Patent Application: US-200913129733-A

Abstract:
the present invention relates to a method for preparing an mof solid of a crystallised and porous aluminium aromatic azocarboxylate , in a non - aqueous organic medium . the invention also relates to solids made up of metal - organic frameworks of aluminium aromatic azocarboxylates capable of being obtained by the method of the invention , as well as to the uses thereof for the storage of liquid or gaseous molecules , for selective separation of gas and for catalysis .

Description:
the purpose of the present invention is precisely to meet this requirement by providing a method for preparing a mof solid of a crystallized and porous aluminum aromatic azocarboxylate , including at least the following steps of : at least a metal inorganic precursor in the form of a metal al , a metal salt al3 + or a coordination complex including metal ion al3 + ; and at least an organic precursor of the ligand l , l being an aromatic azodi -, azotri -, azotetra - carboxylate ligand of formula r 0 r 1 n 2 ( coo − ) q where r 0 and r 1 independently from each other , represent , a mono - or poly - cyclic , fused or non fused , aryl radical , including 6 to 50 carbon atoms , for example 6 to 27 carbon atoms , a mono - or poly - cyclic , fused or non fused , heteroaryl radical including 4 to 50 carbon atoms , for example 4 to 20 carbon atoms , the r 0 radical being optionally substituted by one or more groups independently selected from the group including c 1 - 10 alkyl , c 2 - 10 alkene , c 2 - 10 alkyne , c 3 - 10 cycloalkyl , c 1 - 10 heteroalkyl , c 1 - 10 haloalkyl , c 6 - 10 aryl , c 3 - 20 heterocyclic , c 6 - 10 aryl c 1 - 10 alkyl , c 5 - 10 heteroaryl c 1 - 10 alkyl , f , cl , br , i , — no 2 , — cn , — cf 3 , — ch 2 cf 3 , — oh , — ch 2 oh , — ch 2 ch 2 oh , — nh 2 , — ch 2 nh 2 , — nhcho , — cooh , — conh 2 , — so 3 h , — po 3 h 2 , ( ii ) heating the mixture obtained in ( i ) at a temperature of at least 50 ° c . so as to obtain said solid . in the frame of the present invention the terms “ crystallized solid ” and “ crystalline solid ” may be indifferently used to indicate a solid in which the atoms , the ions or the molecules form long distance ordered arrangements in the three space dimensions , leading to a single signature composed of a specific succession of diffraction peaks ( x - rays for example ) for each solid . an “ amorphous solid ” is a solid where the atoms , ions or molecules , although locally ordered , disorderly stack up at long distance . this leads to a signature of one or more very wide diffraction peaks ( x - rays for example ) preventing a precise identification of the material ( as several solids can coexist and lead to the same diffraction signature ). in many solids , the atoms , ions or molecules can adopt several arrangements according to their formation conditions . these different arrangements constitute the various existing “ phases ” of the solid in a given chemical system . the physical properties like the melting point and the density of the various phases are distinguished , permitting the differentiation of the solids . within the meaning of the present invention , what is meant by “ alkyl ” is a saturated , optionally substituted , linear or branched carbon radical including 1 to 12 carbon atoms , for example 1 to 10 carbon atoms , for example 1 to 8 carbon atoms , for example 1 to 6 carbon atoms . for example , an alkyl radical may be a methyl , ethyl , n - propyl , isopropyl , n - butyl , sec - butyl , isobutyl , tert - butyl , n - pentyl , sec - pentyl , isopentyl , tert - pentyl , n - hexyl , sec - hexyl radical or like radicals . within the meaning of the present invention , what is meant by “ alkene ” is a linear or branched , cyclic or acyclic , unsaturated hydrocarbon radical including at least a double carbon - carbon bond . the alkenyl radical may comprise 2 to 20 carbon atoms , for example 2 to 10 carbon atoms , more particularly 2 to 8 carbon atoms , even more particularly 2 to 6 carbon atoms . for example , an alkenyl radical may be an allyl , ethenyl , propenyl , butenyl , 1 - methyl - 2 - buten - 1 - yl radical or like radicals . the term “ alkyne ” designates a linear or branched , cyclic or acyclic unsaturated hydrocarbon radical , including at least a triple carbon - carbon bond . the alkynyl radical may comprise 2 to 20 carbon atoms , preferably 2 to 10 carbon atoms , more particularly 1 to 8 carbon atoms , even more particularly 2 to 6 carbon atoms . for example , an alkynyl radical may be an ethynyl , 2 - propynyl ( propargyl ), 1 - propynyl radical or like radicals . within the meaning of the present invention , what is meant by “ aryl ” is an aromatic system including at least a ring satisfying hückel &# 39 ; s aromaticity rule . said aryl is optionally substituted and may comprise from 6 to 50 carbon atoms , for example 6 to 27 carbon atoms , in particular 6 to 14 carbon atoms , more particularly 6 to 12 carbon atoms . for example , an aryl radical may be a phenyl , naphthyl , tetrahydronaphthyl , indanyl , indenyl group or like radicals . within the meaning of the present invention , what is meant by “ heteroaryl ”, is a system including at least an aromatic ring of 4 to 50 carbon atoms , for example 4 to 20 carbon atoms , and at least a heteroatom selected from the group including in particular sulfur , oxygen , nitrogen . said heteroaryl may be substituted . for example , a heteroaryl radical may be a pyridyl , pyrazinyl , pyrimidinyl , pyrrolyl , pyrazolyl , imidazolyl , thiazolyl , oxazolyl , isooxazolyl , thiadiazolyl , oxadiazolyl , thiophenyl , furanyl , quinolinyl , isoquinolinyl radical and like radicals . within the meaning of the present invention , what is meant by “ cycloalkyl ” is a cyclic , saturated or unsaturated , optionally substituted carbon radical , which may comprise 3 to 10 carbon atoms . for example , cyclopropyl , cyclobutyl , cyclopentyl , cyclohexyl , cycloheptyl , cyclooctyl , 2 - methylcyclobutyl , 2 , 3 - dimethylcyclobutyl , 4 - methylcyclobutyl , 3 - cyclopentylpropyl may be mentioned . within the meaning of the present invention , what is meant by “ haloalkyl ” is an alkyl radical such as previously defined , said alkyl system including at least a halogen selected from the group including fluorine , chlorine , bromine , iodine . within the meaning of the present invention , what is meant by “ heteroalkyl ”, is an alkyl radical such as previously defined , said alkyl system including at least a heteroatom , particularly , a heteroatom selected from the group including sulfur , oxygen , nitrogen , phosphorus . within the meaning of the present invention , what is meant by “ heterocycle ” is a saturated or unsaturated , optionally substituted , cyclic carbon radical including at least a heteroatom and which may comprise 3 to 20 carbon atoms , preferably 5 to 20 carbon atoms , preferably 5 to 10 carbon atoms . the heteroatom may be for example selected from the group including sulfur , oxygen , nitrogen , phosphorus . for example , a heterocyclic radical may be a pyrrolidinyl , pyrazolinyl , pyrazolidinyl , imidazolinyl , imidazolidinyl , piperidinyl , piperazinyl , oxazolidinyl , isoxazolidinyl , morpholinyl , thiazolidinyl , isothiazolidinyl , or tetrahydrofuryl group . within the meaning of the present invention , what is meant by “ alkoxy ”, “ aryloxy ”, “ heteroalkoxy ” and “ heteroaryloxy ”, respectively , is an alkyl , aryl , heteroalkyl and heteroaryl radical bonded to an oxygen atom . for example , an alkoxy radical may be a methoxy , ethoxy , propoxy , isopropoxy , n - butoxy , tert - butoxy , neopentoxy , n - hexoxy radical or like radicals . the term “ substituted ” designates for example the replacement of a hydrogen atom in a structure given by a group such as previously defined . when more than one position can be substituted , the substituents may be same or different at each position . in the context of the invention , the organic solvent can be made up of only one solvent or a mixture of organic solvents . the term “ nonaqueous solvent ” advantageously refers to a solvent or a mixture of solvents containing up to 5 wt %, preferably 1 wt %, more preferably 0 . 1 wt % and even more preferably up to 0 . 