JP2023504011A - 金属-有機骨格押出物の製造方法 - Google Patents
金属-有機骨格押出物の製造方法 Download PDFInfo
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- JP2023504011A JP2023504011A JP2022530831A JP2022530831A JP2023504011A JP 2023504011 A JP2023504011 A JP 2023504011A JP 2022530831 A JP2022530831 A JP 2022530831A JP 2022530831 A JP2022530831 A JP 2022530831A JP 2023504011 A JP2023504011 A JP 2023504011A
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- metal
- mof
- extrusion
- organic framework
- extrusion aid
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- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000036346 tooth eruption Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Mechanical Engineering (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Glanulating (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
有機配位子
A. アルキルまたはアリールアミンまたはホスフィンおよびそれらの対応するアンモニウム塩またはホスホニウム塩。アルキルアミンまたはホスフィンは、1~20個の炭素原子を有する、直鎖、分枝、または環状の脂肪族基(およびそれらの対応するアンモニウム塩)を含んでよく、アリールアミンまたはホスフィンは複素環を含む1~5の芳香環を含んでよい。単官能アミンの例は、メチルアミン、エチルアミン、n-プロピルアミン、iso-プロピルアミン、n-ブチルアミン、sec-ブチルアミン、iso-ブチルアミン、tert-ブチルアミン、n-ペンチルアミン、neo-ペンチルアミン、n-ヘキシルアミン、ピロリジン、3-ピロリン、ピペリジン、シクロヘキシルアミン、モルホリン、ピリジン、ピロール、アニリン、キノリン、イソキノリン、1-アザフェナンスレンおよび8-アザフェナンスレンである。二官能性および三官能性アミンの例は、1,4-ジアミノシクロヘキサン、1,4-ジアミノベンゼン、4,4'-ビピリジル、イミダゾール、ピラジン、1,3,5-トリアミノシクロヘキサン、1,3,5-トリアジン、1,3,5-トリアミノベンゼンである。
B. 1~20個の炭素原子を含むアルキル基またはシクロアルキル基、あるいは1~5個のフェニル環を含むアリール基を含むアルコール。単官能アルコールの例は、メタノール、エタノール、n-プロパノール、iso-プロパノール、アリルアルコール、n-ブタノール、iso-ブタノール、sec-ブタノール、tert-ブタノール、n-ペンタノール、iso-ペンタノール、sec-ペンタノール、ネオペンタノール、n-ヘキサノール、シクロヘキサノール、フェノール、ベンジルアルコールおよび2-フェニルエタノールである。二官能性および三官能性アルコールの例は、1,4-ジヒドロキシシクロヘキサン、ヒドロキノン、カテコール、レゾルシノール、1,3,5-トリヒドロキシベンゼン、1,3,5-トリヒドロキシシクロヘキサンである。
C. 1~20個の炭素原子を含むアルキル基またはシクロアルキル基、または1~5個のフェニル環を含むアリール基を含むエーテル。エーテルの例は、ジエチルエーテル、フラン、モルホリンである。
D. 1~20個の炭素原子を含むアルキル基またはシクロアルキル基、あるいは1~5個のフェニル環を含むアリール基を含むチオール。単官能チオールの例は、チオメタン、チオエタン、チオプロパン、チオシクロヘキサン、チオフェン、ベンゾチオフェン、およびチオベンゼンである。二官能性および三官能性チオールは、1,4-ジチオシクロヘキサン、1,4-ジチオベンゼン、1,3,5-トリチオシクロヘキサン、1,3,5-トリチオベンゼンである。
E. 1~20個の炭素原子を含むアルキル基またはシクロアルキル基、または1~5個のフェニル環を含むアリール基を含むニトリル。単官能ニトリルの例は、アセトニトリル、プロパンニトリル、ブタンニトリル、n-バレロニトリル、ベンゾニトリル、p-トルニトリルである。二官能性および三官能性ニトリルの例は、1,4-ジニトリロシクロヘキサン、1,4-ジニトリロベンゼン、1,3,5-トリニトロシクロヘキサン、1,3,5-トリニトロベンゼンである。
F. 硫酸(サルフェート)、硝酸(ナイトレート)、亜硝酸(ナイトライト)、亜硫酸、重亜硫酸、リン酸、リン酸水素、リン酸二水素、ジフォスフェート、トリフォスフェート、亜リン酸、塩素、臭素、ヨウ素、炭酸、重炭酸、チオシアン化物およびイソニトリルからなる群からの無機アニオン、並びに前記無機アニオンの対応する酸および塩。
G. 有機酸とそれに対応するアニオン(および塩)。有機酸としては、直鎖状、分岐状、または環状の脂肪族基を含み、1~20個の炭素原子を有するアルキル有機酸、または複素環を含んでもよい1~5個の芳香環を有するアリール有機酸およびそのアリール有機アニオンと塩を挙げることができる。
H.その他、アンモニア、二酸化炭素、メタン、酸素、エチレン、ヘキサン、ベンゼン、トルエン、キシレン、クロロベンゼン、ニトロベンゼン、ナフタレン、チオフェン、ピリジン、アセトン、1-2-ジクロロエタン、塩酸メチレン、テトラヒドロフラン、エタノールアミン、トリエチルアミンまたはトリフルオロメチルスルホン酸等の有機および無機物。
金属イオン
Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo3+、W3+、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3+、In3+、Tl3+、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+、Bi5+、Bi3+、Bi+、Be2+、
の金属イオンの1種または2種以上を用いて製造できる。金属イオンという用語は、金属とメタロイドの両方のイオンを意味する。いくらかの実施形態では、MOF材料の製造に使用するのに適した金属イオンは、対応する金属塩の対アニオンと共に、
Sc3+、Ti4+、V4+、V3+、V2+、Cr3+、Mo3+、Mg2+、Mn3+、Mn2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Al3+、Ga3+、In3+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、Sb5+、Sb3+、Sb+、Bi5+、Bi3+、Bi+、および/またはBe2+、
を含むことができる。いくらかの実施形態では、MOF材料の製造に使用するための金属イオンは、対応する金属塩の対イオンと共に、
Sc3+、Ti4+、V4+、V3+、Cr3+、Mo3+、Mn3+、Mn2+、Fe3+、Fe2+、Co3+、Co2+、Ni2+、Ni+、Cu2+、Cu+、Ag+、Zn2+、Cd2+、Al3+、Sn4+、Sn2+、Bi5+、Bi3+、および/またはBi+、
を含む。いくらかの実施形態では、MOF材料の製造に使用するための金属イオンは、対応する金属塩の対イオンと共に、
Mg2+、Mn3+、Mn2+、Fe3+、Fe2+、Co3+、Co2+、Ni2+、Ni+、Cu2+、Cu+、Pt2+、Ag+、およびZn2+、
からなる群から選択される。
MOF材料の製造
押出助剤
液体押出助剤
固体押出助剤
ポリマー押出助剤
押出助剤のブレンド
任意の添加剤
MOF押出物の製造方法
MOF押出物の性質
用途
Claims (26)
- 金属-有機骨格材料と押出助剤とを混合して、金属-有機骨格押出混合物を形成する工程;および
金属-有機骨格混合物を押出機で押出して金属-有機骨格押出物を製造する工程、
を含む、押出機で金属-有機骨格押出物を製造する方法であって、
押出機内の圧力を、押出助剤なしで金属-有機骨格材料を押出す際の押出機内の圧力と比較して、約10%~約55%減少させる、押出物を製造する方法。 - 押出助剤が、液体押出助剤、固体押出助剤および/またはポリマー押出助剤である、請求項1に記載の方法。
- 液体押出助剤が直鎖状C3~C10アルキルアルコールまたは分岐状C3~C10アルキルアルコールである、請求項2に記載の方法。
- 液体押出助剤が、1-プロパノール、iso-プロパノール、1-ブタノール、iso-ブタノール、1-ヘキサノール、1-ヘプタノールの群から選択される、請求項2に記載の方法。
- 液体押出助剤が約0.1体積%~95体積%の範囲の水を含む、請求項1に記載の押出助剤。
- 固体押出し助剤がグラファイトである、請求項2に記載の方法。
- 固体押出助剤がステアリン酸マグネシウムである、請求項2記載の方法。
- 固体押出助剤が飽和又は不飽和のC10+有機酸又はその塩である、請求項2に記載の方法。
- 固体押出助剤を、約1重量%~約30重量%の範囲で金属-有機骨格材料と混合する、請求項2に記載の方法。
- ポリマー押出助剤が、ポリビニルアミド、ポリアクリレート、ポリカーボネート、ポリアミド、ポリエステル、ポリエーテル、ポリビニルアミン、ポリビニルアルコール、ポリビニルエステル、またはそれらの組み合わせである、請求項1~9のいずれか一項に記載の方法。
- ポリマー押出助剤がポリビニルアルコールである、請求項2記載の方法。
- 金属-有機骨格混合物が約0.5重量%~10重量%のポリビニルアルコールを含む、請求項1~11のいずれか一項に記載の方法。
- 金属-有機骨格混合物が、ポリ酢酸ビニルおよび水を含み、ポリ酢酸ビニルと水の比が約1:1~約1:3である、請求項1~12のいずれか一項に記載の方法。
- 金属-有機骨格押出物を、ロッド、リブ付きロッド、タブレット、リング、環状タブレット、球体、ペレット、ハニカム体、または顆粒として成形する、請求項1~13のいずれかに記載の方法。
- 金属-有機骨格材料が、HKUST-1、UiO-66、ZIF-8、ZIF-7、MIL-100、MOF-74、M2(m-dobdc)、MOF-274、Cu(Qc) 2およびそれらの組み合わせからなる群から選択される、請求項1~14のいずれか一項に記載の方法。
- 金属-有機骨格材料が、
1~10個の炭素原子を有するアルキル基の部分構造;または
1~5個の芳香環を有するアリール基の部分構造、
(ここで、1つ以上の部分構造は、それぞれ少なくとも2つのX基を有し、Xは、金属またはメタロイドに配位するように構成された官能基である。)
のうちの1つ以上を含む有機配位子を含む、請求項1~15のいずれか一項に記載の方法。 - 各Xが、CO2H、OH、SH、OH2、NH2、CN、HCO、CS2H、NO2、SO3H、Si(OH)3、Ge(OH)3、Sn(OH)3、Si(SH)4、Ge(SH)4、Sn(SH)3、PO3H、AsO3H、AsO4H、P(SH)3、As(SH)3、CH(RSH)2、C(RSH)3、CH(RNH2)2、C(RNH2)3、CH(ROH)2、C(ROH)3、CH(RCN)2、C(RCN)3、CH(SH)2、C(SH)3、CH(NH2)2、C(NH2)2、CH(OH)2、C(OH)3、CH(CN)2、C(CN)3、窒素含有複素環、硫黄含有複素環、およびそれらの組み合わせ(Rは1~5の炭素原子を有するアルキル基または1~2のフェニル環から成るアリール基である。)の中性またはイオン形態からなる群から独立して選択される、請求項16に記載の方法。
- 有機配位子が、1,3,5-ベンゼンジカルボキシレート、1,4-ベンゼンジカルボキシレート、1,3-ベンゼンジカルボキシレート、ビフェニル-4,4’-ジカルボキシレート、ベンゼン-1,3,5-トリス(1H-テトラゾール)、アセチレン-1,2-ジカルボキシレート、ナフタレンカルボキシレート、アダマンタンテトラカルボキシレート、ベンゼントリベンゾエート、メタンテトラベンゾエート、アダマンタンテトラベンゾエート、ビフェニル-4,4’-ジカルボキシレート、イミダゾール、2,5-ジヒドロキシ-1,4-ベンゼンジカルボン酸、4,4’-ジヒドロキシ-(1,1’-ビフェニル)-3,3’-ジカルボン酸およびその誘導体の組み合わせからなる群から選択される、請求項1~17のいずれか一項に記載の方法。
- 金属-有機骨格材料が、金属-有機骨格材料が、Be2+、Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo3+、W3+、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3+、In3+、Tl3+、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+、Bi5+、Bi3+、Bi+、およびそれらの組み合わせからなる群から選択される金属イオンを含む、請求項1~18のいずれか一項に記載の方法。
- 金属-有機骨格押出物が、押出前の基材に対して、約40%~約100%の比較BET表面積を有する、請求項1~19のいずれか一項に記載の金属-有機骨格押出物。
- 金属-有機骨格押出物を約40℃~約150℃の温度で約30分以上の期間熟成させる工程をさらに含む、請求項1~20のいずれか一項に記載の方法。
- 金属-有機骨格押出物を約100℃~約300℃の温度で約1時間以上焼成する工程をさらに含む、請求項1~21のいずれか一項に記載の方法。
- 金属-有機骨格を押出す工程を、約0.01mm~約50mmの直径を有するダイを通して行う、請求項1~22のいずれか一項に記載の方法。
- 金属-有機骨格押出物を任意の溶媒で洗浄することをさらに含む、請求項1~23のいずれか一項に記載の方法。
- 任意の溶媒が、水、メタノール、エタノール、ジメチルホルムアミド、アセトン、ジエチルエーテル、アセトニトリル、ケトン、アミド、エステル、エーテル、ニトリル、芳香族炭化水素、脂肪族炭化水素およびそれらの組み合わせからなる群から選択される、請求項1~24のいずれか一項に記載の方法。
- MOF押出混合物が、MOF押出混合物の総重量を基準にして、約20重量%~約70重量%の固体を含む、請求項1~25のいずれか一項に記載の方法。
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