CN103483360A - Preparation method for metal complex functionalized ZIF-8 (zinc 2-methylimidazolate) material - Google Patents
Preparation method for metal complex functionalized ZIF-8 (zinc 2-methylimidazolate) material Download PDFInfo
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Abstract
The invention discloses a preparation method for a metal complex functionalized ZIF-8 (zinc 2-methylimidazolate) material, which belongs to the scopes of physical chemistry and material chemistry. The preparation method is characterized by comprising the following steps of directly introducing the needed metal ions during synthesis for a zeolite-like imidazole framework material ZIF-8, then matching the metal ions supported by the zeolite-like imidazole framework material containing the needed metal ions with a selected ligand in certain conditions, so as to immobilize the metal complex in the zeolite-like imidazole framework material ZIF-8. According to the preparation method, a multi-phase supported catalyst can be prepared by virtue of the unique subject effect of ZIF-8, and a new way can be provided for functionalization for the ZIF-8 material and preparation for a novel functional material.
Description
Technical field
The preparation method of metal complex functionalized ZIF-8 material of the present invention belongs to the category of physical chemistry and materials chemistry, be specifically related to directly introduce required metal ion in class zeolite imidazoles framework material ZIF-8 synthetic, to make containing the ZIF-8 of required metal ion again the metal ion of institute's load coordinate with selected part under certain condition, thus metal complexes is immobilized in the ZIF-8 material.
Background technology
Metal complexes is good homogeneous catalyst, and the various advantages such as have reactive behavior, selectivity is high and reaction conditions is gentle is difficult to product separation and the drawback such as can not reuses but exist.Realizing that on solid carrier the homogeneous catalysis heterogenize is the effective ways that solve these drawbacks by metal complexes is immobilized, is also an important topic in Green Chemistry research.Aspect the immobilized research of metal complexes, selected material of main part be mainly zeolite or mesoporous material etc. these have rigid-skeleton and vestibule microenvironment be difficult for modulation inorganic carrier [D. Srinivas, S. Sivasanker,
catal. Surv. Asia., 7 (2003) 121; S. Verma, M. Nandi, A. Modak, S. Jain, A. Bhaumik,
adv. Synth. Catal., 353 (2011) 1897; M. Maurya, A. Kumar, J. Pessoa,
coord. Chem. Rev., 255 (2011) 2315].For immobilized metal complexes, its physical and chemical performance particularly catalytic performance has very important relation with its residing microenvironment, and concerning zeolite or in the mesoporous material the modulation of microenvironment only can carry out several aspects such as silanization and carry out from changing its pore passage structure, pore size or effects on surface, this limited to a certain extent to immobilized metal complexes microenvironment carry out the degree of modulation, make the character between Subjective and Objective mutually not mate and to merge.Thereby at the metal current title complex in immobilized research, mutual coupling and fusion between the selection of material of main part and itself and object metal complexes are the major issues of the required solution of the good catalytic performance metallic complex polyphase catalyzer of preparation.
A kind of novel material that is referred to as metal-organic framework structure (Metal-Organic Frameworks), caused that people pay close attention to greatly in recent years.This material is the crystalline material with periodic network structure that utilizes the metal-ligand mating reaction between organic ligand and metal ion to form by self-assembly, this stephanoporate framework crystalline material, can be connected with the machine part by different metal ion and various rigid bridges is coordinated, design and the metal-organic framework materials that synthesizes different pore size, thereby make the structural changes of MOFs infinite, and can on organic ligand, be with such as-Br ,-NH
2,-OC
3h
7,-OC
5h
11deng some functional modification groups, make this MOFs microporous polymer can be according to performance requriementss such as catalyzed reaction or absorption and functionalization [J. Li, R. Kuppler, H. Zhou,
chem. Soc. Rev., 38 (2009) 1477; J. Lee, O. Farha, J. Roberts, K. Scheidt,
chem. Soc. Rev., 38 (2009) 1450-1459; Y. Liu, W. Xuan, Y. Cui,
adv. Mater., 22 (2009) 4112].