01 wt % of water with respect to the total weight of all solvents . the nonaqueous organic solvent can be selected from the group including n , n - dimethylformamide ( dmf ), n , n - diethylformamide ( def ), dioxane , methanol , ethanol , n - propanol , isopropanol , n - butanol , isobutanol , tert - butanol , cyclohexanol , pyridine , toluene , ethyl acetate , dimethyl sulfoxide ( dmso ). the nonaqueous organic solvent is more particularly selected from the group including dmf , def , dioxane , methanol , ethanol , dmso . the metal inorganic precursor in step ( i ) may be a metal al , metal salt al 3 + or a coordination complex including metal ion al 3 + . when it is metal salt , the counter - ion may be an inorganic ion selected from the group including sulfate , nitrate , nitrite , sulphite bisulfite , phosphate , phosphite , fluoride , chloride , bromide , iodide , perchlorate , carbonate , bicarbonate . the counter - ion may also be an organic ion selected from the group including acetates , formates , oxalates , citrates , ethoxy , isoproxy . preferably , the metal inorganic precursor is a metal salt al 3 + . the crystalline spatial organization of the solids of this invention forms the basis of the particular characteristics and features of these materials . in particular , it governs the size of the pores , which affects the specific surface area of the materials and the adsorption characteristics . it also governs the density of the materials which is relatively weak , the proportion of metal in these materials , the stability of the materials , the rigidity and the flexibility of the structures , etc moreover , the pore size may be adjusted by the choice of appropriate ligands l . in the method of the invention , the ligand l is more particularly an aromatic azodi - or azotetra - carboxylic ligand , selected from the group including : c 12 h 8 n 2 ( co 2 − ) 2 ( azobenzene - 4 , 4 ′- dicarboxylate ), c 12 h 6 cl 2 n 2 ( co 2 − ) 2 ( dichloro - azobenzene - 4 , 4 ′- dicarboxylate ), c 12 h 6 n 2 ( co 2 − ) 4 ( azobenzene - 3 , 3 ′, 5 , 5 ′- tetracarboxylate ), c 12 h 6 n 2 ( oh ) 2 ( co 2 − ) 2 ( dihydroxy - azobenzene - 4 , 4 ′- dicarboxylate ). in step ( i ) the metal inorganic precursor and the organic precursor of the ligand l can be mixed in a molar ratio comprised between 1 and 5 . as already indicated , mof solids according to the invention have a crystallized structure which provides these materials with specific properties . in the method according to the invention , crystallization is carried out in a precise temperature range . thus , in step ( ii ), the mixture is heated at a temperature ranging from 50 ° c . to 150 ° c . the mixture may be heated for 1 to 10 days . one day corresponds to 24 hours . the mixture may be heated in a closed cell . step ( ii ) may be carried out with an autogenous pressure higher than 10 5 pa . an “ autogenous ” pressure corresponds to the pressure generated by the reagents at a given temperature in a closed reaction cell . the solid obtained at the end of step ( ii ) may be further subjected to an activation step ( iii ) in which said solid is heated at a temperature of 100 ° c . to 300 ° c ., preferably of 100 ° c . to 200 ° c . in this step , the solid may be heated for 1 to 48 hours . the activation step ( iii ) may be optionally carried out in a mixture of solvent ( s ) selected from the group including dmf , def , methanol , ethanol , dmso or water . with this activation step ( iii ) it is particularly possible to empty the pores of the mof solid of the invention and make them available for the intended use of said solid . emptying can be done , for example , by the departure of the water , solvent molecules and / or if necessary , of the molecules of ligands l present in the reaction medium . resulting mof solids will then have a stronger adsorption and storage capacity . the object of the present invention is also an mof solid of a crystallized and porous aluminum aromatic azocarboxylate that may be obtained by the method according to the invention , including a three - dimensional succession of patterns of formula ( i ): al represents the metal ion al 3 + ; m is 1 to 15 , for example 1 to 8 ; k is 0 to 15 , for example 1 to 8 ; l is 0 to 10 , for example 1 to 8 ; p is 1 to 10 , for example 1 to 5 ; m , k , l and p are selected so as to respect the neutrality of the charges of said pattern ; x is an anion selected from the group including oh − , cl − , f − , i − , br − , so 4 2 − , no 3 —, clo 4 − , pf 6 − , bf 3 − , r 2 —( coo − ) n , r 2 —( so 3 − ) n , r 2 —( po 3 − ) n , where r 2 is hydrogen , linear or branched , optionally substituted c 1 - 12 alkyl , n = 1 to 4 ; l is a ligand such as previously defined . aluminum aromatic azocarboxylate mof solids prepared by the method of the invention exhibit some advantages of which : they are crystallized solids , they are highly pure ( no secondary product such as for example aluminum hydroxyl is detected ), and the exhibit a significant porosity ( langmuir surface up to 3500 m 2 / g ) allowing to particularly control the adsorption characteristics of certain molecules . preferably , x is selected from the group including oh − , cl − , f − , clo 4 − . mof solids according to the invention preferably comprise al from 5 to 50 % in wt %. mof solids that may be obtained by the method of the invention have pores , and more particularly micro - and / or meso - pores . the micropores can be defined as pores having a diameter lower than or equal to 2 nm ( diameter ≦ 2 nm ) and the mesopores as pores having a diameter higher than 2 nm and that up to 50 nm ( 2 nm & lt ; diameter & lt ; 50 nm ). preferably , the diameter of the pores of the mof solid of the invention ranges from 0 . 2 to 6 nm . the presence of micro - and meso - pores may be followed by sorption measurements so as to determine the capacity of the mof solid to absorb nitrogen at 77k according to din 66131 . the specific surface area of the solids made up of porous and crystallized aluminum aromatic azocarboxylate mofs , that may be obtained by the method of the invention , may be measured by the bet method and determined and calculated by the langmuir model . said solids may have a bet surface area from 50 to 4200 m 2 / g , more particularly from 100 to 3000 m 2 / g . they may also have a langmuir surface area from 50 to 6000 m 2 / g , more particularly from 150 to 3500 m 2 / g . mof solids according to the invention advantageously have a porous volume of 0 . 3 to 4 cm 3 / g . within the framework of the invention , porous volume means the volume accessible for gas or liquid molecules . within the framework of this invention , mof solids may have a gas load capacity from 0 . 5 to 50 mmol of gas per gram of dry solid . the load capacity means the gas storage capacity or the quantity of gas adsorbed by the solid . these values and this definition also apply to the load capacity of liquids . mof solids of this invention may particularly exhibit the advantage of a thermal stability up to a temperature of 500 ° c . more particularly , these solids may have a thermal stability between 250 ° c . and 450 ° c . mof solids of the invention are crystallized and may preferably be in the form of crystallites with a length which varies from 0 . 05 to 100 μm , more particularly from 0 . 05 to 20 μm . they are preferably in the form of small crystals having a particular morphology ( needles , plates , octahedral , etc .) also permitting their precise identification by examination through a scanning electron microscope ( sem ). as already indicated , mof solids according to the invention have a crystallized structure and are highly pure providing these materials with specific properties . contrary to the known solids , aluminum azocarboxylate mof solids according to the invention are composed of a single phase . that means that the other phases that may exist in the considered chemical system are not present mixed with the solid . moreover , aluminum azocarboxylate mof solids that may be obtained by a preparation process as previously described , exhibit a degree of purity of at least 95 %, in particular at least 98 mass %. the purity of mof solids of the invention may be in particular determined by elementary chemical analysis , x - rays diffraction , scanning electron microscopy . thus , the obtained mof solids , do not comprise , or very little , secondary products such as for example aluminum hydroxide of formula al ( oh ) 3 or alo ( oh ) or the other phases of the considered chemical system appearing under other synthesis conditions . the particular structural characteristics of the solids of the present invention make them high load capacity , highly selective , and highly pure adsorbents . thus , they make the selective adsorption , and thus , the selective separation of gas molecules such as for example of no , n 2 , h 2 s , h 2 , ch 4 , o 2 , co , co 2 . . . ) molecules , possible . the object of the present invention is also the use of a solid composed of crystallized and porous aluminum azocarboxylates mof for the storage of liquid or gas molecules , for selective gas separation [ 25 ] or for catalysis [ 26 ]. other advantages will become more apparent to the skilled person upon reading the examples below , illustrated by the accompanying figures , given by way of illustration . fig1 represents the x - ray diffraction diagram of the phase mil - 130 ( al ) ( cuk d ). the x - coordinate represents the angular variation in 2d ) (°). the ordinate represents the relative diffraction peak intensity . fig2 represents the phase mil - 130 adsorption isotherm n 2 at 77k of . the ratio p / p 0 which corresponds to the relative pressure is given in x - coordinate . the volume of adsorbed gas per gram of product ( cm 3 · g − 1 ) is represented on the ordinate . fig3 represents the thermogravimetric analysis curve of mil - 130 ( al ) ( under o 2 stream , 3 ° c .· min − 1 ). the percentage of the mass loss is represented on the ordinate . the heating temperature is represented on the x - coordinate . fig4 represents the photography ( scanning electron microscopy ) of a sample of mil - 130 ( al ) showing hexagonal rod shaped crystallites . fig5 represents the photography ( scanning electron microscopy ) of a sample of mil - 130 ( al ) showing ovoid crystallite aggregates shaped crystallites . fig6 represents the photography ( scanning electron microscopy ) of a sample of mil - 130 ( al ) showing ovoid plates shaped crystallites . the following examples describe the synthesis of solids made up of mofs of microporous aluminum aromatic azocarboxylate ( noted mil - n ) obtained with azobenzene carboxylate type ligands and more particularly with the azodibenzene - 4 , 4 ′- dicarboxylate . the synthesized compounds ( noted mil - n ) were then characterized by x - ray powder diffraction , by thermogravimetric analysis , scanning electron microscopy ( sem ) and their specific surface areas were measured by the bet method . the diffraction diagrams were recorded using a diffractometer ( siemens d5000 ) in bragg - brentano reflection geometry on an angular 2theta field of 2 to 40 ° with a pitch and a count time of 0 . 02 ° and 1 second , respectively ( cuk d1 , 2 radiation ). the thermogravimetric analysis ( ta instrument 2050 ) was carried out from a sample of 5 or 20 mg heated on a balance at 20 to 600 ° c . under oxygen stream with a heating rate of 3 ° c .· min − 1 . with regard to the examination with the scanning electron microscope ( leo 1530 ), the samples were metallized with carbon then placed in a vacuum room under the electron beam . the specific surface areas were measured on a micromeritics asap2010 apparatus from 100 mg samples which were heated beforehand under vacuum at 200 ° c . for 12 hours . compound mil - 130 ( al ) is obtained from a mixture of 3 . 6 g of aluminum nitrate ( ai ( no 3 ) 3 . 9h 2 o ), 1 . 2 g of azodibenzene - 4 , 4 ′- dicarboxylic acid and 70 ml of dmf ( n , n ′- dimethylformamide ) placed in a 125 ml teflon cell then inserted in a parr steel autoclave ( registered trademark ). the reaction takes place at 100 ° c . for 7 days in an oven . 2 g of mil - 130 ( al ) are obtained . the product is activated by heating at 200 ° c . over night . a second preparation may be prepared from a mixture of 0 . 36 g aluminum perchlorate ( ai ( cio 4 ) 3 . 9h 2 o ), 0 . 1 g of azodibenzene - 4 , 4 ′- dicarboxylic acid , 5 ml of dmf ( n , n ′- dimethylformamide ) placed in a 23 ml teflon cell then a parr type steel autoclave ( trade name ). the reaction takes place at 100 ° c . for 7 days in an oven . 0 . 11 g of mil - 130 ( al ) are obtained . a third preparation may be prepared from a mixture of 0 . 19 g of aluminum chloride hexahydrate ( ai ( cl ) 3 . 6h 2 o ), 0 . 1 g of azodibenzene - 4 , 4 ′- dicarboxylic acid , 5 ml of dmf ( n , n ′- dimethylformamide ) placed in a 23 ml teflon cell then a steel autoclave of trade name parr ( registered trademark ). the reaction takes place at 100 ° c . for 7 days in an oven . 0 . 07 g of mil - 130 ( al ) are obtained . a fourth preparation may be prepared from a mixture of 0 . 1 g of anhydrous aluminum chloride ( ai ( cl ) 3 ), 0 . 1 g of azodibenzene - 4 , 4 ′- dicarboxylic acid , 5 ml of dmf ( n , n ′- dimethylformamide ) placed in a 23 ml teflon cell then a steel autoclave of brand name parr ( registered trademark ). the reaction takes place at 100 ° c . for 7 days in an oven . 0 . 07 g of mil - 130 ( al ) are obtained . a fifth preparation may be prepared from a mixture of 0 . 1 g of anhydrous aluminum chloride ( ai ( cl ) 3 ), 0 . 1 g of azodibenzene - 4 , 4 ′- dicarboxylic acid , 5 ml of dmf ( n , n ′- dimethylformamide ) placed in a 23 ml teflon cell then a steel autoclave of brand name parr ( registered trademark ). the reaction takes place at 100 ° c . for 4 hours in an oven . 0 . 07 g of mil - 130 ( al ) are obtained . the examination of these solids ( for example , the fourth preparation ) with the electron microscope shows the presence of small hexagonal rod - shaped crystals with a mean size of 0 . 2 to 0 . 8 microns ( fig4 ), of ovoid crystallite aggregates ( fig5 ) from the second preparation or of ovoid plates ( fig6 ) from the first preparation . the bragg peaks of the powder diagram may correspond to a hexagonal mesh with parameters a = b = 33 . 264 ( 1 ) â and c = 4 . 681 ( 1 ) â , v = 4417 . 5 ( 1 ) â 3 . the x - ray diffractogram is shown on fig1 . the bet surface area is of 1770 m 2 / g and the langmuir surface is of 3190 m 2 / g . the adsorption isotherm exhibits a step for p / p 0 = 0 . 15 , which is characteristic of mesoporous cavities or tunnels ( fig2 ). the thermogravimetric analysis indicates that the material mil - 100 ( al ) is stable up to 420 ° c . ( fig3 ). the combination of these various characterization analyses ( xrd , sem ) shows that it is a very well identified material with a high crystalline purity . following the xrd observation , a compound , for which phase mil - 130 ( ai ) represents the major part at least up to 95 % ( in mass ) may be defined . reticular synthesis and the design of new materials , o . m . yaghi , m . o &# 39 ; keeffe , n . w . ockwig , h . k . chae , m . eddaoudi and j . kim , nature , 423 , 705 - 14 ( 2003 ). functional porous coordination polymers , s . kitagawa , r . kitaura and s .- l . noro , angew . chem . int . ed ., 43 , 2334 - 75 ( 2004 ). hybrid porous solids : past , present , future , g . férey , chem . soc . rev ., 37 , 191 - 214 ( 2008 ). hydrogen storage in microporous metal - organic frameworks , n . l . rosi , j . eckert , m . eddaoudi , d . t . vodak , j . kim , m . o &# 39 ; keeffe and o . m . yaghi , science , 300 , 1127 - 9 ( 2003 ). hydrogen adsorption in the nanoporous metal - benzenedicarboxylate m ( oh ) ( o 2 c — c 6 h4 - co 2 ) ( m = al 3 + , cr 3 + ), mil - 53 , g . férey , m . latroche , c . serre , f . millange , t . loiseau and a . percheron - guéegan , chem . commun ., 2976 - 7 ( 2003 ). hydrogen storage in the giant - pore metal - organic frameworks mil - 100 and mil - 101 , m . latroche , s . surblé , c . serre , c . mellot - draznieks , p . l . llewellyn , j .- h . lee , j .- s . chang , s . h . jhung and g . férey , angew . chem . int . ed ., 45 , 8227 ( 2006 ). systematic design of pore size and functionality in isoreticular mofs and their application in methane storage , m . eddaoudi , j . kim , n . rosi , d . vodak , j . wächter , m . o &# 39 ; 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synthesis and catalysis properties of mil - 100 ( fe ), an iron ( 111 ) carboxylate with large pores & gt ;& gt ; p . horcajada , s . surble , c . serre , d .- y . hong , y .- k . seo , j .- s chang , j .- m . greneche , i . margiolaki and g . férey , chem . commun . 2820 - 2 ( 2007 ); & lt ;& lt ; catalytic properties of mil - 101 & gt ;& gt ; a . henschel , k . gedrich , r . kraehnert and s . kaskel , chem . commun . 4192 - 4 ( 2008 ); & lt ;& lt ; amine grafting on coordinatively unsaturated metal centers of mofs : consequences for catalytis and metal encapsulation & gt ;& gt ; y . k . hwang , d .- y . hong , j .- s . chang , s . h . jhung , y .- k . seo , j . kim , a . vimont , m . daturi , c . serre and g . férey , angew . chem . int . ed . 47 4144 - 8 ( 2008 ).