-1,2,3-propane tricarboxylic acid, 7-chloro-2; 3,8-quinoline tricarboxylic acid, 1,2; 3-, 1,2,4-benzene tricarboxylic acid, 1; 2,4-butane tricarboxylic acid, 2-phosphino--1,2; 4-butane tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 1-hydroxyl-1; 2,3-propane tricarboxylic acid, 4,5-dihydro-4; 5-dioxy-1H-pyrrolo-[2,3-F] quinoline-2,7; 9-tricarboxylic acid, 5-ethanoyl-3-amino-6-methylbenzene-1,2,4-tricarboxylic acid, 3-amino-5-benzoyl-6-methylbenzene-1; 2; 4-tricarboxylic acid, 1,2,3-propane tricarboxylic acid or aurin tricarboxylic acid.
In addition, a kind of in the tricarboxylic acid more preferably mentioned by above example like this of at least two bidentate organic compounds.
Example derived from least two bidentate organic compounds of tetracarboxylic acid is: 1,1-dioxo perylene [1,12-BCD] thiophene-3,4,9,10-tetracarboxylic acid, perylene tetracarboxylic acid such as perylene-3,4,9,10-tetracarboxylic acid or (perylene-1,12-sulfone)-3,4,9, the 10-tetracarboxylic acid, ethylene-dimalonic acid is as 1,2,3,4-ethylene-dimalonic acid or-1,2,3,4-ethylene-dimalonic acid, decane-2,4,6,8-tetracarboxylic acid, 1,4,7,10,13,16-hexaoxacyclooctadecane-6-2,3,11,12-tetracarboxylic acid, 1,2,4, the 5-benzene tetracarboxylic acid, 1,2,11,12-dodecane tetracarboxylic acid, 1,2,5,6-hexane tetracarboxylic acid, 1,2,7,8-octane tetracarboxylic acid, 1,4,5, the 8-naphthalenetetracarbacidic acidic, 1,2,9,10-decane tetracarboxylic acid, the benzophenone tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, tetrahydrofuran (THF) tetracarboxylic acid or pentamethylene tetracarboxylic acid such as pentamethylene-1,2,3,4-tetracarboxylic acid.
In addition, a kind of in the tetracarboxylic acid more preferably mentioned by above example like this of at least two bidentate organic compounds.
Wherein coordinate bond is following replacement or unsubstituted member ring systems via the heterocycle of preferred conduct at least two bidentate organic compounds of ring hetero atom formation:
Figure BDA00003309639300081
Very particularly preferably can have 1,2,3,4 or optional single at least aromatic dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid of replacing of more rings, wherein each ring can comprise at least one heteroatoms and two or more rings can comprise identical or different heteroatoms.For example preferred monocycle dicarboxylic acid, monocycle tricarboxylic acid, monocycle tetracarboxylic acid, dicyclo dicarboxylic acid, dicyclo tricarboxylic acid, dicyclo tetracarboxylic acid, three ring dicarboxylic acid, three ring tricarboxylic acid, three encircle tetracarboxylic acids, Fourth Ring dicarboxylic acid, Fourth Ring tricarboxylic acid and/or Fourth Ring tetracarboxylic acid.Suitable heteroatoms for example is N, O, S, B, P, and preferred heteroatoms is N, S and/or O.Here suitable substituents especially-OH, nitro, amino or alkyl or alkoxyl group.
Particularly preferred at least two bidentate organic compounds are aethylis imidazoas such as glyoxal ethyline acid esters, acetylene dioctyl phthalate (ADC), the camphor dioctyl phthalate, fumaric acid, succsinic acid, phthalic acid such as phthalic acid, m-phthalic acid, terephthalic acid (BDC), amino terephthalic acid, triethylenediamine (TEDA), methylglycine oxalic acid (MGDA), naphthalic acid (NDC), biphenyl dicarboxylic acid is as 4,4'-biphenyl dicarboxylic acid (BPDC), the pyrazine dioctyl phthalate is as 2,5-pyrazine dioctyl phthalate, the dipyridyl dioctyl phthalate is as 2,2'-dipyridyl dioctyl phthalate is as 2,2'-dipyridyl-5,5 '-dioctyl phthalate, benzene tricarboxylic acid is as 1,2,3-, 1,2,4-benzene tricarboxylic acid or 1,3,5-benzene tricarboxylic acid (BTC), benzene tetracarboxylic acid, diamantane tetracarboxylic acid (ATC), diamantane dibenzoate (ADB), benzene three benzoic ethers (BTB), methane four benzoic ethers (MTB), diamantane four benzoic ethers or dihydric para-phthalic acid are as 2,5-dihydric para-phthalic acid (DHBDC), tetrahydrochysene pyrene-2,7-dioctyl phthalate (HPDC), bibenzene tetracarboxylic (BPTC), two (4-pyridyl) propane (BPP) of 1,3-.
