CN106832314B - 一种稳定的In金属-有机骨架、单晶到单晶的制备方法及其应用 - Google Patents
一种稳定的In金属-有机骨架、单晶到单晶的制备方法及其应用 Download PDFInfo
- Publication number
- CN106832314B CN106832314B CN201710023494.9A CN201710023494A CN106832314B CN 106832314 B CN106832314 B CN 106832314B CN 201710023494 A CN201710023494 A CN 201710023494A CN 106832314 B CN106832314 B CN 106832314B
- Authority
- CN
- China
- Prior art keywords
- metal
- organic framework
- ttta
- monocrystalline
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims abstract description 16
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 7
- -1 methoxyl group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002050 diffraction method Methods 0.000 claims description 2
- 238000002411 thermogravimetry Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000002178 crystalline material Substances 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical compound [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- 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
- Y02C20/20—Capture or disposal of greenhouse gases of methane
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
一种稳定的In金属‑有机骨架、单晶到单晶的制备方法及其应用，属于晶态材料的技术领域。化学分子式为[In3(TTTA)2(CH3O)3]，TTTA为有机配体(2E,2'E,2”E)‑3,3',3”‑(2,4,6‑三甲基)‑均苯三丙烯酸。本发明将[In3(TTTA)2(OH)3H2O]通过浸泡于甲醇溶液中进行活化，使之发生单晶到单晶的转化过程得到的全新材料；此金属‑有机骨架具有较大的孔尺寸以及比表面积，可用作选择性吸附分离C2H2/CO2和C2H2/CH4的吸附材料。
Description
技术领域
本发明属于晶态材料的技术领域，技术涉及金属-有机配位聚合物材料，特别是一种铟(In)的金属-有机骨架(MOF)、单晶到单晶的转化过程及其应用。
技术背景
工业气体被喻为工业的“血液”。随着中国经济的快速发展，工业气体作为国民经济基础工业要素之一，在国民经济中的重要地位和作用日益凸显。根据不同工业生产环节的特定用途，对不同气体的纯度或组成、有害杂质允许的最高含量、产品的包装贮运等都有极其严格的要求，属于高技术，高附加值产品。因此，气体的纯化与选择性分离是当今工业生产中的重点和难点，以乙炔为例，作为一种高度易燃且性质活泼的反应性气体，乙炔被广泛应用于照明、焊接和切割金属(乙炔氧焰)，也是工业中生产乙醛、乙酸、苯、合成橡胶、合成纤维的基本原料，但由于乙炔的制备过程中经常会混入一些杂质气体(如二氧化碳、甲烷等)，严重影响乙炔气体的纯度，进而影响其使用范围与工业价值。传统的低温蒸馏等方法由于分离比低、能耗较高、耗时间长或存在一定的安全隐患，已经不能适应快速发展的经济对于高纯乙炔的需求量。所以寻找一种高效、安全、节能的吸附分离材料迫在眉睫。
金属有机骨架(Metal-Organic Frameworks,简称MOFs)作为一种新型的功能多孔材料，已经吸引了研究人员足够的关注，它是由含金属的节点和有机桥联配体通过配位键连接构筑而成，能在温和而简单的合成条件下制备，具有可随配体功能化、孔道结构多样性设计和调整的多样功能以及独特性质，目前已被研究运用与气体储存与分离、化学分选和催化、离子交换与吸附、生物医药、分子识别和传感等领域。正是由于MOFs材料往往具有较高的孔隙率和比表面积以及特殊孔洞性质，使其表现出非常好的气体储存与离子交换分离性能，尤其是表现在与传统多孔材料相比，MOFs的骨架结构与孔性质更容易调控，具有更高的吸附量以及更强的吸附能力。
发明内容
