TWI304279B - Method of storing, uptaking, releasing of gases by novel framework materials - Google Patents
Method of storing, uptaking, releasing of gases by novel framework materials Download PDFInfo
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- TWI304279B TWI304279B TW091114521A TW91114521A TWI304279B TW I304279 B TWI304279 B TW I304279B TW 091114521 A TW091114521 A TW 091114521A TW 91114521 A TW91114521 A TW 91114521A TW I304279 B TWI304279 B TW I304279B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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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
- B01J20/22—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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/007—Use of gas-solvents or gas-sorbents in vessels for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/526—Sorbent for fluid storage, other than an alloy for hydrogen storage
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Description
1304279 A7 ~___ B7 五、發明説明(1 ) 本發明係關於儲存氣體(包括曱烷及氫)之技術領域,特 定吕之關於燃料電池技術。特定言之,其係關於使用一種 金屬-有機骨架材料(該材料包含細孔及至少一種金屬離子及 至少一種之至少雙配位基之有機化合物,其係結合(較佳係 配位地結合)於該金屬離子)以吸收、或儲存、或釋放、或吸 收及儲存、或吸收及釋放、或儲存及釋放或吸收、儲存及 釋放至少一種氣體之一種方法以及包含以上定義之材料之 一種裝置。 燃料電池技術被認為係2 1世紀之核心技術之一種,例如 關於固定之應用,諸如發電廠,移動之應用諸如汽車、公 共汽車及卡車及可攜帶之應用,諸如蜂巢式移動電話及筆 記型電腦及於所謂輔助動力裝置(APUs)中,諸如於發電廠 中之動力供應。用於其之原因在於,與一般之燃燒引擎比 較,燃料電池之增加之效率。此外,燃料電池產生有意義 地較少之排放物。於燃料電池技術中之目前發展之縱覽可 係於 Hynek 等人 “Int. J· Hydrogen Energy”1,第 6期,第 601-610 頁(1997) ’ J. A· Kerres “ Journal of Membrane Science”,!!^,2001,第 3-27 頁及由 G· March 於 “ Materials
Today”,生,第2期(2001),第20-24頁中之另外之評論文章中 找到。 金屬-有機錯合物用於儲存氣體Cl至C4碳水化合物之用途 係揭示於歐洲專利-A 0 727 608中。然而,於其中揭示之錯 合物係難以合成的。此外,彼等之儲存容量,倘若不是太 低以致於不能在工業上應用,則係低的。 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1304279
提供對於儲存氣體有用之材料之另一種企圖係以鹼添補 或未經添補之碳奈米管之使用。關於此途徑之研究之目前 情況之縱覽可係於Yang,“ Carb〇n” 2^(2000)^623441頁及 Cheng等人 “science” 迦,第 1 127-1 129頁中找到。 由於以上引述之先前技藝,本發明之一項目的係於新穎 材料(其等對於儲存及/或保持及/或釋放氣體係特別有用的) 之提供中見到。 此目的係經由本發明而解決,及本發明係關於用於吸收 、或儲存、或釋放、或吸收及儲存、或吸收及釋放、或儲 存及釋放或吸收、儲存及釋放至少一種氣體之方法,其特 徵為該氣體係經由包含一種金屬-有機骨架材料(該材料包含 細孔及至少一種金屬離子及至少一種之至少雙配位基之有 機化合物,其係結合(較佳係配位地結合)於該金屬離子)之 一種試劑而吸收、或儲存、或釋放、或吸收及儲存、或吸 收及釋放、或儲存及釋放或吸收、儲存及釋放。 本發明進一步係關於用於吸收、或儲存、或釋放、或吸 收及儲存、或吸收及釋放、或儲存及釋放、或吸收、儲存 及釋放至少一種氣體之裝置,較佳係容納金屬_有機骨架材 料(如於本文中定義)之燃料電池。 本發明再進一步係關於使用一種試劑(其包含一種金屬· 有機骨架材料(該材料包含細孔及至少一種金屬離子及至少 一種之至少雙配位基之有機化合物,其係結合(較佳係配位 地結合)於該金屬離子)以於固定、移動及移動可攜帶之應用 中(較佳地於發電廠、汽車、卡車、公共汽車、蜂巢式行動 -6- 本纸張尺度適用中國國家標準(CNS) A4規格(210X297公袭:) '" ---— 1304279 A7 B7 五、發明説明(3 ) 電話、筆記型電腦中)吸收、或儲存、或釋放、或吸收及儲 存、或吸收及釋放、或儲存及釋放或吸收、儲存及釋放至 少一種氣體之方法。 其進一步係關於在本文中敘述之裝置用於對於發電薇、 車、卡車、公共汽車、蜂巢式行動電話、筆記型電腦供 應動力之用途。 含金屬-有機細孔之骨架材料,其轉而包含一種金屬離子 及一種至少雙配位基之有機化合物,該雙配位基之有機化 合物係結合(較佳係配位地結合)於該金屬離子。此種材料本 身係已知的及敘述於例如美國專利5,648,508、歐洲專利-A- 0 709 253、J. Sol. State Chem.,ii2(2000)第 3-20 頁、Nature 生02X1999),第 276頁以下、Topics in Catalysis 2X1999),第 105-111頁、Science 2ϋ(2001),第1021-23頁中。用於彼等之製 備之一種不昂貴之方法係西德專利1〇1 1 1230.0之主題。以 上引述之文獻之内容,其係於本文中提及,係完全併於本 專利申請案之内容中。 金屬-有機骨架材料’如於本發明中使用,包含細孔,特 定言之微細孔及/或中細孔,其中根據於Pure Applied Chem. 第71頁以下(特定言之第79頁)(1976)中之定義,分別地 微細孔係定義如具有2奈米或以下之直徑之細孔及中細孔係 具有於大於2奈米至5 0奈米之範圍内之直徑之細孔。微細孔 及/或中細孔之存在可係經由根據德國工業標準(DIN) 66 13 i 、66134用於測定金屬-有機骨架材料於77凱氏溫度(κ)吸收 氮之谷量之吸附作用測量而監測。類型小形式之等溫曲線 -7- I紙張尺度適用中8 8家料(CNS) Α4規格(21GX 297公复)一 1304279