Especially very particularly preferably use glyoxal ethyline, 2-ethyl imidazol(e), phthalic acid, m-phthalic acid, terephthalic acid, 2,6-naphthalic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 1,2,3-benzene tricarboxylic acid, 1,2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 1,2,4,5-benzene tetracarboxylic acid, aminoBDC, TEDA, fumaric acid, biphenyl dicarboxylic acid ester, 1,5-and 2,6-naphthalic acid, tert-butyl isophthalic acid, resorcylic acid, BTB, HPDC, BPTC, BPP.
Except these at least two bidentate organic compounds, metallic organic framework also can comprise one or more unidentate ligands and/or one or more be not bidentate ligand at least derived from dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid.
Except these at least two bidentate organic compounds, metallic organic framework also can comprise one or more unidentate ligands.
Preferably at least two bidentate organic compounds are formic acid, acetic acid, perhaps aliphatic dicarboxylic acid or poly carboxylic acid, and for example propanedioic acid, fumaric acid etc., particularly fumaric acid are perhaps derived from these.
For the present invention, term " is derived " and is meant at least a at least two bidentate organic compounds and exist with partially or completely deprotonation form.In addition, term " is derived " and is meant at least a at least two bidentate organic compounds and can have other substituting group.Therefore, dicarboxylic acid or poly carboxylic acid not only have carboxylic-acid functional, and have one or more independent substituent as amino, hydroxyl, methoxyl group, halogen or methyl.Preferably there is not other substituting group.For the present invention, term " is derived " and is also meant carboxylic-acid functional and can be used as sulfur analogs and exist.Sulfur analogs Wei – C (=O) SH and tautomer thereof and-C (S) SH.
The solvent that is suitable for preparing metallic organic framework is ethanol, dimethyl formamide, toluene, methyl alcohol, chlorobenzene, diethylformamide, methyl-sulphoxide, water, hydrogen peroxide, methylamine, sodium hydroxide solution, N-Methyl pyrrolidone, ether, acetonitrile, benzyl chloride, triethylamine, ethylene glycol and composition thereof especially.The solvent of other metal ion, at least two bidentate organic compounds and preparation MOF especially is described in US-A5,648,508 or DE-A10111230 in.
The pore size of metallic organic framework can be by the selection control of suitable ligand and/or at least two bidentate organic compounds.Usually, organic compound is more big, and pore size is more big.Pore size is preferably 0.2-30nm based on crystalline material, preferred especially 0.3-3nm.
Provide the example of metallic organic framework below.Except the title of skeleton, also show metal and at least bidentate ligand, solvent and unit cell parameters (with
Figure BDA00003309639300101
Angle α, β and γ and size A, B and the C of expression).The latter measures by X-ray diffraction.
Figure BDA00003309639300111
Figure BDA00003309639300112
Figure BDA00003309639300121
Figure BDA00003309639300122
Figure BDA00003309639300131
Figure BDA00003309639300132
Figure BDA00003309639300141
Figure BDA00003309639300142
Figure BDA00003309639300151
Figure BDA00003309639300152
Figure BDA00003309639300161
Figure BDA00003309639300162
Figure BDA00003309639300171
Figure BDA00003309639300172
Figure BDA00003309639300191
Figure BDA00003309639300192
Figure BDA00003309639300201
Figure BDA00003309639300202
Figure BDA00003309639300221
Figure BDA00003309639300222
Figure BDA00003309639300231
ADC acetylene dioctyl phthalate
The NDC naphthalic acid
The BDC phthalic acid
ATC diamantane tetracarboxylic acid
The BTC benzene tricarboxylic acid
BTB benzene three phenylformic acid
MTB methane four phenylformic acid
ATB diamantane four phenylformic acid
ADB diamantane dibenzoic acid
Other metallic organic framework is MOF-2 to 4, MOF-9, MOF-31 to 36, MOF-39, MOF-69 to 80, MOF103 to 106, MOF-122, MOF-125, MOF-150, MOF-177, MOF-178, MOF-235, MOF-236, MOF-500, MOF-501, MOF-502, MOF-505, IRMOF-1, IRMOF-61, IRMOP-13, IRMOP-51, MIL-17, MIL-45, MIL-47, MIL-53, MIL-59, MIL-60, MIL-61, MIL-63, MIL-68, MIL-79, MIL-80, MIL-83, MIL-85, CPL-1 to 2, SZL-1, it is described in the document.
Particularly preferred metallic organic framework is MIL-53, Zn-tBu-m-phthalic acid, Al-BDC, MOF-5, MOF-177, MOF-505, IRMOF-8, IRMOF-11, Cu-BTC, Al-NDC, Al-AminoBDC, Cu-BDC-TEDA, Zn-BDC-TEDA, Al-BTC, Cu-BTC, Al-NDC, Mg-NDC, fumaric acid aluminium, glyoxal ethyline zinc, 2-aminooimidazole zinc, biphenyl dicarboxylic acid copper-TEDA, MOF-74, Cu-BPP, terephthalic acid scandium.More preferably terephthalic acid scandium, Al-BDC and Al-BTC.Yet, because their environment friendly, special preferable formic acid magnesium, magnesium acetate and composition thereof.Preferred especially fumaric acid aluminium.