本发明的目的在于提供一种全新的In金属-有机骨架的单晶到单晶转化制备方法及其应用。
本发明的一种三维的In金属-有机骨架材料，其特征在于，化学分子式为[In3(TTTA)2(CH3O)3]，其中TTTA为有机配体(2E,2'E,2″E)-3,3',3″-(2,4,6-三甲基)-均苯三丙烯酸。从骨架连接构筑的角度，该三维金属有机骨架材料的晶体结构属于单斜晶系，空间群为P 21/c，晶胞参数为： α＝γ＝90°，β＝106.381(5)°。
该金属-有机骨架单晶结构中存在4个晶体学独立的In3+离子，每个In3+离子和6个O原子配位形成八面体构型。与In3+离子配位的6个O原子中包括4个来自配体的羧基氧原子以及2个来自甲氧基的O原子。配体中羧基和甲氧基所连接的In3+离子形成一维的金属链，此金属链在配体的桥连作用下形成三维金属-有机框架。该金属-有机骨架可进入的孔体积为45.3％。
其中有机配体(2E,2'E,2″E)-3,3',3″-(2,4,6-三甲基)-均苯三丙烯酸(TTTA)四苯甲酸的结构式如下所示。
本发明是在本发明人已发表的专利：《一种稳定的In金属-有机骨架的制备方法及其应用》(专利申请号：2016100389080，公开号CN105664893A)中In金属-有机骨架[In3(TTTA)2(OH)3H2O](以下用X表示)的基础上，通过单晶到单晶的转化过程得到的全新In金属-有机骨架材料[In3(TTTA)2(CH3O)3](以下用Y表示)。
具体步骤如下：将[In3(TTTA)2(OH)3H2O]金属-有机骨架材料置于同位素瓶中，向瓶内加入甲醇，然后拧紧瓶盖，置于常温的干燥通风处，每8小时后打开瓶盖，将瓶内的甲醇吸附后，再加入新鲜的甲醇，每8小时后打开瓶盖，将瓶内的甲醇吸附，加入新鲜的甲醇并吸附的过程进行多次重复，得到[In3(TTTA)2(CH3O)3]金属-有机骨架。
优选每10-200g[In3(TTTA)2(OH)3H2O]金属-有机骨架材料对应每次加入的甲醇为8-40ml；重复进行3-10次。
新鲜的甲醇为干燥纯净的甲醇。
[In3(TTTA)2(OH)3H2O]金属-有机骨架材料中TTTA为有机配体(2E,2'E,2″E)-3,3',3″-(2,4,6-三甲基)-均苯三丙烯酸；有机配体(2E,2'E,2″E)-3,3',3″-(2,4,6-三甲基)-均苯三丙烯酸(TTTA)四苯甲酸的结构式如下所示：
[In3(TTTA)2(OH)3H2O]从骨架连接构筑的角度，该三维In的金属-有机骨架材料的晶体结构属于单斜晶系，空间群为P 21/c，晶胞参数为： α＝γ＝90°β＝105.4324(11)°。每个In3+离子和6个O原子配位形成八面体构型。其中一个In3+离子配位的6个O原子中，其中4个来自配体的羧基氧原子，1个来自溶剂H2O分子的氧原子，1个来自羟基的O原子；其余三个In3+离子配位中，每个In3+离子配位的6个O原子中，其中5个来自配体的羧基氧原子，1个来自羟基的O原子。在该In的金属-有机骨架中，TTTA配体以μ2-η1:η1/μ2-η1:η1/μ1-η1:η0和μ2-η1:η1/μ2-η1:η1/μ2-η1:η1两种配位模式连接In3+离子。
本发明[In3(TTTA)2(OH)3H2O]金属-有机骨架材料单晶到[In3(TTTA)2(CH3O)3]金属-有机骨架材料单晶转化过程可以通过对比单晶结构进行解释说明，具体转化过程如下：[In3(TTTA)2(OH)3H2O]结构中的配位水分子被脱除，而结构中原本存在的含有一个未配位羧基氧原子的配体通过扭转，与脱除配位水分子的In原子进行配位，使结构发生了变化。与此同时，原本连接相邻两个In原子的羟基氧原子被甲醇分子提供的甲氧基中的氧原子所取代。单晶到单晶的转化过程并没有使该In金属-有机骨架的三维孔道结构发生坍塌，而是形成了一种全新的材料。该[In3(TTTA)2(CH3O)3]材料仍然能够在水环境中保持稳定，且在常温(298K)下对C2H2有着非常高的吸附量，而对CO2和CH4的吸附量则很低，表现出选择性吸附分离C2H2/CO2和C2H2/CH4的优良特性。
本发明的[In3(TTTA)2(CH3O)3]金属-有机骨架结构新颖、骨架稳定、比表面积大，在C2H2的纯化中具有潜在的应用。本发明制备方法工艺简单、易于实施、产率高，有利于大规模的推广。
附图说明
图1为[In3(TTTA)2(CH3O)3]金属-有机骨架的次级构筑单元图。
图2为[In3(TTTA)2(CH3O)3]金属-有机骨架的三维结构示意图。
图3为[In3(TTTA)2(CH3O)3]金属-有机骨架的单晶到单晶转化示意图。
图4为[In3(TTTA)2(CH3O)3]金属-有机骨架的傅立叶变换红外光谱图。
图5为[In3(TTTA)2(CH3O)3]金属-有机骨架的差热分析图。
图6为[In3(TTTA)2(CH3O)3]金属-有机骨架的77K氮气吸附等温线图。
图7为[In3(TTTA)2(CH3O)3]金属-有机骨架在298K下对C2H2、CO2、CH4的吸附等温线图。
具体实施方式
