CN110467731A - 一种稳定超薄介孔金属有机框架材料的制备方法 - Google Patents
一种稳定超薄介孔金属有机框架材料的制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000013337 mesoporous metal-organic framework Substances 0.000 title claims abstract description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 63
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002604 ultrasonography Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000013110 organic ligand Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 241000446313 Lamella Species 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 53
- 239000012621 metal-organic framework Substances 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 9
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- 239000007767 bonding agent Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012922 MOF pore Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910009045 WCl2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910015224 MoCl2 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal chalcogenide Chemical class 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及一种稳定的介孔金属有机框架材料制备方法,采用两步法:先超声后水热或溶剂热处理方法。分别取N,N‑二甲基甲酰胺、乙醇、水置于反应釜内衬中,然后将对苯二甲酸超声分散在混合液中,加入不同组合的二价金属盐搅拌使之分散均匀,之后加入三乙胺作为酸结合剂。先进行一定时间的超声反应,然后将其转移至高压反应釜继续反应。冷却至室温后,离心洗涤干燥得到超薄金属有机框架材料。本发明制备的超薄金属有机框架材料具有连续的介孔结构,催化活性提高。
Description
技术领域
本发明涉及一种稳定的超薄介孔金属有机框架材料的制备方法。用该方法得到的超薄金属有机框架纳米片存在连续的介孔结构,制备方法简单易行,主要用于催化材料、吸附材料和储能材料等。
背景技术
近年来,以石墨烯和过渡金属硫族化物为代表的二维材料受到了科学界和工业界的广泛关注。得益于它们的超薄厚度(通常几个原子层厚)和片状结构,这些纳米材料展现出很多独特性质,在能源和器件等领域具有巨大的应用前景。金属有机骨架化合物(MetalOrganic Frameworks,MOF)是一种利用金属离子/原子团簇与有机配体(以含羧基有机阴离子配体为主)之间通过配位作用自组装而形成的多孔周期性网状骨架材料,是一种近年来得到日益关注的新型多孔材料。由于其良好的结构特点,在气体存储与分离、催化、传感等领域得到广泛应用。
在此背景下,二维MOF成为一种有应用广泛的重要材料。然而,已经报道的MOF材料大多限于微孔结构,其小的孔径尺寸阻碍了传质运动,且阻止了较大客体分子与MOF内部活性位点的接触。因此,制备具有分层结构、更大连通孔隙的MOF材料十分必要。
为扩大孔径尺寸,已经报道了模板法制备MOF材料,在移去模板后可以得到有序/无序孔结构,这类方法优点是通过调整模板结构,可以实现对MOF孔的控制,但是,移除模板时MOF的孔结构可能会塌陷,且牺牲模板的控制过程较复杂,故急需一种无模板的制备方法避免上述问题。
发明内容
本发明的目的在于公开一种稳定的超薄介孔金属有机框架材料的合成方法,这是首次采用无模板法合成多级结构的多孔MOF的技术。
为了实现上述目标,该方法采用超声-水热或溶剂热两步法,超声后的二维MOF在水热或溶剂热过程中移除不稳定的MOF结构从而产生连续的介孔,并增强了MOF的活性位点,进而提高了其催化活性、吸附能力和储能能力。
具体工艺过程如下:
(1)将N,N-二甲基甲酰胺、乙醇、水按照一定的体积份数量取,置于反应釜内衬中,然后加入有机配体超声分散在混合液中;
(2)将二价金属盐加入步骤(1)得到的混合液,搅拌使之分散均匀;
(3)向步骤(2)得到的混合液中加入三乙胺作为酸结合剂,搅拌使之分散均匀,然后在超声环境下反应一定时间;
(4)将步骤(3)超声得到的产物转移至高压反应釜,进行水热或者溶剂热处理;
(5)将步骤(4)水热后所得产物冷却至室温,离心洗涤,干燥得到更加稳定的超薄金属有机框架材料。
进一步地,步骤(1)所述混合溶液中N,N-二甲基甲酰胺、乙醇、水的体积比为8:0~4:0~4。所述有机配体为对苯二甲酸;有机配体占混合溶液的摩尔体积比为0.01~0.04mmol/ml。
进一步地,步骤(2)所述二价金属盐包括铁、钴、镍、钼、钒、钨、铌的金属盐中的一种或者两种及其以上的金属盐。
进一步地,步骤(3)所述超声环境下反应时间为1-12小时,超声前在混合液中加入了0~5%的三乙胺作为酸结合剂。
进一步地,步骤(4)中所述水热或者溶剂热处理温度为100-260℃,时间为8-50小时。
进一步地,所述金属有机框架材料存在明显的2-10纳米的介孔结构。
本发明所述方法制备得到的稳定超薄介孔金属有机框架材料进行吸附性能测试、储能能力测试或者电化学性能测试。例如电化学性能测试步骤为:将所得到的MOF材料、乙醇、水、全氟磺酸-聚四氟乙烯共聚物(Nafion)混合后滴在玻碳电极上为工作电极,Ag/AgCl电极作为参比电极,石墨电极作为对电极,电解液为配制的标准的1mol/L的KOH溶液。测试时电压的扫描区间为0.0-0.8V,扫描速率为5mV/s,进行电解水析氧活性测试。
本发明的优点:
(1)本发明提供了一种更加稳定的超薄介孔金属有机框架材料的制备方法。本发明首次采用无模板的方法制备出分层多孔金属有机框架材料。与之前的模板法相比,该方法的控制过程简单易行,还可以避免移除模板时对MOF孔结构的破坏。
(2)目前合成的MOF材料基本只有微孔,而且厚度较大。与两者相比,本发明采用两步法制备的金属有机框架材料具有超薄的片状结构(单层片状厚度<2nm),同时,超薄的纳米片上还具有连续的介孔结构(平均孔径<10nm)。
(3)本发明制备的超薄介孔金属有机框架材料具有大量活性位点,有利于底物分子与活性位点的接触,进而可以提高MOF在催化、传感、储能、吸附等领域的性能。在氧析出反应的测试过程中,采用两步法制备的MOF纳米片电流密度10mA·cm-2时过电位仅为277mV,塔菲尔斜率为31mV·dec-1(仅采用超声法制备的材料过电位为300mV,塔菲尔斜率40mV·dec-1;仅采用水热法制备的材料过电位为310mV,塔菲尔斜率56mV·dec-1),证明了其结构优点。
附图说明
图1为本发明实例1得到的MOF的透射电镜图片。从本图可知制得的MOF材料为具有介孔的纳米片。
图2为本发明实例1得到的CoFe-MOF材料和商用RuO2析氧反应的线性扫描伏安法曲线对比图。从图2可知制得的CoFe-MOF材料具有更优的性能。
图3为本发明实例3得到的NiV-MOF材料的透射电镜图片。从图3可知制得的NiV-MOF材料为具有介孔的纳米片。
图4为本发明实例4得到的Ni-MOF材料的透射电镜图片。从图4可知制得的Ni-MOF材料为具有介孔的纳米片。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mLN,N-二甲基甲酰胺(DMF),2mL乙醇和2mL去离子水加入反应釜内衬中。将0.75mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向上述溶液中添加0.375mmol CoCl2.6H2O和0.375mmol FeCl2.4H2O,分散均匀后,快速加入0.8mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声8h。
(3)将超声后得到的混合液转移至高压反应釜中,于140℃反应48h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔CoFe-MOF材料。
电化学性能测试:将5mg CoFe-MOF、0.8mL水、0.2mL乙醇、50μL 5%的全氟磺酸-聚四氟乙烯共聚物(Nafion)超声30min,滴在玻碳电极上,干燥20min,作为工作电极;Ag/AgCl电极作为参比电极,石墨电极作为对电极,电解液为配制的标准的1mol/L的KOH溶液。测试时电压的扫描区间为0.0-0.8V,扫描速率为5mV/s,进行电解水析氧活性测试。
本实施例制备的CoFe-MOF材料透射电镜图片如图1所示,从图1可知,该材料为具有介孔的纳米片状结构。本实施例制备的CoFe-MOF材料析氧反应的线性扫描伏安法曲线对比如图2,表明该方法制备的超薄介孔CoFe-MOF材料催化活性得到了明显提高,能够比商用的RuO2催化活性更高。
实施例2:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF),0.5mL乙醇和0.5mL去离子水加入反应釜内衬中。将0.33mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向上述溶液中添加0.165mmol NiCl2.6H2O和0.165mmol FeSO4.7H2O,分散均匀后,快速加入0.35mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声1h。
(3)将超声后得到的混合液转移至高压反应釜中,于260℃反应10h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiFe-MOF材料。
实施例3:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF),2mL乙醇和2mL去离子水加入反应釜内衬中。将0.75mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.375mmol NiCl2.6H2O和0.375mmol VCl2,分散均匀后,快速加入0.8mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声8h。
(3)将超声后得到的混合液转移至高压反应釜中,于140℃反应48h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiV-MOF材料。
本实施例制备的NiV-MOF材料透射电镜图片如图3所示,从图3可知,该材料为具有介孔的纳米片状结构。
实施例4:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF),2mL乙醇和2mL去离子水加入反应釜内衬中。将0.75mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.75mmol NiCl2.6H2O,分散均匀后,快速加入0.8mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声8h。
(3)将超声后得到的混合液转移至高压反应釜中,于140℃反应48h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔Ni-MOF材料。
本实施例制备的Ni-MOF材料透射电镜图片如图4所示,从图4可知,该材料为具有介孔的纳米片状结构。
实施例5:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF),2mL乙醇和2mL去离子水加入反应釜内衬中。将0.75mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.25mmol NiCl2.6H2O,0.25mmol CoCl2.6H2O和0.25mmolFeCl2.4H2O,分散均匀后,快速加入0.8mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声8h。
(3)将超声后得到的混合液转移至高压反应釜中,于140℃反应48h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiCoFe-MOF材料。
实施例6:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF)和16mL乙醇加入反应釜内衬中。将1.92mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.64mmol NiCl2.6H2O,0.64mmol CoCl2.6H2O和0.64mmol WCl2,分散均匀后,将其超声5h。
(3)将超声后得到的混合液转移至高压反应釜中,于100℃反应50h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiCoW-MOF材料。
实施例7:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF)和16mL去离子水加入反应釜内衬中。将1.92mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.64mmol NiCl2.6H2O,0.64mmol CoCl2.6H2O和0.64mmol WCl2,分散均匀后,快速加入2.4mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声12h。
(3)将超声后得到的混合液转移至高压反应釜中,于130℃反应50h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiCoW-MOF材料。
实施例8:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将32mL N,N-二甲基甲酰胺(DMF),4mL乙醇和4mL去离子水加入反应釜内衬中。将1.2mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.4mmol NiCl2.6H2O,0.4mmol CoCl2.6H2O,0.4mmol MoCl2,分散均匀后,快速加入01.28mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声10h。
(3)将超声后得到的混合液转移至高压反应釜中,于150℃反应40h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiCoMo-MOF材料。
实施例9:一种超薄介孔金属有机框架材料的制备方法,具体步骤如下:
(1)将36mL N,N-二甲基甲酰胺(DMF),1.8mL乙醇和1.8mL去离子水加入反应釜内衬中。将0.81mmol对苯二甲酸(BDC)加入上述混合溶液中,分散均匀。
(2)向溶液中添加0.27mmol NiCl2.6H2O,0.27mmol CoCl2.6H2O,0.27mmol NbCl2,分散均匀后,快速加入0.7mL的三乙胺(TEA)作为金属离子与有机配体的结合剂,搅拌待形成均匀的胶体悬浮液,将其超声7h。
(3)将超声后得到的混合液转移至高压反应釜中,于130℃反应45h。
(4)将所得产物冷却至室温,离心洗涤,干燥得到超薄片层介孔NiCoNb-MOF材料。
Claims (6)
1.一种稳定超薄介孔金属有机框架材料的制备方法,其特征在于步骤包括:
(1)将N,N-二甲基甲酰胺、乙醇、水按照一定的体积份数量取,置于反应釜内衬中,然后加入有机配体超声分散在混合液中;
(2)将二价金属盐加入步骤(1)得到的混合液,搅拌使之分散均匀;
(3)向步骤(2)得到的混合液中加入三乙胺作为酸结合剂,搅拌使之分散均匀,然后在超声环境下反应一定时间;
(4)将步骤(3)超声得到的产物转移至高压反应釜,进行水热或者溶剂热反应;
(5)将步骤(4)水热后所得产物冷却至室温,离心洗涤,干燥得到超薄片层金属有机框架材料。
2.根据权利要求1所述超薄介孔金属有机框架材料的制备方法,其特征在于:步骤(1)所述混合溶液中N,N-二甲基甲酰胺、乙醇、水的体积比为8:0~4:0~4;所述有机配体为对苯二甲酸;有机配体占混合溶液的摩尔体积比为0.01~0.04mmol/ml。
3.根据权利要求1所述超薄介孔金属有机框架材料的制备方法,其特征在于:步骤(2)中二价金属盐包括铁、钴、镍、钼、钒、钨、铌的金属盐中的一种或者两种及其以上的金属盐。
4.根据权利要求1所述超薄介孔金属有机框架材料的制备方法,其特征在于:步骤(3)中超声环境下反应1-12小时,超声前在混合液中加入了0~5%的三乙胺作为酸结合剂。
5.根据权利要求1所述超薄介孔金属有机框架材料的制备方法,其特征在于:步骤(4)中的处理方式为反应釜内水热或者溶剂热处理,温度为100-260℃,时间为8-50小时。
6.根据权利要求1所述超薄介孔金属有机框架材料的制备方法,其特征在于:金属有机框架材料存在明显的2-10纳米的介孔结构。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100172814A1 (en) * | 2005-12-14 | 2010-07-08 | Basf Catalysts Llc | Zeolite Catalyst With Improved NOx Reduction in SCR |
CN105732728A (zh) * | 2016-01-26 | 2016-07-06 | 国家纳米科学中心 | 金属有机骨架配合物纳米片、制备方法及其用途 |
CN108114699A (zh) * | 2017-12-22 | 2018-06-05 | 华东理工大学 | 一种孔径可调的多级孔金属有机骨架纳米材料的制备方法以及由此得到的纳米材料及其应用 |
-
2019
- 2019-07-25 CN CN201910678910.8A patent/CN110467731B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100172814A1 (en) * | 2005-12-14 | 2010-07-08 | Basf Catalysts Llc | Zeolite Catalyst With Improved NOx Reduction in SCR |
CN105732728A (zh) * | 2016-01-26 | 2016-07-06 | 国家纳米科学中心 | 金属有机骨架配合物纳米片、制备方法及其用途 |
CN108114699A (zh) * | 2017-12-22 | 2018-06-05 | 华东理工大学 | 一种孔径可调的多级孔金属有机骨架纳米材料的制备方法以及由此得到的纳米材料及其应用 |
Non-Patent Citations (2)
Title |
---|
GUANGTONG HAI等: "High-performance oxygen evolution catalyst using two-dimensional ultrathin metal-organic frameworks nanosheets", 《NANO ENERGY》 * |
YING CHEN等: "Enhanced photocatalytic degradation of RhB by two-dimensional composite photocatalyst", 《COLLOIDS AND SURFACES A》 * |
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