The layer of porous metal-organic framework preferably has 0.1-100g/m 2, more preferably 1-80g/m 2, even more preferably 3-50g/m 2Quality.
Embodiment
Following examples show the whole bag of tricks that applies filter paper with fumaric acid aluminium MOF by directly synthesizing.
For all embodiment, two kinds of solution of preparation as described below:
Solution 1: deionized water (72.7g) put into container and with Al 2(SO 4) 3* 18H 2O (16.9g, 25.5 mmoles) is dissolved in wherein, stirs simultaneously.
Solution 2: deionized water (87.3g) is put into container and NaOH (6.1g, 152.7 mmoles) is dissolved in wherein stirring simultaneously.Add fumaric acid (5.9g, 50.9 mmoles) subsequently, stir simultaneously, and stir the mixture until forming clear solution.
For embodiment 1, use the strainer (d=150mm) from Macherey-Nagel.From Schleicher﹠amp; The filter paper of Schuell (d=90-110mm) is used for embodiment 2.The surface-area of filter paper of being untreated is～1-2m 2/ g (by the specific surface area of Langmuir method (LSA) mensuration).The surface-area of coated paper use little strainer sample (～100mg) measure.
In all embodiments, room temperature is 22 ℃.
Embodiment 1: by at room temperature in the rotating spraying drum solution spray being applied filter paper
Experimental technique:
Be fixed in spraying drum by adhesive tape filter paper and under the rotation of room temperature and drum by the pump with shower nozzle with solution 1 spraying.After simple drying or under dampness, at room temperature by pump spray solution 2.Subsequently that filter paper is at room temperature dry in compressed air jet in cylinder.Must arrive the uniform coating that the edge has a little flocculus.The quality of filtrate rises to 1.2-2.3g.With the paper of drying on the suction filter under slight pump vacuum with the H of each 10ml 2O washing 4 times, and at room temperature dry again.The gained filtrate is activated 16 hours down at 150 ℃ in vacuum drying oven.The XRD analysis of selected sample demonstrates outside the Ibeta Mierocrystalline cellulose, the weak peak at 102 θ places, and it can be appointed as fumaric acid aluminium MOF.Corresponding surface-area is 51m 2/ g LSA.
Embodiment 2: apply filter paper by while spray solution 1 and 2
Experimental technique:
Filter paper is suspended and with two kinds of solution of 1ml at the most spray simultaneously (Eco-Spray atomizer and Desaga SG-1 atomizer).The filter paper handled at room temperature at air drying, is suspended simultaneously.Obtain having the homogeneous layer of a little little flocculus.The filtrate quality that improves is 80-290mg.Subsequently with the H of paper with each 10ml 2O washing 4 times, and following dry 16 hours at 100 ℃ in the convection drying case.Detect 31-279mg at filter paper then.This is equivalent to 4.9-42g/m 2The XRD analysis of selected sample demonstrates outside the Ibeta Mierocrystalline cellulose, and at the strong peak (degree of crystallinity～3000) at 102 θ places, it can be appointed as fumaric acid aluminium MOF.
Embodiment 3: the coating of other carrier surface
With tea napkin (90% cotton, 10% flax) A, mitten B, Mierocrystalline cellulose cloth 10 * 10cm sheet of C, bandage refuse (viscose glue) D and Basotect E (melamine resin foam) is handled in the mode identical with filter paper among the embodiment 2.The quality that absorbs after spraying and drying is 770-500mg.Wash Sample A-D with water and subsequently at room temperature after the drying, obtaining the coating of 440-580mg.This is equivalent to 4.4-5.8g/m 2The analysis of all samples shows that except the signal of each material, at the peak that 10 ° (2-θ) locate, it can be appointed as fumaric acid aluminium MOF.The surface-area of handling material is 17-22m 2/ g LSA.

Claims (10)

1. with comprising the method that is coated to the small part carrier surface at least with the porous metal-organic framework of at least a two bidentate organic compounds of at least a metallic ion coordination, it comprises the steps:
(a) with at least a portion carrier surface first solution spray that comprises at least a metal ion;
(b) with at least a portion carrier surface second solution spray that comprises at least a at least two bidentate organic compounds,
Wherein step (b) is before step (a), carry out forming the porous metal-organic framework layer later on or simultaneously.
2. dry according to the process of claim 1 wherein described layer.
3. according to the method for claim 2, wherein that described layer is dry down at least 150 ℃.
4. according to each method among the claim 1-3, wherein carry out in the spraying drum with first, second or with two kinds of solution sprays.
5. according to each method among the claim 1-4, wherein first, second or two kinds of solution are at room temperature.
6. according to each method among the claim 1-5, wherein first, second or two kinds of solution are the aqueous solution.
7. according to each method among the claim 1-6, wherein carrier surface is fiber or foam surface.
8. according to each method among the claim 1-7, wherein said at least a metal ion is selected from Mg, Ca, Al and Zn.
9. according to each method among the claim 1-8, wherein said at least a at least two bidentate organic compounds are derived from dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid.
10. according to each method among the claim 1-9, wherein said porous metal-organic framework layer has 0.1-100g/m 2Quality.
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