下面结合实施例对本发明作进一步说明，但本发明并不限于以下实施例。
X[In3(TTTA)2(OH)3H2O]及制备方法可参见专利申请号：2016100389080，公开号CN105664893A。
实施例1
将合成后的X(10mg～20mg)置于10mL的同位素瓶中，向瓶内加入8mL甲醇，然后拧紧瓶盖，置于常温的干燥通风处，每8小时后打开瓶盖，将瓶内的甲醇吸出后，再加入新鲜的甲醇(8mL)，此过程重复3～5次，得到Y(10mg～20mg)。
实施例2
将合成后的X(20mg～30mg)置于10mL的同位素瓶中，向瓶内加入8mL甲醇，然后拧紧瓶盖，置于常温的干燥通风处，每8小时后打开瓶盖，将瓶内的甲醇吸出后，再加入新鲜的甲醇(8mL)，此过程重复3～5次，得到Y(20mg～30mg)。
实施例3
将合成后的X(100mg～200mg)置于20mL的同位素瓶中，向瓶内加入15mL甲醇，然后拧紧瓶盖，置于常温的干燥通风处，每8小时后打开瓶盖，将瓶内的甲醇吸出后，再加入新鲜的甲醇(15mL)，此过程重复5～7次，得到Y(100mg～200mg)。
实施例4
将合成后的X(100mg～200mg)置于50mL的同位素瓶中，向瓶内加入40mL甲醇，然后拧紧瓶盖，置于常温的干燥通风处，每8小时后打开瓶盖，将瓶内的甲醇吸出后，再加入新鲜的甲醇(40mL)，此过程重复3～5次，得到Y(100mg～200mg)。
上述实施例所得的产品的测试结果相同，具体见下述：
(1)晶体结构测定：
在显微镜下选取合适大小的单晶，室温下在Agilent Technologies SuperNova单晶衍射仪上，用经石墨单色器单色化的Mo-Kα射线，以方式收集衍射数据。所有衍射数据使用SADABS程序进行吸收校正。晶胞参数使用最小二乘法确定。数据还原和结构解析分别使用SAINT和SHELXTL程序完成。先用差值函数法和最小二乘法确定全部非氢原子坐标，并用理论加氢法得到氢原子位置，然后用SHELXTL对晶体结构进行精修。结构图见图1和图2，单晶到单晶的转化过程图见图3，晶体学数据见表1。
表1金属有机骨架材料的晶体学数据
图1的结构图表明：在该金属-有机骨架中，配体羧基和甲氧基连接相邻的In原子形成了一维金属链。
图2的结构图表明：金属链在配体的桥连作用下形成三维金属-有机框架。
(2)单晶到单晶转化过程描述
图3的结构转化图表明：原来的In金属-有机骨架材料(X)在经过甲醇的浸泡后会发生结构的转化，变为现在的In金属-有机骨架材料(Y)。
(3)傅里叶变换红外光谱表征
图4为本发明材料的傅里叶变换红外光谱，表明该材料确实发生了金属原子与配体羧基的配位。
(4)热稳定性表征
图5为本发明材料的热重分析图，表明该材料的热稳定性达400℃左右。
(5)比表面积表征
图6为本发明材料的77K氮气吸附等温线。从图中可以看出，该金属-有机骨架最大的N2吸附量为128.0cm3/g，用Langmuir法计算出的比表面积(BET)为545.1m2/g。
(6)选择性吸附性能表征：
图7为本发明材料在298K，1个大气压下C2H2、CO2、CH4的吸附等温线。从图中可以看出，该材料的C2H2吸附量为69.5cm3/g，CO2吸附量为19.3cm3/g，CH4吸附量为7.3cm3/g，表现出该材料选择性吸附分离C2H2/CO2和C2H2/CH4的性质。
Claims (7)
1.一种三维的In金属-有机骨架材料，其特征在于，化学分子式为[In3(TTTA)2(CH3O)3]；其中TTTA为有机配体(2E,2'E,2”E)-3,3',3”-(2,4,6-三甲基)-均苯三丙烯酸；(2E,2'E,2”E)-3,3',3”-(2,4,6-三甲基)-均苯三丙烯酸的结构式如下所示；
从骨架连接构筑的角度，该三维金属有机骨架材料的晶体结构属于单斜晶系，空间群为P21/c，晶胞参数为： α＝γ＝90°，β＝106.381(5)°；该金属-有机骨架单晶结构中存在4个晶体学独立的In3+离子，每个In3+离子和6个O原子配位形成八面体构型，与In3+离子配位的6个O原子中包括4个来自配体的羧基氧原子以及2个来自甲氧基的O原子；配体中羧基和甲氧基所连接的In3+离子形成一维的金属链，此金属链在配体的桥连作用下形成三维金属-有机框架。
2.按照权利要求1的一种三维的In金属-有机骨架材料，其特征在于，该金属-有机骨架可进入的孔体积为45.3％。
3.按照权利要求1的一种三维的In金属-有机骨架材料，其特征在于，该金属-有机骨架通过热重分析测定，使结构坍塌最低温度为400℃。
4.权利要求1-3任一项所述的三维的In金属-有机骨架材料的制备方法，其特征在于，具体步骤如下：将[In3(TTTA)2(OH)3H2O]金属-有机骨架材料置于同位素瓶中，向瓶内加入甲醇，然后拧紧瓶盖，置于常温的干燥通风处，每8小时后打开瓶盖，将瓶内的甲醇吸附后，再加入新鲜的甲醇，每8小时后打开瓶盖，将瓶内的甲醇吸附，加入新鲜的甲醇并吸附的过程进行多次重复，得到[In3(TTTA)2(CH3O)3]金属-有机骨架。