The design that appears as metallic complex polyphase catalyzer of MOFs material and the selection of material of main part provide new opportunity.But poor heat, hydrothermal stability and the solvent resistance of MOFs self be the restriction its widespread use principal element [M. Ranocchiari, J. Bokhoven,
phys. Chem. Chem. Phys., 13 (2011) 6388; A. Dhakshinamoorthy, M. Alvaro, A. Corma, H. Garcia,
dalton Trans., 40 (2011) 6344].For this reason, people have good stability and can meet on the MOFs material that catalyzed reaction requires and carried out many-sided effort having synthesized.Class zeolite imidazoles skeleton (Zeolitic imidazolate framework, ZIF) material is the nano-porous materials that a class is novel, have the zeolite topological framework, and it is formed by connecting by transition metal atoms (Zn/Co) and imidazoles/imdazole derivatives.With zeolite molecular sieve, compare, due to the diversity of imidazoles/imdazole derivatives, the pore structure of material is adjustable more flexibly, it is compared with metallic organic framework (MOF) and have better thermostability and chemical stability [H. Hayashi, A.P. C te; H. Furukawa; M. O ' Keeffe; O.M. Yaghi,
nat. Mater.6 (2007) 501; R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. O ' Keeffe,
science319 (2008
)939; B. Wang, A.P. C te; H. Furukawa; M. O ' Keeffe; O.M. Yaghi,
nature453 (2008
)207].Therefore, the ZIF material is as a kind of focus that becomes research for absorption, separation and the promising material of catalysis aspect tool.But these its degree of functionalization of ZIF material with good stability are lower.Prepare the ZIF material that degree of functionalization is high, need to select to have organic linker of functional group, but the formation of ZIF network structure is very responsive to chemical reactivity, the solvability of the organic linker with functional group, even very small variation also can cause generating different networks and pore structure [R. Fischer, C. W ll
angew. Chem. Int. Ed.,47 (2008) 8164].Therefore, proposed to the ZIF material carry out rear functionalized (post-functionalization) technological line [Z. Wang, S. Cohen,
angew. Chem. Int. Ed., 47 (2008) 4699].Although this technological line can improve the degree of functionalization of ZIF material to a certain extent, but require must there is come-at-able reactive functionality on the ZIF parent, and selected functionalization must very gentle (soft), can, on the structure generation impact of ZIF material, can not discharge and remain in the by product that may stop up duct in reaction process in addition.With respect to functionizing method after adopting, it is more convenient and efficient introducing the reaction with catalytic activity in the vestibule of ZIF material.In this regard, research mainly concentrate on immobilized metal nanoparticle and heteropolyacid anions [D. Esken, S. Turner, O.I. Ledebev, G.V. Tendeloo, R.A. Fischer,
chem. Mater., 22 (2010) 6393].ZIF-8 is the most representative a kind of in the ZIF material, and its specific surface area can reach 1400 m
2/ g, thermostability can reach 420
oC, orifice diameter is 3.4, and the diameter of cage is 11.6, and its applied research has been related to gas adsorption, separation, and a plurality of fields such as Chu Qing and catalysis are the class ZIF materials the most widely of research at present.And for take research report that ZIF-8 is the immobilized metal complexes of main body aspect seldom.The present invention adopts and introduce the metal center ion in the synthetic system of ZIF-8, is then coordinating the class zeolite imidazoles skeleton ZIF-8 material of successfully preparing metal complex functionalized with the metal center ion with part.
Summary of the invention
Preparation method's purpose of metal complex functionalized ZIF-8 material of the present invention is: the higher thermostability had based on class zeolite imidazoles material, solvent resistance, flexible skeleton structure and flexibly adjustable duct microenvironment and structure and material of main part in immobilized homogeneous catalyst-metal complexes with good catalytic performance existing with metal complexes, can not mutually mate and fusion etc. main not enough, thereby disclose a kind of employing and introduce the metal center ion in the synthetic system of ZIF, then coordinating the class zeolite imidazoles framework material method of successfully preparing metal complex functionalized with the metal center ion with part.
The preparation method of metal complex functionalized ZIF-8 material of the present invention, it is characterized in that: the metal-salt of glyoxal ethyline, zinc hydroxide and required introducing metal ion is added in anhydrous methanol, and then ammoniacal liquor is added in above-mentioned solution, stir, carry out crystallization under room temperature, the gained solid product is through H
2dry after the mixing solutions washing of O and MeOH, gained sample after drying is joined containing in the ethanolic soln of selected part and coordinated, after having coordinated, after filtering, the gained solid sample obtains required sample, wherein glyoxal ethyline and Zn (OH) after the strict extracting of ethanol drying
2mol ratio be 0.5-8, the mol ratio of metal-salt and zinc hydroxide is less than 5.
The preparation method of above-mentioned metal complex functionalized ZIF-8 material, is characterized in that selected part is for coordinating with introduced metal ion and can enter the part of ZIF-8 vestibule.
The preparation method of above-mentioned metal complex functionalized ZIF-8 material, is characterized in that selected metal ion is Cu
2+, Fe
2+, Ni
2+, Mn
2+or Co
2+.
The preparation method of above-mentioned metal complex functionalized ZIF-8 material, is characterized in that selected metal-salt is chlorate, nitrate or acetate.
The preparation method of metal complex functionalized ZIF-8 material of the present invention, its advantage mainly concentrate on following some: the ZIF-8 material is different from inorganic zeolitic material and mesoporous material commonly used, it not only has the similar skeleton structure of same zeolite facies, and the easy modulation of its surface properties, more approaching with the character of the protein housing of the enzyme catalyst of occurring in nature, more approach in the bionic enzyme catalyticing research requirement to material of main part; The 3rd, the preparation of the ZIF-8 material being carried out to the functionalized and new function material of the functionalized ZIF of can be material with metal complexes provides a new approach.
The accompanying drawing explanation
The XRD spectra of Fig. 1 ZIF-8 (a) and Cu-Phen/ZIF-8 (b) sample
The DRS spectrogram of Fig. 2 ZIF-8 (a) and Cu-Phen/ZIF-8 (b).
Embodiment
Realize that embodiments of the present invention are as follows:
embodiment 1: by 2 mmol glyoxal ethylines, 1 mmol Zn (OH)
2cuCl with 0.5 mmol
22H
2o adds in 3 mL anhydrous methanols, and then 15 mL ammoniacal liquor are added wherein, and stirring reaction 5 h under room temperature, normal pressure, after question response finishes, filter, and solid product is through H
2the mixing solutions washing of O/MeOH (1:1 V/V) three times, be dried, and obtains required containing Cu
2+the ZIF-8 material, be designated as Cu
2+/ ZIF-8.
embodiment 2:by 2 mmol glyoxal ethylines, 4 mmol Zn (OH)
2co (CH with 0.5 mmol
3cOO)
22H
2o adds in 10 mL anhydrous methanols, and then 20 mL ammoniacal liquor are added wherein, and stirring reaction 24 h under room temperature, normal pressure, after question response finishes, filter, and solid product is through H
2the mixing solutions washing of O/MeOH (1:1 V/V) three times, be dried, and obtains required containing Co
2+the ZIF-8 material, be designated as Co
2+/ ZIF-8.
embodiment 3:by 8 mmol glyoxal ethylines, 1 mmol Zn (OH)
2ni (NO with 5 mmol
3)
26H
2o adds in 15 mL anhydrous methanols, and then 30 mL ammoniacal liquor are added wherein, and stirring reaction 48 h under room temperature, normal pressure, after question response finishes, filter, and solid product is through H
2the mixing solutions washing of O/MeOH (1:1 V/V) three times, be placed on 60
ocarry out drying under C, obtain required containing Ni
2+the ZIF-8 material, be designated as Ni
2+/ ZIF-8.
embodiment 4:by 2 mmol glyoxal ethylines, 1 mmol Zn (OH)
2mn (CH with 0.5 mmol
3cOO)
2add in 3 mL anhydrous methanols, and then 15 mL ammoniacal liquor are added wherein, stirring reaction 48 h under room temperature, normal pressure, after question response finishes, filter, and solid product is through H
2the mixing solutions washing of O/MeOH (1:1 V/V) three times, be dried, and obtains required containing Mn
2+the ZIF-8 material, be designated as Mn
2+/ ZIF-8.
embodiment 5: by 2 mmol glyoxal ethylines, 1 mmol Zn (OH)
2feCl with 0.5 mmol
2add in 3 mL anhydrous methanols, and then 15 mL ammoniacal liquor are added wherein, stirring reaction 5 h under room temperature, normal pressure, after question response finishes, filter, and solid product is through H
2the mixing solutions washing of O/MeOH (1:1 V/V) three times, be dried, and obtains required containing Fe
2+the ZIF-8 material, be designated as Fe
2+/ ZIF-8.
embodiment 6:by 1.5 mmol 1,10-phenanthroline and prepared Cu/ZIF-8 1g adds in 20 ml dehydrated alcohols by embodiment 1, stir 24 h, and dehydrated alcohol extracting 24 h, be placed on 60
ocarry out dry 6h in the C thermostatic drying chamber, obtain the functionalized ZIF-8 material of copper phenanthroline title complex, be designated as Cu-Phen/ZIF-8.Its XRD spectra and DRS spectrogram are shown in respectively accompanying drawing 1 (b) and accompanying drawing 2.
embodiment 7:by 0.5 mmol Whitfield's ointment with by embodiment 1, prepared Cu/ZIF-8 1g adds in 20 ml dehydrated alcohols, stirs 24 h, dehydrated alcohol extracting 24 h, by it in 60
oafter dry 6 h of C, obtain the functionalized ZIF-8 material of copper Whitfield's ointment title complex, be designated as Cu-BHA/ZIF-8.
embodiment 8:by 2 mmol 2,2-second bipyridine and prepared Mn/ZIF-8 1g adds in 20 ml dehydrated alcohols by embodiment 4, reflux 24h, dehydrated alcohol extracting 24 h, by it in 60
odry 6 h of C, obtain the functionalized ZIF-8 material of manganese second bipyridine title complex, is designated as Cu-Bipy/ZIF-8.