表示微細孔之存在。於一種較佳具體實施例中,比表面積 ’如根據郎格繆爾(Langmuir)模型計算,較佳係大於$平方 米/克、更佳係大於20平方米/克、再更佳係大於5〇平方米/ 克’特定言之係大於500平方米/克及可增加進入大於2〇〇〇 平方米/克之區域中。 作為於如根據本發明使用之骨架材料之範圍内之金屬組 份,特別被提及者係週期表之Ia、IIa、IIIa、IVas vHIa& lb至VIb族之元素之金屬離子;於特別被提及者中係、
Ca、Sr、Ba、Sc、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、M〇 、W、Mn、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、 Cu、Ag、Au、Zn、Cd、Hg、A卜 Ga、In、ΤΠ、Si、Ge、
Sn、Pb、As、Sb、及 Bi,更佳係 Zn、Cu、Ni、Pd、Pt、Ru 、Rh及Co。作為此等之金屬離子,特別被提及者係Mg2+、
Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ti4+、Zr4+、Hf4+、V4 + 、V3+、V2、Nb3+、Ta;+、、M〇3+、W3+、Mn3+、
Mn2+、Reh、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、〇s3+、
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+、Pb“、Pb2+、As5.、As3+、As+、 Sb5+、Sb3+、Sb+及 Bi5+、Bi3+、Bi+。 關於較佳之金屬離子及關於該等金屬離子之進一步之細 節’本發明人等特別提及:歐洲專利-A- 0 790 253,特別 係第10頁,1. 8-30部分、、金屬離子(The Metal Ions),,,該 -8- 本紙張尺度適用中s a家標準(CNS) M規格(灿χ 297公董) 裝 訂
1304279 A7 B7 五、發明説明(5 ) 部分係以提及之方式併於本文。 理論上可使用適合於此種與金屬離子配位之目的並符合 係至少雙配位基之以上要求之所有化合物,以作為該至少 雙配位基之有機化合物,其具有與金屬離子配位之能力。 該有機化合物必須具有至少兩個中心,其等具有與金屬鹽 (特定言之與前述族群之金屬之鹽)之金屬離子配位之能力。 關於至少雙配位基之有機化合物,特別提及者係具有下列 次結構之化合物: i) 烷基次結構,具有1至10個碳原子, ii) 芳基次結構,具有1至5個苯基環, iii) 烷基或芳基胺次結構,係由具有1至10個碳原子之烷 基或具有1至5個苯基環之芳基組成, 該次結構已結合於其之至少一種之至少雙配位基之官能基 "X”,其係共價地結合於該化合物之次結構,及其中X係由 下列組成之族群選出: C02H、CS2H、N02 ' S03H、Si(OH)3、Ge(〇H)3、Sn(〇H)3 、Si(SH)4、Ge(SH)4、Sn(SH)3、P〇3H、As〇3H、As04H、 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, 其中R係具有1至5個碳原子之烷基、或由1至2個苯基環組成 之芳基,及 CH(SH)2 ' C(SH)3、CH(NH2)2、C(NH2)2、 CH(OH)2、C(OH)3、CH(CN)2及 C(CN)3。 特別被提及者係經取代或未經取代、單-或多核之芳族 二-、三-及四羧酸類及經取代或未經取代、芳族、包含至少 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 ____ B7 五、發明説明(6 ) 一個雜原子之芳族二-、三-及四羧酸類,其等具有一個或多 個核。 一種較佳之配位子係對酜酸,特定言之較佳之金屬離子 係 Co2+ 及 Zn2+。 除了該至少雙配位基之有機化合物以外,作為根據本發 明使用之骨架材料亦可包含一個或多個單-配位基之配位子 ’其等較佳係衍生自下列之單-配位基之物質: a·烧基胺類及彼等之對應之烷基銨鹽類,其等包含線型 、分枝或環狀之脂族基,具有1至2〇個碳原子(及彼等 之對應之銨鹽類); b·具有1至5個苯基環之芳基胺類及彼等之對應之芳基銨 鹽類; c. 烷基鱗鹽類,其等包含線型、分枝、或環狀之脂族基 ,具有1至20個碳原子; d. 芳基鱗鹽類,其等具有1至5個苯基環; e·烷基有機酸類及對應之烷基有機陰離子類(及鹽類), 其等包含線型、分枝、或環狀之脂族基,具有1至2〇個 碳原子; f·芳基有機酸類及彼等之對應之芳基有機陰離子類及鹽 類,其等具有1至5個苯基環; g·脂族醇類,其等包含線型、分枝、或環狀之脂族基, 具有1至20個碳原子; h·具有1至5個苯基環之芳基醇類; 1·來自由下列組成之族群之無機陰離子: -10- 本紙張尺度適用中國國家標準(CNS) A4規格(21〇X 297公釐) 1304279 A7 B7 五、發明説明(7 ) 硫酸根、硝酸根、亞硝酸根、亞硫酸根、亞硫酸氫根 、磷酸根、磷酸氫根、磷酸二氫根、二磷酸根、三磷 酸根、磷酸根、亞磷酸根、氣離子、氯酸根、溴離子 、溴酸根、埃離子、議酸根、碳酸根、碳酸氫根、及 前述無機陰離子之對應之酸類及鹽類; j·氨、二氧化石炭、甲烷、氧、乙烯、己烷、苯、甲苯、 二甲苯、氣苯、硝基苯、萘、噻吩、吡啶、丙酮、 1,2-二氣乙烷、二氣甲烷、四氫呋喃、乙醇胺、三乙 胺及三氟甲基磺酸。 關於該等至少雙配位基之有機化合物及單配位基之物質 之進一步細節,如於本專利申請案中使用之骨架材料之配 位子係自彼等衍生,可係自歐洲專利-A 0 790 253推論,其 之各別之内容係以提及之方式併入本專利申請案中。 作為實例’以下提供已合成及描述之金屬-有機骨架材料 之表。此表亦包含新穎之等細網狀(isoreticular)金屬有機骨 架材料(IR-MOFs),其等可係使用於本專利申請案之骨架材 料中。敘述具有相同之骨架位相學(topology)而顯示不同之 細孔大小及晶體密度之此等材料,例如於M· Eddouadi等人 ,Science 295(2002)469中敘述,該文章係以提及之方式併 入本專利申請案中。 使用之溶劑對於此等材料之合成係特別重要的及因此於 該表中提及。用於細胞參數(cell parameter)之值(角度α、 /3及r以及間隔a、b及c,以埃表示)係已經由χ_射線繞射而 獲得及亦代表於該表中提供之空間群(space gr〇up)。 -11- ^紙張尺度適用中國國家標準(CNS)人4規‘_(21〇 X 297公€-- 1304279 A7 B7 五、發明説明(8 ) MOF-n 成分 莫耳比 M + L 溶劑s a β r a b c 空間群 MOF-O Zn(N03)2 · 6H20 H3(BTC) 乙醇 90 90 120 16.711 16.711 14.189 P6(3)/ Mem MOF-2 Zn(N03)2 . 6H20 (0.246毫莫耳) H2(BDC) (0.241毫莫耳) 二甲基 甲醯胺 (DMF) 甲笨 90 10.2.8 90 6.718 15.49 12.43 P2(l)/n MOF-3 Zn(N03)2 · 6H20 (1.89毫莫耳) H2(BDC) (1·93毫莫耳) DMF MeOH 99.72 111.11 108.4 9.726 9.911 10.45 P-1 MOF-4 Ζη(Ν03)2 · 6H20 (1.00毫莫耳) H3(BTC) (0.5毫莫耳) 乙醇 90 90 90 14.728 14.728 14.728 P2(l)3 MOF-5 Zn(N03)2 · 6H20 (2.22毫莫耳) H2(BDC) (2.17毫莫耳) DMF 氣苯 90 90 90 25.669 25.669 25.669 Fm-3m MOF-38 Zn(N03)2 · 6H20 (0.27毫莫耳) H3(BTC) (0·15毫莫耳) DMF 氣苯 90 90 90 20.657 20.657 17.84 14cm MOF-31 Zn(ADC)2 Ζη(Ν03)2 · 6H20 0.4毫莫耳 H2(ADC) 0.8毫莫耳 乙醇 90 90 90 10.821 10.821 10.821 Pn(-3)m MOF-12 Zn2(ATC) Zn(N03)2 . 6H20 0.3毫莫耳 H4(ATC) 0.15毫莫耳 乙醇 90 90 90 15.745 16.907 18.167 Pbca MOF-20 ZnNDC Zn(N03)2 · 6H20 0.37毫莫耳 H2NDC 0.36毫莫耳 DMF 氯苯 90 92.13 90 8.13 16.444 12.807 P2(l)/c MOF-3 7 Zn(N03)2 * 6H20 0.2毫莫耳 H2NDC 0.2毫莫耳 二乙基 甲釅胺 (DEF) 氣苯 72.38 83.16 84.33 9.952 11.576 15.556 P-1 -12- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(9 ) MOF-8 Tbz(ADC) Tb(N03)3 · 5H20 0.10毫莫耳 H2ADC 0.20毫莫耳 二甲亞 颯 (DMSO) MeOH 90 115.7 90 19.83 9.822 19.183 C2/c MOF-9 Tb2(ADC) Tb(N03)3 · 5H20 0.08毫莫耳 H2ADB 0.12毫莫耳 DMSO 90 102.09 90 27.056 16.795 28.139 C2/c MOF-6 Tb(N03)3 · 5H20 0.30毫莫耳 H2(BDC) 0.30毫莫耳 DMF MeOH 90 91.28 90 17.599 19.996 10.545 P21/c MOF-7 Tb(N03)3 * 5H20 0.15毫莫耳 H2(BDC) 0.15毫莫耳 H20 102.3 91.12 101.5 6.142 10.069 10.096 p-i MOF-69A Zn(N03)2 · 6H20 0.083毫莫耳 4’4’BPDC 0.041毫莫耳 二乙亞 硪(DEF) H2〇2 MeNH2 90 111.6 90 23.12 20.92 12 C2/c MOF-69B Zn(N03)2 * 6H20 0.083毫莫耳 2,6-NCD 0.041毫莫耳 DEF H202 MeNH2 90 95.3 90 20.17 18,55 12.16 C2/c MOF-11 Cu2(ATC) Cu(N03)2 · 2.5H20 0.47毫莫耳 H2ATC 0.22毫莫耳 H20 90 93.86 90 12.987 11.22 11.336 C2/c MOF-11 無水 Cu2(ATC) 90 90 90 8.4671 8.4671 14.44 P42/mmc MOF-14 Cu3(BTB) Cu(N03)2 · 2.5H20 0.28毫莫耳 H3BTB 0.052毫莫耳 h2o DMF EtOH 90 90 90 26.946 26.946 26.946 Im-3 MOF-32 Cd(ATC) Cd(N03)2 · 4H20 0.24毫莫耳 H4ATC 0.10毫莫耳 H20 NaOH 90 90 90 13.468 13.468 13.468 P(-4)3m MOF-33 Zn2(ATB) ZnCl2 0.15毫莫耳 H4ATB 0.02毫莫耳 H20 DMF EtOH 90 90 90 19.561 15.255 23.404 Imma -13- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(1〇 ) MOF-34 Ni(ATC) Ni(N03)2 * 6H20 0.24毫莫耳 H4ATC 0.10毫莫耳 H20 NaOH 90 90 90 10.066 11.163 19.201 P2.2.2, MOF-36 Zn2(MTB) Zn(N03)2 * 4H20 0.20毫莫耳 H4MTB 0.04毫莫耳 H20 DMF 90 90 90 15.745 16.907 18.167 Pbca MOF-39 Ζη30 (HBTB) Zn(N03)2 . 4H20 0.27毫莫耳 H3BTB 0.07毫莫耳 H20 DMF EtOH 90 90 90 17.158 21.591 25.308 Pnma NO305 FeCl2 · 4H20 5.03毫莫耳 曱酸 86.90毫莫耳 DMF 90 90 120 8.2692 8.2692 63.566 R-3c NO306A FeCl2 · 4H20 5.03毫莫耳 曱酸 86.90毫莫耳 DEF 90 90 90 9.9364 18.374 18.374 Pbcn N029 相似於 MOF-O Mn(Ac): · 4H20 0.46毫莫耳 H3BTC 0.69毫莫耳 DMF 120 90 90 14.16 33.521 33.521 P-1 BPR48 A2 Zn(N03)2 . 6H20 0.012毫莫耳 H3BDC 0.012毫莫耳 DMSO 甲苯 90 90 90 14.5 17.04 18.02 Pbca BPR69 B1 Cd(N03)2 · 4H20 0.0212毫莫耳 H2BDC 0.0428毫莫耳 DMSO 90 98.76 90 14.16 15.72 17.66 Cc BPR92 A2 C〇(N03)2 * 6H20 0.018毫莫耳 H2BDC 0.018毫莫耳 N-甲 基。比 咯啶 m (NMP) 106.3 107.63 107.2 7.5308 10.942 11.025 PI BPR95 C5 Cd(N03)2 · 4H20 0.012毫莫耳 H2BDC 0.36毫莫耳 NMP 90 112.8 90 14.460 11.085 15.829 P2(l)/n -14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(”)
CuC6H4〇6 Cu(N03)2 · 2.5H20 0.370毫莫耳 H2BDC(OH)2 0.37毫莫耳 DMF 氯苯 90 105.29 90 15.259 14.816 14.13 P2(l)/c M(BTC) 相似於 MOF-O Co(S〇4)H20 0.055毫莫耳 H3BTC 0.037毫莫耳 DMF 相同於MOF-O Tb(C6H4〇6) Tb(N03)3 · 5H20 0.370毫莫耳 h2(c6h4o6) 0.56毫莫耳 DMF 氯苯 104.6 107.9 97.147 10.491 10.981 12.541 P-1 Zn(C2〇4) ZnCl2 0.370毫莫耳 草酸 0.37毫莫耳 DMF 氣苯 90 120 90 9.4168 9.4168 8.464 P(-3)lm Co(CHO) Co(N03)2 · 5H20 0.043毫莫耳 曱酸 1.60毫莫耳 DMF 90 91.32 90 11.328 10.049 14.854 P2(l)/n Cd(CHO) Cd(N03)2 . 4H20 0.185毫莫耳 甲酸 0.185毫莫耳 DMF 90 120 90 8.5168 8.5168 22.674 R-3c Cu(C3H204) Cu(N03)2 * 2.5H20 0.043毫莫耳 丙二酸 0.192毫莫耳 DMF 90 90 90 8.366 8.366 11.919 P43 Zn6(NDC)5 MOF-48 Zn(N03)2 * 6H20 0.097毫莫耳 14NDC 0.069毫莫耳 DMF 氣苯 H2〇2 90 95.902 90 19.504 16.482 14.64 C2/m MOF-47 Ζη(Ν03)2 · 6H20 0.185毫莫耳 H2(BDC [ CH3〕4) 0.185毫莫耳 DMF 氯苯 H2〇2 90 92.55 90 11.303 16.029 17.535 P2(l)/c M025 Cu(N03)2 * 2.5H20 0.084毫莫耳 BPhDC 0.085毫莫耳 DMF 90 112.0 90 23.880 16.834 18.389 P2(l)/c -15- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(12 )
Cu-Thio Cu(NO,)2 · 2.5H20 0.084毫莫耳 噻吩二曱酸 0.085毫莫耳 DEF 90 113.6 90 15.4747 14.514 14.032 P2(l)/c CIBDCI Cu(N03)2 · 2.5H20 0.084毫莫耳 H2(BDCCI2) 0.085毫莫耳 DMF 90 105.6 90 14.911 15.622 18.413 C2/c MOF-101 Cu(N03)2 · 2.5H20 0.084毫莫耳 BrBDC 0.085毫莫耳 DMF 90 90 90 21.607 20.607 20.073 Fm3m Zn3(BTC)2 ZnCl2 0.033毫莫耳 H3BTC 0.033毫莫耳 DMF EtOH 添加之 鹼 90 90 90 26.572 26.572 26.572 Fm-3m MOF-j Co(CH3C02)2 . 4H20 (1.65毫莫耳) H3(BZC) (0.95毫莫耳) H20 90 112.0 90 17.482 12.963 6.599 C2 MOF-n Zn(N03)2 · 6H20 H3(BTC) 乙醇 90 90 120 16.711 16.711 14.189 P6(3)/ mcm PbBDC Pb(N03)2 (0.181毫莫耳) H2(BDC) (0.181毫莫耳) DMF 乙醇 90 102.7 90 8.3639 17.991 9.9617 P2(l)/n Znhex Zn(N03)2 · 6H20 (0.171毫莫耳) H3BTB (0.114毫莫耳) DMF 對二曱 苯乙酵 90 90 120 37.1165 37.117 30.019 P3(l)c AS 16 FeBr2 0.927毫莫耳 H2(BDC) 0.927毫莫耳 無水 DMF 90 90.13 90 7.2595 8.7894 19.484 P2(l)c AS27-2 FeBr2 0.927毫莫耳 H3(BDC) 0.464毫莫耳 無水 DMF 90 90 90 26.735 26.735 26.735 Fm3m AS32 FeCl3 1.23毫莫耳 H2(BDC) 1.23毫莫耳 無水 DMF 正丙酵 90 90 120 12.535 12.535 18.479 P6(2)C -16 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(13 ) AS54-3 FeBr2 0.927毫莫耳 BPDC 0.927毫莫耳 無水 DMF 正丙酵 90 109.98 90 12.019 15.286 14.399 C2 AS61-4 FeBr2 0.927毫莫耳 m-BDC 0.927毫莫耳 無水 吡啶 90 90 120 13.017 13.017 14.896 P6(2)c AS68-7 FeBr2 0.927毫莫耳 m-BDC 1.204毫莫耳 無水 DMF 吡啶 90 90 90 18.3407 10.036 18.039 Pca2i Zn(ADC) Zn(N03)2 · 6H20 0.37毫莫耳 H2(ADC) 0.36毫莫耳 DMF 氣苯 90 99.85 90 16.764 9.349 9.635 C2/c MOF-12 Zn2(ATC) Zn(N03)2 · 6H20 0.30毫莫耳 H4(AtC) 0.15毫莫耳 乙醇 90 90 90 15.745 16.907 18.167 Pbca MOF-20 ZnNDC Zn(N03)2 * 6H20 0.37毫莫耳 H2NDC 0.36毫莫耳 DMF 氣苯 90 92.13 90 8.13 16.444 12.807 P2(l)/c MOF-37 • Zn(N03)2 · 6H20 0.20毫莫耳 H2NDC 0.20毫莫耳 DEF 氣苯 72.38 83.16 84.33 9.952 11.576 15.556 P-1 Zn(NDC) (DMSO) Zn(N03)2 · 6H20 h2ndc DMSO 68.08 75.33 88.31 8.631 10.207 13.114 P-1 Zn(NDC) Zn(N03)2 · 6H20 h2ndc 90 99.2 90 19.289 17.628 15.052 C2/c Zn(HPDC) Zn(N03)2 · 4H20 0.23毫莫耳 H2(HPDC) 0.05毫莫耳 DMF H20 107.9 105.06 94.4 8.326 12.085 13.767 P-1 Co(HPDC) Co(N03)2 · 6H20 0.21毫莫耳 H2(HPDC) 0.06毫莫耳 DMF H20/ 乙酵 90 97.69 90 29.677 9.63 7.981 C2/c -17- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(14 )
Zn3(PDC)2.5 Zn(N03)2 * 4H20 0.Π毫莫耳 H2(HPDC) 0.05毫莫耳 DMF/ CIBz H20/ TEA 79.34 80.8 85.83 8.564 14.046 26.428 P-I Cd2(TPDC)2 Cd(N03)2 · 4H20 0.06毫莫耳 H2(HPDC) 0.06毫莫耳 甲醇/ CHP H20 70.59 72.75 87.14 10.102 14.412 14.964 P-1 Tb(PDC)1.5 Tb(N03)3 · 5H20 0.21毫莫耳 H2(PDC) 0.034毫莫耳 DMF H20/ 乙酵 109.8 103.61 100.14 9.829 12.11 14.628 P-1 ZnDBP Zn(N03)2 · 6H20 0.05毫莫耳 磷酸二苯甲酯 0.10毫莫耳 MeOH 90 93.67 90 9.254 10.762 27.93 P2/n Zn3(BPDC) ZnBr2 0.021毫莫耳 4,4’BPDC 0.005毫莫耳 DMF 90 102.76 90 11.49 14.79 19.18 P21/n CdBDC Cd(N03)2 . 4H20 0.100毫莫耳 H2(BDC) 0.401毫莫耳 DMF Na2Si03 (水溶液) 90 95.85 90 11.2 11.11 16.71 P21/n Cd-mBDC Cd(N03)2 · 4H20 0.009毫莫耳 H2(mBDC) 0.018毫莫耳 DMF MeNH2 90 101.1 90 13.69 18.25 14.91 C2/c Ζα,ΟΒΝΟΟ Ζη(Ν03)2 · 6H20 0.041毫莫耳 BNDC DEF MeNH2 H202 90 90 90 22.35 26.05 59.56 Fmmm Eu(TCA) Eu(N03)3 · 6H20 0.14毫莫耳 TCA 0.026毫莫耳 DMF 氯苯 90 90 90 23.325 23.325 23.325 Pm-3n Tb(TCA) Tb(N〇3)3 · 6H20 0.069毫莫耳 TCA 0.026毫莫耳 DMF 氯笨 90 90 90 23.272 23.272 23.272 Pm-3n 甲酸鹽 Ce(N03)3 · 6H20 0.138毫莫耳 甲酸 0.43毫莫耳 H20 乙醇 90 90 120 10.668 10.667 4.107 R-3m -18- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1304279 A7 B7 五、發明説明(15 )
Fe Cl2 · 4H20 5.03毫莫耳 甲酸 86.90毫莫耳 DMF 90 90 120 8.2692 8.2692 63.566 R-3c Fe CI2 · 4H20 5.03毫莫耳 甲酸 86.90毫莫耳 DEF 90 90 90 9.9364 18.374 18.374 Pbcn Fe Cl2 · 4H20 5.03毫莫耳 甲酸 86.90毫莫耳 DEF 90 90 90 8.335 8.335 13.34 P-31c NO330 Fe Cl2 · 4H20 0.50毫莫耳 甲酸 8.69毫莫耳 甲醞胺 90 90 90 8.7749 11.655 8.3297 Pnna N0332 Fe Cl2 · 4H20 0.50毫莫耳 曱酸 8.69毫莫耳 DIP 90 90 90 10.0313 18.808 18.355 Pbcn N0333 Fe Cl2 · 4H20 0.50毫莫耳 甲酸 8.69毫莫耳 DBF 90 90 90 45.2754 23.861 12.441 Cmcm N0335 Fe Cl2 · 4H20 0.50毫莫耳 甲酸 8.69毫莫耳 CHF 90 91.372 90 11.5964 10.187 14.945 P21/n N0336 Fe Cl2 · 4H20 0.50毫莫耳 甲酸 8.69毫莫耳 MFA 90 90 90 11.7945 48.843 8.4136 Pbcm N013 Mn(Ac)2 · 4H20 0.46毫莫耳 苯曱酸 0.92毫莫耳 雙吡咬 0.46毫莫耳 乙醇 90 90 90 18.66 11.762 9.418 Pbcn N029 相似於 MOF-0 Mn(Ac)2 · 4H20 0.46毫莫耳 H3BTC 0.69毫莫耳 DMF 120 90 90 14.16 33.521 33.521 P-1 Mn(hfac)2 Mn(Ac)2 * 4H20 醚 90 95.32 90 9.572 17.162 14.041 C2/c -19- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(16 ) (02CCr,H5) 0.46毫莫耳 Hfac 0.92毫莫耳 雙吡啶 0.46·毫莫耳 BPR43G2 Ζη(Ν〇ι)2 · 6Η20 0.0288毫莫耳 H2BDC 0.0072毫莫耳 DMF CHiCN 90 91.37 90 17.96 6.38 7.19 C2/c BPR48A2 Ζη(ΝΟ.ι)2 · 6H20 0.012毫莫耳 H2BDC 0.012毫莫耳 DMSO 甲苯 90 90 90 14.5 17.04 18.02 Pbca BPR49B1 Ζη(Ν03)2 . 6H20 0.024毫莫耳 H2BDC 0.048毫莫耳 DMSO 甲醇 90 91.172 90 33.181 9.824 17.884 C2/c BPR56E1 Ζη(Ν03)2 · 6H20 0.012毫莫耳 H2BDC 0.024毫莫耳 DMSO 正丙醇 90 90.096 90 14.5873 14.153 17.183 P2(l)/n BPR68D10 Ζη(Ν03)2 * 6H20 0.0016毫莫耳 H3BTC 0.0064毫莫耳 DMSO 苯 90 95.316 90 10.0627 10.17 16.413 P2(l)/c BPR69B1 Cd(NO:,)2 · 4H20 0.0212毫莫耳 H2BDC 0.0428毫莫耳 DMSO 90 98.76 90 14.16 15.72 17.66 Cc BPR73E4 Cd(N03)2 · 4H20 0.006毫莫耳 H2BDC 0.003毫莫耳 DMSO 甲苯 90 92.324 90 8.7231 7.0568 18.438 P2(l/n) BPR76D5 Zn(N03)2 · 6H20 0.0009毫莫耳 H2B2PDC 0.036毫莫耳 DMSO 90 104.17 90 14.4191 6.2599 7.0611 Pc BPR80B5 Cd(N03)2 · 4H20 0.018毫莫耳 H2BDC 0.036毫莫耳 DMF 90 115.11 90 28.049 9.184 17.837 C2/c BPR80H5 Cd(NO,)2 · 4H20 0.027毫莫耳 H2BDC 0.027毫莫耳 DMF 90 119.06 90 11.4746 6.2151 17.268 P2/c -20- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1304279 A7 B7 五、發明説明(17 ) BPR82C6 Cd(NO,)2 · 4H20 0.0068毫莫耳 H2BDC 0.202毫莫耳 DMF 90 90 90 9.7721 21.142 27.77 Fdd2 BPR86C3 Co(N〇3)2 · 6H20 0.0025毫莫耳 H2BDC 0.075毫莫耳 DMF 90 90 90 18.3449 10.031 17.983 Pca2(l) BPR86H6 Cd(N03)2 . 6H2〇 0.010毫莫耳 H2BDC 0.010毫莫耳 DMF 80.98 89.69 83.412 9.8722 10.263 15.362 P-1 Co(N〇3)26H20 NMP 106.3 107.63 107.2 7.5308 10.942 11.025 PI BPR95A2 Zn(C03)2 · 6H20 0.012毫莫耳 H2BDC 0.012毫莫耳 NMP 90 102.9 90 7.4502 13.767 12.713 P2(l)/c CuCr,F4〇4 Cu(N03)2 · 2.5H20 0.370毫莫耳 H2BDC(OH)2 0.37毫莫耳 DMF 氣苯 90 98.834 90 10.9675 24.43 22.553 P2(l)/n 曱酸Fe Fe Cl2 · 4H20 0.370毫莫耳 曱酸 0.37毫莫耳 DMF 90 91.543 90 11.495 9.963 14.48 P2(l)/n 甲酸Mg Mg(N03)2 . 6H20 0.370毫莫耳 甲酸 0.37毫莫耳 DMF 90 91.359. 90 11.383 9.932 14.656 P2(l)/n MgC6H4〇6 Mg(N03)2 · 6H20 0.370毫莫耳 H2BDC(OH)2 0.37毫莫耳 DMF 90 96.624 90 17.245 9.943 9.273 C2/c ZnC2H4BDC MOF-38 ZnCl2 0.44毫莫耳 CBBDC 0.261毫莫耳 DMF 90 94.714 90 7.3386 16.834 12.52 P2(l)/n MOF-49 ZnCl2 0.44毫莫耳 m-BDC 0.261毫莫耳 DMF CH3CN 90 93.459 90 13.509 11.984 27.039 P2/c -21 -
裝 訂 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 五、發明説明(18 ) MOF-26 Cu(NO〇2 · 5H20 0.084毫莫耳 DCPE 0.085毫莫耳 DMF 90 95.607 90 20.8797 16.017 26.176 P2(l)/n MOF-112 CulNO.O: · 2.5H20 0.084毫莫耳 o-Br-m-BDC 0.085毫莫耳 DMF 乙醇 90 107.49 90 29.3241 21.297 18.069 C2/c MOF-109 Cu(N03)2 · 2.5H20 0.084毫莫耳 KDB 0.085$莫耳 DMF 90 111.98 90 23.8801 16.834 18.389 P2(l)/c MOF-lli Cu(NO.)2 · 2.5H20 0.084毫莫耳 o-BrBDC 0.085毫莫耳 DMF 乙醇 90 102.16 90 10.6767 18.781 21.052 C2/c MOF-110 Cu(NO〇2 · 2.5H20 0.084毫莫耳 噻吩二甲酸 0.085毫莫耳 DMF 90 90 120 20.0652 20.065 20.747 R-3/m MOF-107 Cu(N03)2 · 2.5H20 0.084毫莫耳 噻吩二曱酸 0.085毫莫耳 DEF 104.8 97.075 95.206 11.032 18.067 18.452 P-1 MOF-108 Cu(NO,)2 · 2.5H20 0.084毫莫耳 噻吩二甲酸 0.085毫莫耳 DBF/ 甲醇 90 113.63 90 15.4747 14.514 14.032 C2/c MOF-102 Cu(N03)2 · 2·5Η20 0.084毫莫耳 H2(BDCC12) 0.085毫莫耳 DMF 91.63 106.24 112.01 9.3845 10.794 10.831 P-1 Clbdcl Cu(NO,)2 · 2.5H20 0.084毫莫耳 H2(BDCC12) 0.085毫莫耳 DEF 90 105.56 90 14.911 15.622 18.413 P-1 Cu(NMOP) Cu(N03)2 · 2.5H20 0.084毫莫耳 NBDC 0.085毫莫耳 DMF 90 102.37 90 14.9238 18.727 15.529 P2(l)/m -22-
裝 訂
本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1304279 A7 B7 五、發明説明(19 )
Tb(BTC) Tb(N03)3 . 5H20 0.033毫莫耳 H3BTC 0.033毫莫耳 DMF 90 106.02 90 18.6986 11.368 19.721 Zn3(BTC)2 Honk ZnCl2 0.033毫莫耳 H3BTC 0.033毫莫耳 DMF 乙醇 90 90 90 26.572 26.572 26.572 Fm-3m Zn4〇(NDC) Zn(N03)2 · 4H20 0.066毫莫耳 14NDC 0.066毫莫耳 DMF 乙醇 90 90 90 41.5594 18.818 17.574 aba2 CdTDC Cd(N03)2 · 4H20 0.014毫莫耳 噻吩 0.040毫莫耳 DABCO 0.020毫莫耳 DMF H20 90 90 90 12.173 10.485 7.33 Pmma IRMOF-2 Ζη(Ν03)2 · 4H20 0.160毫莫耳 o-Br-BDC 0.60毫莫耳 DEF 90 90 90 25.772 25.772 25.772 Fm-3m IRMOF-3 Ζη(Ν03)2 · 4H20 0.20毫莫耳 H2N-BDC 0.60毫莫耳 DEF 乙醇 90 90 90 25.747 25.747 25.747 Fm-3m IRMOF-4 Zn(N03)2 · 4H20 0.11毫莫耳 〔c3h7o〕2-bdc 0.48毫莫耳 DEF 90 90 90 25.849 25.849 25.849 Fm-3m IRMOF-5 Zn(N03)2 · 4H20 0.Π毫莫耳 (C5Hu〇)2-BDC 0.50毫莫耳 DEF 90 90 90 12.882 12.882 12.882 Fm-3m IRMOF-6 Zn(N03)2 · 4H20 0.20毫莫耳 (C2H4)-BDC 0.60毫莫耳 DEF 90 90 90 25.842 25.842 25.842 Fm-3m IRMOF-7 Zn(N03)2 · 4H20 0.07毫莫耳 1,4NDC 0.20毫莫耳 DEF 90 90 90 12.914 12.914 12.914 Fm-3m -23- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1304279 A7 B7 IRMOF-8 Zn(N03)2 * 4H20 0.55毫莫耳 2,6NDC 0.42毫莫耳 DEF 90 90 90 30.092 30.092 30.092 Fm-3m IRMOF-9 Ζη(Ν03)2 · 4H20 0.05毫莫耳 BPDC 0.42毫莫耳 DEF 90 90 90 17.147 23.322 25.255 Pnnm IRMOF-10 Ζη(Ν03)2 · 4H20 0.02毫莫耳 BPDC 0.012毫莫耳 DEF 90 90 90 34.281 34.281 34.281 Fm-3m IRMOF-11 Ζη(Ν03)2 · 4H20 0.05毫莫耳 HPDC 0.20毫莫耳 DEF 90 90 90 24.822 24.822 56.734 R-3m IRMOF-12 Ζη(Ν03)2 · 4H20 0.017毫莫耳 HPDC 0.12毫莫耳 DEF 90 90 90 34.281 34.281 34.281 Fm-3m IRMOF-13 Zn(N03)2 · 4H20 0.048毫莫耳 PDC 0.31毫莫耳 DEF 90 90 90 24.822 24.822 56.734 R-3m IRMOF-14 Zn(N03)2 · 4H20 0.17毫莫耳 PDC 0.12毫莫耳 DEF 90 90 90 34.381 34.381 34.381 Fm-3m IRMOF-15 Zn(N03)2 · 4H20 0.063毫莫耳 TPDC 0.025毫莫耳 DEF 90 90 90 21.459 21.459 21.459 Im-3m IRMOF-16 Zn(N03)2 · 4H20 0.0126毫莫耳 TPDC 0.05毫莫耳 DEF NMP 90 90 90 21.49 21.49 21.49 Pm-3m 五、發明説明(2Q ) ADC 乙炔 二 甲酸 NDC 萘二 甲 酸 BDC 苯二 甲 酸 ATC 金剛 烷 四甲酸 -24-本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1304279 A7 ___B7五、發明説明(21 ) 苯三甲酸 苯三苯f酸 甲烷四苯甲酸 金剛烷四苯甲酸 金剛烷二苯甲酸 特別較佳者係於本文中敘述之種類之本專利申請案骨架 材料之範圍内,其等包含Zn2 +作為金屬離子及衍生自對酜 酸之配位子作為雙配位基之化合物,其等於文獻中係以 MOF-5知曉。 另外之金屬離子及至少雙配位基之有機化合物及單-配位 基之物質’其等對於在本發明中使用之骨架材料之製備以 及用於彼專之製備之方法分別係有用的,係特別地揭示於 歐洲專利-A 0 790 253、美國專利5,648,5〇8及西德專利 101 1 1230.0 中。 作為溶劑,其等對於MOF-5之製備係特別有用的,除了 於以上提及之文獻中揭示之溶劑以外,可單獨地使用二甲 基甲醯胺、二乙基甲醯胺、及斗甲基吡咯啶酮,與彼此共 同使用或與其他溶劑共同使用。於骨架材料之製備之範圍 内,特定言之於MOF-5之製備之範圍内,溶劑及母液係於 結晶作用之後循環使用,俾能節省成本及材料。 骨架材料,特定言之MOF-5,自結晶作用之母液之分離 可係經由於此技藝中已知之程序而達成,諸如固體_液體分 離諸如離心、萃取、過濾、膜過遽、交又流過濾、使用 絮凝作用佐劑(非離子、陽離子及陰離子佐劑)或經由 移添加劑(諸如鹽類、酸類或鹼類)之添加而絮凝、經由上浮 、喷霧-乾燥或噴霧粒化以及經由母液於提高之溫度及/或於 -25- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐)
BTC ΒΤΒ ΜΤΒ ΑΤΒ ADB
裝· 訂
k 1304279 A7 B7 五 、發明説明(22 ) '"---- 真空中之蒸發及固體之濃縮。 經分離之骨架材料,特定言之M0F_5,可係根據於塑膠 口工之範圍内已知之程序而分別地混合、熔融、擠製、共_ 擠製、壓製、抽絲、發泡及粒化。通常,對於本發明之目 的,材料係以顆粒之形式或以膜或似片狀之形式使用。然 而,以上之方法容許製備多種另外及不同之幾何及形狀, 其等對於根據本發明之該材料之廣泛應用領域,特定言之 使用於移動及移動可攜帶之應用中,係必要的。 作為被保持及/或儲存及/或釋放之氣體,特別被提及者係 烴類、醇類、氫、氮、惰性氣體、c〇、c〇2、天然氣、合 成軋產生及/或供應此等氣體之化合物類及兩種或兩種以 上其等之混合物◎特別較佳者係氫、含氫之氣體混合物、 產生或供應氫之物質、包含至少一種產生及/或供應氫之物 質之氣體混合物。 於另一種具體實施例中,金屬-有機骨架材料係與至少一 種由下列組成之族群中選出之容量-增進劑接觸:溶劑類、 複合物類、金屬類、金屬氫化物類、合金類、及兩種或兩 種以上其等之混合物,諸如以上自Pd、pt、Ni、及Ru作為 金屬而衍生之具體實施例。 此外,本發明係關於容納一種金屬_有機骨架材料,如於 本文中定義,以吸收、或儲存、或釋放、或吸收及儲存、 或吸收及釋放、或儲存及釋放、或吸收、儲存及釋放至少 一種氣體之裝置。 該裝置可包含下列進一步之組件: -26- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公董) " ----— 1304279
容納該金屬-有機骨架材料之一容器. 容許該至少一種氣體進入或離開該裝置之一進入/離開開 口 ; 具有維持氣體於容器内之壓力下之能力之一維持氣體·密 閉之機構。 本發明進一步係關於容納如於本文中敘述之試劑之燃料 電池。 其亦係關於使用一種包含於本文中敘述之金屬_有機骨架 材料之試劑以於固定、移動及移動可攜帶之應用中(較佳係 於發電廠、汽車、卡車、公共汽車、蜂巢式行動電話、筆 β己型電腦中)吸收、或儲存、或釋放、或吸收及儲存、或吸 收及釋放、或儲存及釋放或吸收、儲存及釋放至少一種氣 體之方法,及使用根據本發明之裝置以對於發電廠、汽車 、卡車、公共汽車、蜂巢式行動電話、筆記型電腦供應動 力之方法。 使用根據申請專利範圍第10項之燃料電池以對於發電廠 /1車、卡車、公共Ά車、蜂巢式行動電話、筆記型電腦 供應動力之方法。 本發明現在係經由下列之實例而進一步敘述,然而,彼 專不是計劃以限制本專利申請案之範圍。 實例 圖1顯示如根據實例1製備之MOF-5骨架材料之χ_射線粉 末繞射圖(diffractogramm)。 -27-
1304279 A7 B7 五、發明説明(24 ) 圖2顯示氬於87凱氏溫度對於MOF-5之吸收等溫線 圖3顯示氫於30°C對於MOF-5之吸收等溫線。 fAUM〇F-5之製備) 原料 莫耳數量 計算值 實驗值 對酜 12.3毫莫 2.04 克 2.04 克 耳 石肖酸辞-四水合物 36.98毫莫 9.67 克 9.68 克 耳 二乙基甲醢胺 2568.8 毫 282.2 克 282.2 克 (Merck) 莫耳 於燒杯中,將上述數量之原料以二乙基甲醯胺、對酜酸 及硝酸鋅之次序溶解。將生成之溶液引進入兩個熱壓器 (250毫升)中,此等熱壓器分別具有以聚四氟乙烯覆蓋之内 壁〇 於105t於20小時之内發生結晶作用。其後,將橙色溶劑 自黃色晶體傾析出,將該晶體再以2〇毫升二甲基甲醯胺覆 蓋’再將二甲基甲醯胺傾析出。重複此種程序三次。其後 ’將20毫升氯仿傾倒於固體上,該固體係以該溶劑洗條及 傾析兩次。 將晶體(14.4克),其仍然係濕的,引進入一真空裝置中及 首先於室溫於真空(1〇_4毫巴)中乾燥,其後K12(rc乾燥。 其後’生成之產物係以X-射線粉末繞射及微細孔之吸附 測定而描述。生成之產物顯示根據圖1之χ_射線繞射圖,其 -28 - 本紙張尺度適用中國國豕標準(CNS) A4規格(210X297公爱)
1304279
係與MOF-5相符合。 以氬(87凱氏溫度;Micromeritics ASAP 20 10)之吸收等溫 線之測定,如於圖2中描述,顯示類型I之等溫線,該等溫 線對於微細孔材料係典型的、及具有根據郎格繆爾 (Langmuir)計算之3020平方米/克之比表面積、及〇97毫升/ 克之微細孔體積(於相對壓力p/p〇= 0 4)。 實例2 經由使用 Rubotherm Prazissionsmesstechnik GmbH,Bochum 公司之磁性懸浮天平,實例丨之樣本對於氫之儲存容量係如 下測定。將樣本稱重、引進入裝置中。於將該裝置封閉及經 由隔膜prepump及渦輪分子泵而抽真空至1〇—5亳巴之壓力之 後,將該樣本於真空下K10(rc加熱歷時16小時。 於30C之溫度熬平衡該樣本之後,將氫(純度99,999%,
Me·公司)以根據圖3之各種壓力力口人。生成之吸收等溫線 係於圖3中顯示。此圖顯示,於約15〇亳巴之氫壓力,相對 於、、二活化之樣本之總重量,該樣本具有儲存約1重量%氫之 能力。於進一步提高之壓力下,該儲存容量甚至增加。 f例3(比卓$) 經由使用如於實例2中之相同實驗裝置及相同程序,測量 活1*生厌(CECA a司,AC 4〇 ;根據郎格谬爾之比表面積加7 平方米./克)對於氫之儲存容量。圖3顯示,與比較, 活性碳之有意義地較低之容量。 -29-
Claims (1)
- A BCD 13 04179114521號專利申請案 中文申請專利範圍替換本(97年8月) 一 申請專利範圍 公告 1 · 一種吸收、或儲k…产貧丁滅吸收及儲存、或吸收及 釋放、或儲存及釋放或吸收、儲存及釋放至少一種氣體 之方法,其中該氣體係經由包含一種金屬-有機骨架材料 之一種試劑而吸收、或儲存、或釋放、或吸收及儲存、 或吸收及釋放、或儲存及釋放或吸收、儲存及釋放,該 材料包含細孔及至少一種金屬離子及至少一種之至少雙 配位基有機化合物,其係結合於該金屬離子; 其中該包含細孔之金屬有機骨架材料顯示大於2〇〇〇平 方米/克之比表面積,如經由吸附作用(根據德國工業標 準(DIN) 66131 之 BET)測定; 其中該氣體包含至少一種由下列組成之族群中之氣體 :氯、氮、惰性氣體、CO、C〇2、及產生及/或供應此等 氣體之化合物; 其中該金屬離子係於元素週期表之Ia、Ha、nIa、lva 至Villa及lb至VIb族之元素之離子中選出;且 其中該雙配位基之有機化合物係於經取代或未經取代 之芳族多羧酸(該等多羧酸可包含—個或多個核)、及經取 代或未經取代之芳族多羧酸(該等多羧酸包含至少一個雜 原子及其可具有一個或多個核)中選出。 2. 根據申請專利範圍第!項之方法,其中該氣體係選自由氫 、含氫之氣體混合物、產生或供應氫之物質、包含至少 -種產生及/或供應氫之物質之氣體混合物及其組合所組 成之群組。 3. 根據申請專利範圍第〗項之方法’其進一步包含將該金 79081-970808.doc . ! _ 本紙i尺度適用巾η η家鮮(CNS) A4規格(21GX297公爱厂 裝 訂 1304279 as B8 C8屬^機骨架材料與至少一種由溶劑、複合物、 金 二虱:物:金屬合金、及兩種或兩種以上其等之混合物 斤、、且成之族群中選出之容量-增進劑接觸。 4·根據中請專利範圍第1項之方法,其中該至少_種之至少 雙配位基有機化合物係配位結合於該金屬離子。 5·種供吸收、或儲存、或釋放、或吸收及儲存、或吸收 及釋放、或儲存及釋放或吸收、㈣及釋放至卜種氣 體之裝置,其包含一種如申請專利範圍第1項所定義之金 屬-有機骨架材料。 6·根據申請專利範圍第5項之裝置,其進一步包括 包含該金屬-有機骨架材料之一容器; 容許該至少一種氣體進入或離開該裝置之一進入/離開 開口; 具有維持該氣體於該容器内之壓力下之能力之一維持 氣體-密閉機構。 7· 一種燃料電池,其包含根據申請專利範圍第1項所定義之 金屬-有機骨架材料。 8· 一種包含一種金屬_有機骨架材料之一種試劑之使用方 法,其中該材料包含細孔及至少一種金屬離子及至少一 種之至少雙配位基有機化合物,其係結合於該金屬離 子, 其中該使用包括於至少一種固定、移動或移動可攜帶 之應用中吸收、或儲存、或釋放、或吸收及儲存、或吸 收及釋放、或儲存及釋放或吸收、儲存及釋放至少一種 79081-970808.doc 本紙張尺度適用中國國家標準(CNS) A4規格(210χ297公董) A BCD 1304279 —----- 六、申請專利範圍 其中5亥包含細孔之金屬右嫩 方平/克之比m 材料顯示大於2_平 方未/克之比表面積,如經由吸附作 準(DIN) 06131之BET)測定; 康仏Θ工業払 其中該氣體包含至少一籀ώ ^ ^ z 種由下列組成之族群中之氣體 •氫、氮、惰性氣體、C0、c〇”月“野K虱體 氣體之化合物; 生及/或供應此等 其中該金屬離子係於元素週期表之ia、心、仙、^ 至Villa及lb至VIb族之元素之離子中選出;且 其中該雙配位基之有機化合物係於經取代或未經取代 之芳族多㈣(該等多㈣可包含_個或多個核)、及經取 代或未經取代之芳族多羧酸(該等多羧酸包含至少一個雜 原子及其可具有一個或多個核)中選出。 9 ·根據申响專利範圍第8項之使用方法,其中該至少一種應 用係選自由發電廠、汽車、卡車、公共汽車、蜂巢式行 動電話、筆記型電腦及其組合所組成之群組。 10·根據申請專利範圍第8項之使用方法,其中該至少一種之 至少雙配位基有機化合物係配位結合於該金屬離子。 11 · 一種根據申請專利範圍第5項之裝置之使用方法,其中該 使用包含: 對選自由發電廠、汽車、卡車、公共汽車、蜂巢式行 動電話、筆記型電腦及其組合所組成之群組之應用供應 動力。 12· —種根據申請專利範圍第7項之燃料電池之使用方法,其 79081-970808.doc 本紙痕尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 8 8 8 8 A B c D 1304279 六、申請專利範圍 包括使用燃料電池以對選自由發電廠、汽車、卡車、公 共汽車、蜂巢式行動電話、筆記型電腦及其組合所組成 之群組之應用供應動力。 79081-970808.doc - 4 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
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