5.按照权利要求4的方法，其特征在于，每10-200g[In3(TTTA)2(OH)3H2O]金属-有机骨架材料对应每次加入的甲醇为8-40ml；重复进行3-10次。
6.权利要求1-3任一项所述的三维的In金属-有机骨架材料的应用，用于选择性吸附分离C2H2/CO2。
7.权利要求1-3任一项所述的三维的In金属-有机骨架材料的应用，用于选择性吸附分离C2H2/CH4。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710023494.9A CN106832314B (zh) | 2017-01-12 | 2017-01-12 | 一种稳定的In金属-有机骨架、单晶到单晶的制备方法及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710023494.9A CN106832314B (zh) | 2017-01-12 | 2017-01-12 | 一种稳定的In金属-有机骨架、单晶到单晶的制备方法及其应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106832314A CN106832314A (zh) | 2017-06-13 |
| CN106832314B true CN106832314B (zh) | 2019-10-29 |
Family
ID=59123806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710023494.9A Expired - Fee Related CN106832314B (zh) | 2017-01-12 | 2017-01-12 | 一种稳定的In金属-有机骨架、单晶到单晶的制备方法及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106832314B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108424526B (zh) * | 2018-04-16 | 2020-09-25 | 北京工业大学 | 一种Fe的金属-有机骨架材料及其制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2691171A1 (en) * | 2011-03-31 | 2014-02-05 | Council of Scientific & Industrial Research | Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof |
| EP2464635B1 (en) * | 2009-08-11 | 2015-09-16 | The Scripps Research Institute | Copper catalyzed cycloaddition of organic azides and 1-haloalkynes |
| CN105664893A (zh) * | 2016-01-20 | 2016-06-15 | 北京工业大学 | 一种稳定的In金属-有机骨架材料、制备方法及其应用 |
-
2017
- 2017-01-12 CN CN201710023494.9A patent/CN106832314B/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2464635B1 (en) * | 2009-08-11 | 2015-09-16 | The Scripps Research Institute | Copper catalyzed cycloaddition of organic azides and 1-haloalkynes |
| EP2691171A1 (en) * | 2011-03-31 | 2014-02-05 | Council of Scientific & Industrial Research | Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof |
| CN105664893A (zh) * | 2016-01-20 | 2016-06-15 | 北京工业大学 | 一种稳定的In金属-有机骨架材料、制备方法及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106832314A (zh) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Synthesis of metal–organic framework MIL-101 in TMAOH-Cr (NO3) 3-H2BDC-H2O and its hydrogen-storage behavior | |