embodiment 9:by 1.5 mmol quadrols with by embodiment 1, prepared Cu/ZIF-8 1g adds in 20 ml dehydrated alcohols, stirs 24h, and dehydrated alcohol extracting 24h, be placed on 60
ocarry out dry 6h in the C thermostatic drying chamber, obtain the functionalized ZIF-8 material of cupri ethylene diamine title complex, be designated as Cu-EDA/ZIF-8.
embodiment 10:by 5 mmol oxines with by embodiment 3, prepared Ni/ZIF-8 1g adds in 20 ml dehydrated alcohols, reflux 24h, dehydrated alcohol extracting 24 h, by it in 60
ocarry out dry 6 h in the C loft drier, obtain the functionalized ZIF-8 material of nickel 8-hydroxy-quinoline title complex, be designated as Cu-HQL/ZIF-8.
embodiment 11:by 1 mmol 1,10-phenanthroline and prepared Fe/ZIF-8 1g adds in 20 ml dehydrated alcohols by embodiment 5, then add a small amount of oxammonium hydrochloride, stir 24 h, dehydrated alcohol extracting 24 h, by it in 60
odry 6 h of C, obtain the functionalized class zeolite imidazoles framework material of iron phenanthroline title complex, is designated as Fe-Phen/ZIF-8.
Claims (4)
1. the preparation method of metal complex functionalized ZIF-8 material, it is characterized in that: the metal-salt of glyoxal ethyline, zinc hydroxide and required introducing metal ion is added in anhydrous methanol, and then ammoniacal liquor is added in above-mentioned solution, stir, carry out crystallization under room temperature, the gained solid product is through H
2dry after the mixing solutions washing of O and MeOH, gained sample after drying is joined containing in the ethanolic soln of selected part and coordinated, after having coordinated, after filtering, the gained solid sample obtains required sample, wherein glyoxal ethyline and Zn (OH) after the strict extracting of ethanol drying
2mol ratio be 0.5-8, the mol ratio of metal-salt and zinc hydroxide is less than 5.
2. according to the preparation method of the described metal complex functionalized ZIF-8 of claim 1 material, it is characterized in that selected part is for coordinating with introduced metal ion and can enter the part of ZIF-8 vestibule.
3. according to the preparation method of the described metal complex functionalized ZIF-8 of claim 1 material, it is characterized in that selected metal ion is Cu
2+, Fe
2+, Ni
2+, Mn
2+or Co
2+.
4. according to the preparation method of the described metal complex functionalized ZIF-8 of claim 1 material, it is characterized in that selected metal-salt is chlorate, nitrate or acetate.
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|---|---|---|---|---|
| CN104772165A (en) * | 2014-04-22 | 2015-07-15 | 北京林业大学 | ZIF-8 material-based hydrogenation catalyst and synthetic method thereof |
| CN105819424A (en) * | 2016-03-21 | 2016-08-03 | 太原理工大学 | Preparation method of porous carbon material |
| CN105833919A (en) * | 2016-04-25 | 2016-08-10 | 张哲夫 | Composite visible-light response catalyst Ag2CO3/TiO2/M-ZIF-8 and application thereof |
| CN105854955A (en) * | 2016-04-25 | 2016-08-17 | 张哲夫 | Preparation method and application of compound visible-light responding catalyst Ag2CO3/TiO2/M-ZIF-8 |
| CN107644129A (en) * | 2017-09-08 | 2018-01-30 | 武汉大学 | It is a kind of to predict method of the multi-functional MOFs materials to the releasing effect of guest molecule |
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| US20210047741A1 (en) * | 2018-02-13 | 2021-02-18 | Gaznat Sa | Fe-N-C CATALYST, METHOD OF PREPARATION AND USES THEREOF |
| CN112588324A (en) * | 2020-12-28 | 2021-04-02 | 湖南金联星特种材料股份有限公司 | Method for preparing composite photocatalyst CdS/ZIF-8 by one-pot method and application thereof |
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| CN112993281A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Fe-based multi-metal electrocatalyst, preparation and application thereof |
| CN114653374A (en) * | 2022-04-02 | 2022-06-24 | 北京师范大学 | Double-metal hydroxide and preparation method and application thereof |
| CN114906801A (en) * | 2022-05-26 | 2022-08-16 | 重庆大学 | MgH 2 @ Fe-ZIF hydrogen storage material and preparation method thereof |
| CN115069306A (en) * | 2022-07-06 | 2022-09-20 | 南京大学 | Absorbent CO for promoting decarburization 2 Process for preparing catalyst with absorption rate |
| CN116926616A (en) * | 2023-09-16 | 2023-10-24 | 山东海化集团有限公司 | Preparation method and application of flaky Cu-ZIF-8 material |
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