WO2007091828A1 - A preparation method of porous hybrid inorganic-organic materials - Google Patents
A preparation method of porous hybrid inorganic-organic materials Download PDFInfo
- Publication number
- WO2007091828A1 WO2007091828A1 PCT/KR2007/000648 KR2007000648W WO2007091828A1 WO 2007091828 A1 WO2007091828 A1 WO 2007091828A1 KR 2007000648 W KR2007000648 W KR 2007000648W WO 2007091828 A1 WO2007091828 A1 WO 2007091828A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hybrid inorganic
- porous hybrid
- organic materials
- preparation
- organic
- Prior art date
Links
- 239000011368 organic material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 16
- XTUBPKVLOAIMQY-UHFFFAOYSA-H chromium(3+);terephthalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1.[O-]C(=O)C1=CC=C(C([O-])=O)C=C1.[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 XTUBPKVLOAIMQY-UHFFFAOYSA-H 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- JSCNZPJYIJBBJI-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O.[O-]C(=O)c1ccc(cc1)C([O-])=O JSCNZPJYIJBBJI-UHFFFAOYSA-D 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- XTWMRBJKMXZQDS-UHFFFAOYSA-N iron;terephthalic acid Chemical compound [Fe].OC(=O)C1=CC=C(C(O)=O)C=C1 XTWMRBJKMXZQDS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- KVQQRFDIKYXJTJ-UHFFFAOYSA-N naphthalene-1,2,3-tricarboxylic acid Chemical class C1=CC=C2C(C(O)=O)=C(C(O)=O)C(C(=O)O)=CC2=C1 KVQQRFDIKYXJTJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical class OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims 3
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 26
- 238000003786 synthesis reaction Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000005485 electric heating Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical group [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carboxylate anions Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
-
- 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
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- 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
Definitions
- the present invention relates to a preparation method of porous hybrid inorganic- organic material useful as adsorbents, gas storages, catalysts, catalyst supports, carriers and templates for nanomaterials and electronic and electric materials. More particularly, present invention relates to a preparation method of porous hybrid inorganic- organic material, with particle size less than 500 nm, by using microwave heating rather than conventional electric heating as a heat source for a hydrothermal or sol- vothermal synthesis.
- the porous hybrid inorganic-organic materials that are explained in this invention are defined as inorganic-organic coordination polymers composed of central metallic ions and organic ligands coordinated to the metal ions.
- the porous hybrid inorganic-organic materials are crystalline materials having porous structures with the pore sizes of molecules or nanometers, and the framework structures of porous hybrid inorganic- organic materials are composed of both organic materials and inorganic species.
- the porous hybrid inorganic-organic material is wide terminology and also can be called as porous coordination polder (Angew. Chem. Intl. Ed., 43, 2334. 2004) or metal- organic framework (Chem. Soc. Rev., 32, 276, 2003).
- porous hybrid inorganic-organic materials can be synthesized by several methods including solvent-diffusion method, hydrothermal synthesis using water as solvent and a solvothermal synthesis using an organic solvent (Microporous Mesoporous Mater., 73, 15, 2004; Accounts of Chemical Research, 38, 217, 2005).
- the synthesis of porous hybrid inorganic-organic materials can be executed, similar to the synthesis of inorganic porous materials including zeolites and mesoporous materials, under autogenous pressure in the presence of water or suitable solvents at zeolites and mesoporous materials, during several days at high temperature after loading reactants in a high pressure reactor such as an autoclave.
- the heat source for high temperature has generally been electric or resistive heating.
- an autoclave containing precursors including metal salts, organic ligands and water or solvent was heated using an electric heater or an electric oven at a constant temperature.
- the methods of the previous embodiments have drawbacks of using excessive energy because the nucleation or crystallization is very slow.
- the methods are very inefficient because the synthesis can be carried out only by batch reactions (Accounts of Chemical Research, 38, 217, 2005). The previous synthesis methods are considered as inefficient methods to implement commercial applications because of high production cost.
- porous catalytic materials with small particle size have advantages of increased activity and facile regeneration of used catalysts because diffusivity increases with decreasing the crystal size of catalysts (Catalysis Today, 41, 37, 1998; Polymer Degradation and Stability 70, 365, 2000).
- nanocrystalline porous materials have many applications inthe fields of sensors, optoelectronics and medicines (Chem. Mater., 17, 2494, 2005).
- it is not easy to synthesize small crystals and so-called nanoparticles smaller than 100 nm is especially difficult to obtain because of easy aggregation or coagulation.
- Carbon or polymer templates may be used to synthesize nanoparticles even though the synthesis process is complex.
- it is not easy to obtain pure nanoparticles without a template because small particles grow easily to a big size when the template is removed.
- porous hybrid inorganic-organic materials with homogeneous particle size and membrane or thin film of the materials for the applications in sensors or opto-electronic devices.
- membranes or thin films were made by two steps of synthesizing and making a simple composite by impregnation of porous hybrid inorganic-organic materials on a polymer.
- the process is complex and it is difficult to apply for insoluble porous hybrid inorganic- organic materials.
- Another method using a gold plate on which an organic functional group is anchored is reported; however, the method is complicated due to the anchoring and recrystallization (Journal of the American Chemical Society, 127, 13744, 2005).
- porous hybrid inorganic-organic materials are very different to that of inorganic porous materials.
- Organic molecules do not remain or incorporated in an inorganic porous material because organic molecules are removed by calcination after synthesis even though some organic amines or ammonium salts are used as templating molecules in the synthesis of inorganic porous materials.
- organic molecules construct a framework structure of porous hybrid inorganic-organic materials. In aninorganic porous material, oxygen atoms link a metal and another metal, whereas ligand, derived from an organic molecule, connects metal species.
- the present inventors have made intensive researches to fulfill the targets described above, and as a result, found a novel synthesis method of porous hybrid inorganic- organic materials in which microwave irradiation is used as a heat source.
- the present method is directed to synthesize porous hybrid inorganic-organic materials, in more environment-friendly way and in increased energy efficiency, with nanocrystalline morphology.
- the object of this invention is to provide a process for producing nanocrystalline porous hybrid inorganic-organic materials that have many applications in an economical and environment-friendly way, especially in a short reaction time.
- this invention is also to provide a method for producing a thin film or membrane of porous hybrid inorganic-organic materials by the direct microwave irradiation in one step.
- the present invention is directed to a novel process for preparing nanocrystalline porous hybrid inorganic-organic materials by utilizing microwave irradiation as a heat source of a hydrothermal or solvothermal reaction.
- the present invention providing porous hybrid inorganic-organic materials with particle size of 500 nm or less, includes following steps in the preparation.
- porous hybrid inorganic-organic materials obtained by the present method are powder, thin film or membrane in shape.
- porous hybrid inorganic-organic materials in thin film or membrane are easily prepared from the reactant mixtures by microwave irradiation after dipping a substrate in the reactant mixtures.
- the present invention provides a preparation method of porous hybrid inorganic- organic materials which have regular pore size of nanometers and the average particle size less than 500 nm, preferably less than 200 nm, and more preferably less than lOOnm and most preferably less than 50 nm.
- the present invention utilizes microwave irradiation rather than conventional electric heating as a heat source for high temperature reaction.
- the microwaves described in this invention are any microwaves that have frequency of 300 MHz -300 GHz.
- the commercially available microwaves with frequency of 2.45GHz or 0.915 GHz are convenient and effective to use in the invention.
- the metallic species can be any metallic materials such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi.
- Transition metals to make a coordination compound easily, are suitable for the invention.
- transition metals Cr, Ti, V, Mn, Fe, Co, Ni and Cu are more suitable, and Cr is most suitable.
- Main group elements which makea coordination compound easily and lanthanides can also be used as a metal component.
- Al and Si are suitable metallic components among main group elements, whereas Ce andLa are suitable elements among lanthanides.
- metallic precursors metals themselves and any compounds containing metallic components can be used.
- Any organic molecules are suitable as another component of a porous hybrid inorganic-organic material as long as the molecules contain functional groups that can coordinate to a metal center.
- the functional groups that can coordinate to a metal are carboxylic acid, carboxylate, amino (-NH ), imino(
- Multidentates having multiple coordinating sites, such as bidentates and tridentates are suitable for preparing stable porous hybrid inorganic-organic materials.
- Any organicmolecules can be used irrespective of the charges such as cationic, anionic and neutral compounds as long as they have coordination sites.
- neutral molecules such as bipyridine and pyrazine and anionic molecules such as terephthalate, naphthalenedicarboxylate, ben- zenetricarboxylate, glutarate and succinate can be used.
- Ions containing aromatic rings such as terephthalate, ions without aromatic rings such as formate, and ions containing non-aromatic rings such as cyclo- hexyldicarboxylate are suitable for carboxylate anions.
- organic species containing coordination sites but also organic species containing potential sites that can be transformed into a state suitable for coordination under the reaction conditions are applicable to organic precursors.
- organic acids such as terephthalic acid can be used because it can be converted to terephthalate to coordinate to a metal center under reaction conditions.
- Typical organic species are benzenedicarboxylic acids, naphthalenedicarboxylic acids, benzenetricarboxylic acids, naphthalenetricarboxylic acids, pyridinedicarboxylic acids, bipyridyldicarboxylic acids, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedionic acid, heptanedionic acid, cy- clohexyldicarboxylic acids, etc.
- Anions of the above described acids are also suitable.
- Pyrazine and bipyridines are neutral species that can be applied as organic ligands. Mixtures of two or more of the above mentioned organic moieties are also applicable.
- Chromium terephthalate, vanadium terephthalate and iron terephthalate are typical examples of porous hybrid inorganic-organic materials, and chromium terephthalate is one of the well-known porous hybrid inorganic-organic materials. Cubic chromium terephthalate with huge surface area and large pore size has great commercial interest. [26] Instead of metallic components and organic ligands, suitable solvents are necessary for the synthesis of porous hybrid inorganic-organic materials.
- solvents water, alcohols such as methanol, ethanol and propanol, and ketones such as acetone and methylethyl ketone and hydrocarbons such as hexanes, heptanes and octanes are suitable. Mixtures of above solvents can be applied and water is the most suitable solvent.
- the reaction temperature does not have any practical limitation. However, temperature above 100 °C is suitable, and temperature of 100 -250 °C is more suitable, and temperature of 150 -220 °C is most suitable. When the reaction temperature is too low, the reaction rate is too slow and the productivity is too low, whereas when the temperature is too high, dense species without pore is obtained and impurities can be byproduced because the reaction rate is too high. Moreover, it is costly to construct a reactor for high pressure reaction when the reaction temperature is too high.
- the reaction pressure does not have any limitation. It is convenient to perform a reaction under the autogenous pressure at the reaction temperature. Moreover, the reaction can be performed under higher pressure by adding inert gases such as nitrogen or helium.
- the reaction can be carried out both in a batch mode and in a continuous mode.
- the batch mode operation is suitable for production in small scale because the throughput per time is low, whereas continuous mode is suitable for mass production of porous hybrid inorganic-organic materials even though investment cost is high.
- the reaction time of batch mode operation is from 1 min to 8 h. When the reaction time is too long, byproducts are mixed in the product and it is hard to get nanoparticles because of crystal growth. On the contrary, the conversion is low when the reaction time is too short. Reaction time of 1 min -60 min is more suitable. The residence time of lmin -60 min is suitable for a continuous reaction.
- the residence time When the residence time is too long, byprodu cts are mixed in theproduct and it is hard to get nanoparticles.
- the throughput per time is low when the residence time is long.
- reaction conversion is low when the residence time is short.
- the residence time of lmin -20 min is more suitable.
- the reactant mixtures can be agitated, and the agitation speed of 100-lOOOrpm is suitable.
- the reaction can be performed statically and the static reaction is more suitable because of low investment cost and easy op- erability.
- the pretreatment can be accomplished either by treatment using ultrasonics or by vigorous mixing.
- the pretreatment temperature is suitable between room temperature and the reaction temperature. If the pretreatment temperature is too low, the pretreatment effect is too small, whereas if the pretreatment temperature is too high, the equipment for pretreatment is complex and impurities may be byproduced.
- Pretreatment time longer than 1 min is suitable. Pretreatment time between 1 min and 5 h is more suitable for the ultrasonic treatment, whereas pretreatment for 5 min or more is more suitable for the vigorous stirring. If the pretreatment time is too short, the pretreatment effect is too small, whereas if the pretreatment time is too long, the efficiency of pretreatment is low.
- Pretreatment using ultrasonics is effective in pretreatment time and homogeneity of the reactant mixtures.
- the membrane or thin film of porous hybrid inorganic-organic materials can be made by microwave irradiation after dipping a substrate in the reaction mixtures- mentioned above.
- the substrate can be alumina, silicon, glass, indium tin oxide (ITO), indium zinc oxide (IZO) and heat-resistant polymers. Any surface-treated substrate mentioned above will be more suitable.
- Fig. 1 represents the scanning electron microscopes of chromium terephthalate, obtained in Example 1.
- Fig. 2 represents the scanning electron microscopes of chromium terephthalate, obtained in Example 3.
- Fig. 3 represents the X-ray diffraction patterns of chromium terephthalate, obtained in Examples.
- Fig. 3a and Fig. 3b are obtained from Examples 2 and 3, respectively.
- Fig. 4 represents the adsorption isotherms of nitrogen and benzene of chromium terephthalate, obtained in Example 2.
- Fig. 5 represents the scanning electron microscope of chromium terephthalate thin film, obtained in Example 6.
- the reactant mixtures were loaded in a Teflon reactor,and pretreated by ultrasonic wave treatment for 1 min in order to homogenize the mixture and facilitate the nucleation.
- the Teflon reactor containing pretreated reactant mixtures was put in a microwave oven (CEM, Mars-5). The synthesis was carried out under microwave irradiation (2.45 GHz) for 1 min at 210 °C after the reaction temperature was reached for 3 min under microwave irradiation.
- the porous hybrid inorganic- organic material, chromium terephthalate, Cr-BDCA-I was recovered by cooling to room temperature, centrifugation, washing with deionized water and drying. It was confirmed that a cubic chromium terephthalate was obtained by the XRD result to show characteristic diffraction peaks at 3.3, 5.2, 5.9, 8.5 and 9. 1 (2 ⁇ ).
- the SEM (scanning electron microscope) image of Cr-BDAC-I obtained in this example is shown in Fig. 1, and shows that the crystals are 30-40 nm and very homogeneous in size.
- Example 1 except that ultrasonic pretreatment was omitted and the reaction time was 2 min.
- X-ray diffraction patterns of Fig. 3a show that a material with structure same as Example 1 was obtained, and SEM image confirms that a porous hybrid inorganic- organic material with homogeneous size of 40-50 nm was obtained.
- the adsorption isotherms of nitrogen and benzene are shown in Fig. 4. Therefore, the nanocrystalline porous hybrid inorganic-organic material, chromium terephthalate, synthesizedin this example has very high adsorption capacity to be used successfully as adsorbents, catalysts, catalyst supports, etc.
- Example 2 except that the reaction time was 40 min.
- X-ray diffraction patterns of Fig. 3b show that a material with structure same as Example 1 was obtained, and SEM image (Fig. 2) confirms that a porous hybrid inorganic-organic material with homogeneous size of 200 nm was obtained even though the crystal size increased considerably compared with the size of Example 2.
- Example 2 except that FeCl was used instead of Cr(NO ) -9H O.
- X-ray diffraction patterns showed that a material with structure same as Example 1 was obtained, and SEM image confirmed that a porous hybrid inorganic-organic material with homogeneous size of 50-100 nm was obtained.
- Example 2 except that VCl was used instead of Cr(NO ) -9H O.
- X-ray diffraction patterns showed that a material with structure same as Example 1 was obtained, and SEM image confirmed that a porous hybrid inorganic-organic material with homogeneous size of 50-80 nm was obtained.
- the reactant mixtures were loaded in a Teflon reactor, and an alumina plate was aligned vertically in the reactant mixture.
- the Teflon reactor containing reactant mixtures and alumina plate was put in a microwave oven (CEM, Mars-5). The synthesis was carried out under microwave irradiation (2.45 GHz) for 30 min at 210 °C after the reaction temperature was reached for 3 min under microwave irradiation.
- the porous hybrid inorganic-organic material, chromium terephthalate,Cr-BDCA-l both powder and thin film was recovered by cooling to room temperature, centrifugation, washing with deionized water and drying.
- the XRD patterns of the thin film were very similar to those of experiment 1.
- the SEM image of the thin film is shown in Fig. 5, and illustrates that the thin film, Cr-BDCA/alumina, is coated homogeneously with small particles.
- Example 2 except that conventional electric oven was used instead of a microwave oven, and the reaction temperature and time was 220 °C and 1O h, respectively.
- X-ray diffraction patterns showed that a material with structure same as Example 1 was obtained.
- SEM image showed that a porous hybrid inorganic-organic material with big size of 1000-2000 nm was obtained.
- the crystal size was not homogeneous.
- Comparative Example 1 except that the reaction time was 2 h. X-ray diffraction patterns showed that amorphous material was obtained rather than a crystalline material.
- the synthesis of porous hybrid inorganic-organic material by using microwave irradiation has the advantage of reduction of reaction time, energy saving, high productivity. Therefore, the synthesis method in this invention can be competitive method in the point of environment and economics. Especially, the synthesis of nanocrystalline porous hybrid inorganic-organic material, less than 500 nm, is fulfilled by microwave synthesis. Moreover, a thin film and membrane can be easily fabricated directly.
- This porous hybrid inorganic-organic material has the applications such as catalysts, catalyst supports, adsorbents, gas storages, ion exchangers, nanoreactors and templates or carriers of nanomaterials.
- the nanocrystalline porous hybrid inorganic-organic materials can be used in active catalysts, sensors, optoelectronic materials and medical materials.
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Abstract
The present invention relates to a synthesis method of porous hybrid inorganic-organic materials that can be applied for adsorbents, gas storages, sensors, membranes, functional thin films, catalysts, catalyst supports, encapsulating guest molecules and separation of molecules by the pore structures. More specifically, the present invention relates to the synthesis method of nanocrystalline porous hybrid inorganic-organic materials.
Description
Description
A PREPARATION METHOD OF POROUS ORGANIC INORGANIC HYBRID MATERIALS
Technical Field
[1] The present invention relates to a preparation method of porous hybrid inorganic- organic material useful as adsorbents, gas storages, catalysts, catalyst supports, carriers and templates for nanomaterials and electronic and electric materials. More particularly, present invention relates to a preparation method of porous hybrid inorganic- organic material, with particle size less than 500 nm, by using microwave heating rather than conventional electric heating as a heat source for a hydrothermal or sol- vothermal synthesis. Background Art
[2] The porous hybrid inorganic-organic materials that are explained in this invention are defined as inorganic-organic coordination polymers composed of central metallic ions and organic ligands coordinated to the metal ions. The porous hybrid inorganic-organic materials are crystalline materials having porous structures with the pore sizes of molecules or nanometers, and the framework structures of porous hybrid inorganic- organic materials are composed of both organic materials and inorganic species. The porous hybrid inorganic-organic material is wide terminology and also can be called as porous coordination polder (Angew. Chem. Intl. Ed., 43, 2334. 2004) or metal- organic framework (Chem. Soc. Rev., 32, 276, 2003). The studies on these materials have been recently developed by the combination of coordination chemistry and materials science. These materials are widely studied because they have many applications such as adsorbents, gas storages, sensors, membranes, functional thin films, catalysts and catalyst supports due to high surface area and pores of size of molecules or nanometers. Moreover, they can be used to encapsulate molecules or separate molecules depending on the sizes of molecules. These porous hybrid inorganic-organic materials can be synthesized by several methods including solvent-diffusion method, hydrothermal synthesis using water as solvent and a solvothermal synthesis using an organic solvent (Microporous Mesoporous Mater., 73, 15, 2004; Accounts of Chemical Research, 38, 217, 2005).
[3] The synthesis of porous hybrid inorganic-organic materials can be executed, similar to the synthesis of inorganic porous materials including zeolites and mesoporous materials, under autogenous pressure in the presence of water or suitable solvents at
zeolites and mesoporous materials, during several days at high temperature after loading reactants in a high pressure reactor such as an autoclave. The heat source for high temperature has generally been electric or resistive heating. For example, an autoclave containing precursors including metal salts, organic ligands and water or solvent was heated using an electric heater or an electric oven at a constant temperature. However, the methods of the previous embodiments have drawbacks of using excessive energy because the nucleation or crystallization is very slow. Moreover, the methods are very inefficient because the synthesis can be carried out only by batch reactions (Accounts of Chemical Research, 38, 217, 2005). The previous synthesis methods are considered as inefficient methods to implement commercial applications because of high production cost.
[4] Moreover, it is known that porous catalytic materials with small particle size have advantages of increased activity and facile regeneration of used catalysts because diffusivity increases with decreasing the crystal size of catalysts (Catalysis Today, 41, 37, 1998; Polymer Degradation and Stability 70, 365, 2000). Moreover, nanocrystalline porous materials have many applications inthe fields of sensors, optoelectronics and medicines (Chem. Mater., 17, 2494, 2005). However, it is not easy to synthesize small crystals, and so-called nanoparticles smaller than 100 nm is especially difficult to obtain because of easy aggregation or coagulation. Carbon or polymer templates may be used to synthesize nanoparticles even though the synthesis process is complex. However, it is not easy to obtain pure nanoparticles without a template because small particles grow easily to a big size when the template is removed.
[5] Moreover, it is necessary to prepare porous hybrid inorganic-organic materials with homogeneous particle size and membrane or thin film of the materials for the applications in sensors or opto-electronic devices. In a previous method, membranes or thin films were made by two steps of synthesizing and making a simple composite by impregnation of porous hybrid inorganic-organic materials on a polymer. However, the process is complex and it is difficult to apply for insoluble porous hybrid inorganic- organic materials. Another method using a gold plate on which an organic functional group is anchored is reported; however, the method is complicated due to the anchoring and recrystallization (Journal of the American Chemical Society, 127, 13744, 2005).
[6] Hence, it is an object of the present invention to provide a new preparation method of a porous hybrid inorganic-organic material and, especially nanocrystalline porous hybrid inorganic-organic material including thin film or membrane.
[7] On the other hand, there have been mass production methods such as hydrothermal crystallization for inorganic porous materials including zeolites because they have been used for 50 years or so in the petrochemistry or refinery. However, the general hy-
drothermal method using electric heating is ineffective due to long crystallization time. Therefore, since 1988, microwave heating has been suggested to increase the efficiency or productivity in the synthesis of inorganic porous materials (USP 4,778,666; Catal. Survey Asia, 8, 91, 2004). It was reported that synthesis time could be decreased by using microwave heating compared with conventional electric heating, and continuous synthesis was also reported for a few cases using microwave heating. However, the synthesis mechanisms of porous hybrid inorganic-organic materials are very different to that of inorganic porous materials. Organic molecules do not remain or incorporated in an inorganic porous material because organic molecules are removed by calcination after synthesis even though some organic amines or ammonium salts are used as templating molecules in the synthesis of inorganic porous materials. On the other hands, organic molecules construct a framework structure of porous hybrid inorganic-organic materials. In aninorganic porous material, oxygen atoms link a metal and another metal, whereas ligand, derived from an organic molecule, connects metal species. Therefore, the synthesis of porous hybrid inorganic- organic materials has been accomplished by using electric heating only because the synthesis is just at the beginning stage of development (Science, 2005, 309, 2040). Therefore, there have been few attemptsto synthesize a porous hybrid inorganic- organic material by using microwave heating.
[8] Recently, the synthesis of porous hybrid inorganic-organic materials by using microwave irradiation, after adequatepretrements, has been reported by the present inventors (Kor. Pat. Application 2005-0045153); however, there has been no report on the crystal size control or the synthesis of nanocrystalline porous hybrid inorganic- organic materials.
[9] Moreover, to synthesize nanocrystalline porous hybrid inorganic-organic materials, preferably in a short reaction time, and more preferably in a continuous reaction mode, is very important for commercial applications of porous hybrid inorganic-organic materials in catalysts, catalyst supports, adsorbents, ion exchangers, magnetic materials, thin films, gas storages, nanoreactors and nanosciences such as storage, preparation and separation of nanomaterials.
[10]
Disclosure of Invention Technical Problem
[11] The present inventors have made intensive researches to fulfill the targets described above, and as a result, found a novel synthesis method of porous hybrid inorganic- organic materials in which microwave irradiation is used as a heat source. The present method is directed to synthesize porous hybrid inorganic-organic materials, in more
environment-friendly way and in increased energy efficiency, with nanocrystalline morphology. [12] Accordingly, the object of this invention is to provide a process for producing nanocrystalline porous hybrid inorganic-organic materials that have many applications in an economical and environment-friendly way, especially in a short reaction time. Moreover, this invention is also to provide a method for producing a thin film or membrane of porous hybrid inorganic-organic materials by the direct microwave irradiation in one step.
Technical Solution
[13] The present invention is directed to a novel process for preparing nanocrystalline porous hybrid inorganic-organic materials by utilizing microwave irradiation as a heat source of a hydrothermal or solvothermal reaction.
[14] The present invention, providing porous hybrid inorganic-organic materials with particle size of 500 nm or less, includes following steps in the preparation.
[15] 1) the step to prepare reactant mixtures by mixing metal precursors, organic molecules that can be used as ligands and solvent; and
[16] 2) the step to heat the reactant mixtures higher than 100 °C by irradiation of microwave with the frequency of 0.3-300 GHz
[17] The porous hybrid inorganic-organic materials obtained by the present method are powder, thin film or membrane in shape.
[18] The porous hybrid inorganic-organic materials in thin film or membrane are easily prepared from the reactant mixtures by microwave irradiation after dipping a substrate in the reactant mixtures.
[19] The present invention provides a preparation method of porous hybrid inorganic- organic materials which have regular pore size of nanometers and the average particle size less than 500 nm, preferably less than 200 nm, and more preferably less than lOOnm and most preferably less than 50 nm.
[20] The present invention will be described in more detail as follows:
[21] The present invention utilizes microwave irradiation rather than conventional electric heating as a heat source for high temperature reaction. The microwaves described in this invention are any microwaves that have frequency of 300 MHz -300 GHz. The commercially available microwaves with frequency of 2.45GHz or 0.915 GHz are convenient and effective to use in the invention.
[22] The metallic species, one of the components of porous hybrid inorganic-organic materials, can be any metallic materials such as Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. Transition metals, to make a coordination
compound easily, are suitable for the invention. Among transition metals, Cr, Ti, V, Mn, Fe, Co, Ni and Cu are more suitable, and Cr is most suitable. Main group elements which makea coordination compound easily and lanthanides can also be used as a metal component. Al and Si are suitable metallic components among main group elements, whereas Ce andLa are suitable elements among lanthanides. As metallic precursors, metals themselves and any compounds containing metallic components can be used. [23] Any organic molecules are suitable as another component of a porous hybrid inorganic-organic material as long as the molecules contain functional groups that can coordinate to a metal center. The functional groups that can coordinate to a metal are carboxylic acid, carboxylate, amino (-NH ), imino(
. NH
), amide (-CONH ), sulfonic acid (-SO H), sulfonate (-SO ), methanedithionic acid (-CS H), methanedithionate (-CS "), pyridine, pyrazine, etc. Multidentates, having multiple coordinating sites, such as bidentates and tridentates are suitable for preparing stable porous hybrid inorganic-organic materials. Any organicmolecules can be used irrespective of the charges such as cationic, anionic and neutral compounds as long as they have coordination sites. For example, neutral molecules such as bipyridine and pyrazine and anionic molecules such as terephthalate, naphthalenedicarboxylate, ben- zenetricarboxylate, glutarate and succinate can be used.
[24] Ions containing aromatic rings such as terephthalate, ions without aromatic rings such as formate, and ions containing non-aromatic rings such as cyclo- hexyldicarboxylate are suitable for carboxylate anions. Not only organic species containing coordination sites but also organic species containing potential sites that can be transformed into a state suitable for coordination under the reaction conditions are applicable to organic precursors. For example, organic acids such as terephthalic acid can be used because it can be converted to terephthalate to coordinate to a metal center under reaction conditions. Typical organic species are benzenedicarboxylic acids, naphthalenedicarboxylic acids, benzenetricarboxylic acids, naphthalenetricarboxylic acids, pyridinedicarboxylic acids, bipyridyldicarboxylic acids, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedionic acid, heptanedionic acid, cy- clohexyldicarboxylic acids, etc. Anions of the above described acids are also suitable. Pyrazine and bipyridines are neutral species that can be applied as organic ligands. Mixtures of two or more of the above mentioned organic moieties are also applicable.
[25] Chromium terephthalate, vanadium terephthalate and iron terephthalate are typical examples of porous hybrid inorganic-organic materials, and chromium terephthalate is one of the well-known porous hybrid inorganic-organic materials. Cubic chromium terephthalate with huge surface area and large pore size has great commercial interest.
[26] Instead of metallic components and organic ligands, suitable solvents are necessary for the synthesis of porous hybrid inorganic-organic materials. As the solvents, water, alcohols such as methanol, ethanol and propanol, and ketones such as acetone and methylethyl ketone and hydrocarbons such as hexanes, heptanes and octanes are suitable. Mixtures of above solvents can be applied and water is the most suitable solvent.
[27] The reaction temperature does not have any practical limitation. However, temperature above 100 °C is suitable, and temperature of 100 -250 °C is more suitable, and temperature of 150 -220 °C is most suitable. When the reaction temperature is too low, the reaction rate is too slow and the productivity is too low, whereas when the temperature is too high, dense species without pore is obtained and impurities can be byproduced because the reaction rate is too high. Moreover, it is costly to construct a reactor for high pressure reaction when the reaction temperature is too high. The reaction pressure does not have any limitation. It is convenient to perform a reaction under the autogenous pressure at the reaction temperature. Moreover, the reaction can be performed under higher pressure by adding inert gases such as nitrogen or helium.
[28] The reaction can be carried out both in a batch mode and in a continuous mode. The batch mode operation is suitable for production in small scale because the throughput per time is low, whereas continuous mode is suitable for mass production of porous hybrid inorganic-organic materials even though investment cost is high. The reaction time of batch mode operation is from 1 min to 8 h. When the reaction time is too long, byproducts are mixed in the product and it is hard to get nanoparticles because of crystal growth. On the contrary, the conversion is low when the reaction time is too short. Reaction time of 1 min -60 min is more suitable. The residence time of lmin -60 min is suitable for a continuous reaction. When the residence time is too long, byprodu cts are mixed in theproduct and it is hard to get nanoparticles. The throughput per time is low when the residence time is long. On the contrary, reaction conversion is low when the residence time is short. The residence time of lmin -20 min is more suitable. During the batch-mode reaction, the reactant mixtures can be agitated, and the agitation speed of 100-lOOOrpm is suitable. The reaction can be performed statically and the static reaction is more suitable because of low investment cost and easy op- erability.
[29] It is advisable to irradiate microwaves on pretreated reactant mixtures because the reaction using microwaves is very fast and homogeneous or nucleated reaction mixtures are suitable for the reaction. When the microwaves are irradiated on reaction mixtures without a pretreatment, the reaction rate is low or impurities may be mixed in or the crystal sizes can be inhomogeneous even though the process will be simple.
[30] The pretreatment can be accomplished either by treatment using ultrasonics or by
vigorous mixing. The pretreatment temperature is suitable between room temperature and the reaction temperature. If the pretreatment temperature is too low, the pretreatment effect is too small, whereas if the pretreatment temperature is too high, the equipment for pretreatment is complex and impurities may be byproduced. Pretreatment time longer than 1 min is suitable. Pretreatment time between 1 min and 5 h is more suitable for the ultrasonic treatment, whereas pretreatment for 5 min or more is more suitable for the vigorous stirring. If the pretreatment time is too short, the pretreatment effect is too small, whereas if the pretreatment time is too long, the efficiency of pretreatment is low. Pretreatment using ultrasonics is effective in pretreatment time and homogeneity of the reactant mixtures.
[31] The membrane or thin film of porous hybrid inorganic-organic materials can be made by microwave irradiation after dipping a substrate in the reaction mixtures- mentioned above. The substrate can be alumina, silicon, glass, indium tin oxide (ITO), indium zinc oxide (IZO) and heat-resistant polymers. Any surface-treated substrate mentioned above will be more suitable.
[32]
Brief Description of the Drawings
[33] Fig. 1 represents the scanning electron microscopes of chromium terephthalate, obtained in Example 1.
[34] Fig. 2 represents the scanning electron microscopes of chromium terephthalate, obtained in Example 3.
[35] Fig. 3 represents the X-ray diffraction patterns of chromium terephthalate, obtained in Examples. Fig. 3a and Fig. 3b are obtained from Examples 2 and 3, respectively.
[36] Fig. 4 represents the adsorption isotherms of nitrogen and benzene of chromium terephthalate, obtained in Example 2.
[37] Fig. 5 represents the scanning electron microscope of chromium terephthalate thin film, obtained in Example 6.
[38]
Mode for the Invention
[39] The following specific examples are intended to be illustrative of the invention and should not be construed as limiting the scope of the invention as defined by appended claims.
[40] EXAMPLE 1 (Cr-BDCA-I)
[41] Reactant mixtures with the molar composition of Cr:HF:BDCA:H 2 O=I : 1 : 1 :275 were prepared from Cr(NO ) -9H O, aqueous HF, 1,4-benzenedicarboxylic acid (BDCA) and water. The reactant mixtures were loaded in a Teflon reactor,and pretreated by ultrasonic wave treatment for 1 min in order to homogenize the mixture
and facilitate the nucleation. The Teflon reactor containing pretreated reactant mixtures was put in a microwave oven (CEM, Mars-5). The synthesis was carried out under microwave irradiation (2.45 GHz) for 1 min at 210 °C after the reaction temperature was reached for 3 min under microwave irradiation. The porous hybrid inorganic- organic material, chromium terephthalate, Cr-BDCA-I was recovered by cooling to room temperature, centrifugation, washing with deionized water and drying. It was confirmed that a cubic chromium terephthalate was obtained by the XRD result to show characteristic diffraction peaks at 3.3, 5.2, 5.9, 8.5 and 9. 1 (2Θ). The SEM (scanning electron microscope) image of Cr-BDAC-I obtained in this example is shown in Fig. 1, and shows that the crystals are 30-40 nm and very homogeneous in size. These results show that a porous hybrid inorganic-organic material can be obtained very efficiently in a short reaction time by adequate pretreatment and microwave irradiation.
[42] EXAMPLE 2 (Cr-BDCA-2)
[43] The synthesis of a porous hybrid inorganic-organic material was carried out as
Example 1, except that ultrasonic pretreatment was omitted and the reaction time was 2 min. X-ray diffraction patterns of Fig. 3a show that a material with structure same as Example 1 was obtained, and SEM image confirms that a porous hybrid inorganic- organic material with homogeneous size of 40-50 nm was obtained. The porous hybrid inorganic-organic material, after evacuation at 150°C, has nitrogen adsorption capacity of 1050 mL/g or 46.9 mmol/g at relative pressure of 0.5 (P/Po=0.5, at liquid nitrogen temperature). Moreover, the porous hybrid inorganic-organic material has high benzene adsorption capacity (16 mmol/g) at 30 °Cand relative pressure of 0.5 (P/Po=0.5). The adsorption isotherms of nitrogen and benzene are shown in Fig. 4. Therefore, the nanocrystalline porous hybrid inorganic-organic material, chromium terephthalate, synthesizedin this example has very high adsorption capacity to be used successfully as adsorbents, catalysts, catalyst supports, etc.
[44] EXAMPLE 3 (Cr-BDCA-3)
[45] The synthesis of a porous hybrid inorganic-organic material was carried out as
Example 2, except that the reaction time was 40 min. X-ray diffraction patterns of Fig. 3b show that a material with structure same as Example 1 was obtained, and SEM image (Fig. 2) confirms that a porous hybrid inorganic-organic material with homogeneous size of 200 nm was obtained even though the crystal size increased considerably compared with the size of Example 2.
[46] EXAMPLE 4 (Fe-BDCA-I)
[47] The synthesis of a porous hybrid inorganic-organic material was carried out as
Example 2, except that FeCl was used instead of Cr(NO ) -9H O. X-ray diffraction patterns showed that a material with structure same as Example 1 was obtained, and
SEM image confirmed that a porous hybrid inorganic-organic material with homogeneous size of 50-100 nm was obtained.
[48] EXAMPLE 5 (V-BDCA-I)
[49] The synthesis of a porous hybrid inorganic-organic material was carried out as
Example 2, except that VCl was used instead of Cr(NO ) -9H O. X-ray diffraction patterns showed that a material with structure same as Example 1 was obtained, and SEM image confirmed that a porous hybrid inorganic-organic material with homogeneous size of 50-80 nm was obtained.
[50] EXAMPLE 6 (Cr-BDCA- 1 thin film)
[51] Reactant mixtures with the molar composition of Cr:HF:BDCA:H O=I : 1 : 1 :275 were prepared from Cr(NO ) -9H O, aqueous HF, 1,4-benzenedicarboxylic acid (BDCA) and water. The reactant mixtures were loaded in a Teflon reactor, and an alumina plate was aligned vertically in the reactant mixture. The Teflon reactor containing reactant mixtures and alumina plate was put in a microwave oven (CEM, Mars-5). The synthesis was carried out under microwave irradiation (2.45 GHz) for 30 min at 210 °C after the reaction temperature was reached for 3 min under microwave irradiation. The porous hybrid inorganic-organic material, chromium terephthalate,Cr-BDCA-l (both powder and thin film) was recovered by cooling to room temperature, centrifugation, washing with deionized water and drying. The XRD patterns of the thin film were very similar to those of experiment 1. The SEM image of the thin film is shown in Fig. 5, and illustrates that the thin film, Cr-BDCA/alumina, is coated homogeneously with small particles. These results show that a porous hybrid inorganic-organic material thin film can be obtained directly and efficiently in a short reaction time by microwave irradiation.
[52] COMPARATIVE EXAMPLE 1 (Cr-BDCA-4)
[53] The synthesis of a porous hybrid inorganic-organic material was carried out as
Example 2, except that conventional electric oven was used instead of a microwave oven, and the reaction temperature and time was 220 °C and 1O h, respectively. X-ray diffraction patterns showed that a material with structure same as Example 1 was obtained. However, SEM image showed that a porous hybrid inorganic-organic material with big size of 1000-2000 nm was obtained. Moreover, the crystal size was not homogeneous.
[54] COMPARATIVE EXAMPLE 2 (Cr-BDCA-4)
[55] The synthesis of a porous hybrid inorganic-organic material was carried out as
Comparative Example 1, except that the reaction time was 2 h. X-ray diffraction patterns showed that amorphous material was obtained rather than a crystalline material.
[56]
[57] From the Comparative Examples, it can be known that to synthesize a nanocrystalline porous hybrid inorganic-organic material with size less than 500 nm is impossible by usingconventional electric heating. Moreover, synthesis method using microwave irradiation has the advantage of rapid, economical and effective preparation of nanocrystalline porous hybrid inorganic-organic material.
[58]
Industrial Applicability
[59] As described above, the synthesis of porous hybrid inorganic-organic material by using microwave irradiation has the advantage of reduction of reaction time, energy saving, high productivity. Therefore, the synthesis method in this invention can be competitive method in the point of environment and economics. Especially, the synthesis of nanocrystalline porous hybrid inorganic-organic material, less than 500 nm, is fulfilled by microwave synthesis. Moreover, a thin film and membrane can be easily fabricated directly. This porous hybrid inorganic-organic material has the applications such as catalysts, catalyst supports, adsorbents, gas storages, ion exchangers, nanoreactors and templates or carriers of nanomaterials. The nanocrystalline porous hybrid inorganic-organic materials can be used in active catalysts, sensors, optoelectronic materials and medical materials.
[60]
Claims
[1] A preparation method of porous hybrid inorganic-organic materials with size smaller than 500 nm, comprising:
1) the step to prepare reaction mixtures by mixing metal precursors, organic compounds that can be used as ligands and solvent; and
2) the step to irradiate microwave on the reaction mixtures prepared as above and to heat the temperature higher than 100 °C.
[2] The preparation method of porous hybrid inorganic-organic materials according to claim 1, wherein metal precursors are one or more of metals selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, or Bi; or metal compounds containing one or more components selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, or Bi.
[3] The preparation method of porous hybrid inorganic-organic materials according to claim 1, wherein the organic compounds are the molecules or molecular mixtures containing one or more of the functional groups selected from carboxylic acid, carboxylate, amino (-NH ), imino(
), amide (-CONH ), sulfonic acid (-SO H), sulfonate (-SO "), methanedithionic acid (-CS H), methanedithionate (-CS ), pyridine or pyrazine.
[4] The preparation method of porous hybrid inorganic-organic materials according to claim 3, wherein the organic compounds containing carboxylic functional groups are selected from benzenedicarboxylic acids, naphthalenedicarboxylic acids, benzenetricarboxylic acids, naphthalenetricarboxylic acids, pyridinedi- carboxylic acids, bipyridyldicarboxylic acids, formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedionic acids, heptanedionic acids and cy- clohexyldicarboxylic acids.
[5] The preparation method of porous hybrid inorganic-organic materials according to claim 1, wherein the reaction temperature is 100 -250°C.
[6] The preparation method of porous hybrid inorganic-organic materials according to claim 5, wherein the reaction temperature is 150 -220°C.
[7] The preparation method of porous hybrid inorganic-organic materials according to claim 1, wherein the reaction is carried out by using a batch reactor or a continuous reactor.
[8] The preparation method of porous hybrid inorganic-organic materials according
to claim 1, wherein the reaction mixtures are treated additionally by ultrasonic treatment for 1 min or more or by agitation for 5 min or more between Step 1 and
Step 2. [9] The preparation method of porous hybrid inorganic-organic materials according to claim 1, wherein the average particle size of porous hybrid inorganic-organic materials is less than 200 nm. [10] The preparation method of porous hybrid inorganic-organic materials according to claim 9, wherein the average particle size of porous hybrid inorganic-organic materials is less than 100 nm. [11] The preparation method of porous hybrid inorganic-organic materials according to claim 10, wherein the average particle size of porous hybrid inorganic-organic materials is less than 50 nm. [12] The preparation method of porous hybrid inorganic-organic materials according to claim 1, whereinthe porous hybrid inorganic-organic material is one selected from chromium terephthalate, iron terephthalate or vanadium terephthalate. [13] The preparation method of porous hybrid inorganic-organic materials according to claim 12, whereinthe porous hybrid inorganic-organic material is chromium terephthalate. [14] The preparation method of porous hybrid inorganic-organic materials according to claim 13, wherein the porous hybrid inorganic-organic material is a cubic chromium terephthalate that has pores. [15] The preparation method of porous hybrid inorganic-organic materials according to claim 1, wherein the porous hybrid inorganic-organic materials are states of thin films or membranes. [16] The preparation method of porous hybrid inorganic-organic materials according to claim 15, whereinthe porous hybrid inorganic-organic materials in thin films or membranes are prepared by dipping alumina, silicon, glass, indium tin oxide
(ITO), indium zinc oxide (IZO) or heat resistant polymers in the reactant mixtures.
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