| Liu et al. | Co-based zeolitic imidazolate framework ZIF-9 membranes prepared on α-Al2O3 tubes through covalent modification for hydrogen separation | |
| Lee et al. | Preparation of Ni-MOF-74 membrane for CO2 separation by layer-by-layer seeding technique | |
| CN111266089B (zh) | 一种金属有机框架复合材料及其制备方法与应用 | |
| US11530174B2 (en) | Method for adsorption and separation of propylene, propyne, propane and propadiene | |
| CN105664893B (zh) | 一种稳定的In金属‑有机骨架材料、制备方法及其应用 | |
| CN113019330B (zh) | 一种铜基金属-有机框架材料的制备及其乙炔/二氧化碳分离应用 | |
| Guo et al. | Post-synthetic modification of highly stable UiO-66-NH2 membranes on porous ceramic tubes with enhanced H2 separation | |
| Xie et al. | Synthesis, characterization and experimental investigation of Cu-BTC as CO2 adsorbent from flue gas | |
| Yang et al. | Advances in metal-organic frameworks for efficient separation and purification of natural gas | |
| Yan et al. | Room temperature fabrication of oriented Zr-MOF membrane with superior gas selectivity with zirconium-oxo cluster source | |
| CN108339522A (zh) | 一种氨基酸@Cu-BTC复合吸附剂及其制备方法 | |
| CN110016145A (zh) | 多孔金属-有机骨架材料、制备方法及其吸附分离应用 | |
| CN113201144A (zh) | 一种刚性的四羧基氢键有机框架材料及其制备和应用 | |
| Jia et al. | (CH3) 2NH‐assisted synthesis of high‐purity Ni‐HKUST‐1 for the adsorption of CO2, CH4, and N2 | |
| Hou et al. | Selection-diffusion-selection mechanisms in ordered hierarchically-porous MOF-on-MOF: ZIF-8@ NH2-MIL-125 for efficient CO2 separation | |
| Schneemann et al. | Alkyl decorated metal–organic frameworks for selective trapping of ethane from ethylene above ambient pressures | |
| CN110563957B (zh) | 一种三维铁基金属-有机骨架的制备方法及应用 | |
| CN106832314B (zh) | 一种稳定的In金属-有机骨架、单晶到单晶的制备方法及其应用 | |
| Bu et al. | A binary all-nanoporous composite membrane constructed via vapor phase transformation for high-permeance gas separation | |
| CN114634628B (zh) | 一种分离甲烷和氮气的钡基金属有机框架材料的制备方法 | |
| Lv et al. | In-situ synthesis of KAUST-7 membranes from fluorinated molecular building block for H2/CO2 separation | |
| CN113214493B (zh) | 一种钴基金属有机骨架材料的制备及其低碳烃分离应用 | |
| CN109485870A (zh) | 一种稳定的多孔钴配合物及其制备方法和在吸附、分离气体小分子中的应用 | |
| CN106732407B (zh) | 一种在沸水和盐酸水溶液中稳定的In金属-有机骨架、制备方法及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |