CN102993221A - Method for preparing nano-zeolite metal-organic framework compounds by microreactor - Google Patents
Method for preparing nano-zeolite metal-organic framework compounds by microreactor Download PDFInfo
- Publication number
- CN102993221A CN102993221A CN2012105391731A CN201210539173A CN102993221A CN 102993221 A CN102993221 A CN 102993221A CN 2012105391731 A CN2012105391731 A CN 2012105391731A CN 201210539173 A CN201210539173 A CN 201210539173A CN 102993221 A CN102993221 A CN 102993221A
- Authority
- CN
- China
- Prior art keywords
- solution
- organic framework
- microreactor
- framework compound
- metal precursor
- 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.)
- Granted
Links
Abstract
The invention relates to a method for preparing nano-zeolite metal-organic framework compounds by a microreactor, and belongs to the technical field of preparation of nano-particles, which is characterized by comprising the following steps of: constructing a microreactor by a porous film; respectively dissolving a metal precursor and an organic ligand in a solvent to prepare a metal precursor solution A and an organic ligand solution B; respectively arranging the metal precursor solution A and the organic ligand solution B at two sides of the film; by a pressure difference of the two sides of the film, uniformly pressing reactants at one side of the film into reactants at the other side of the film through the pores of the film, to generate nano-particles; and centrifuging, washing and drying to obtain the target product. The method for preparing the nano-zeolite metal-organic framework compounds by the microreactor is simple in operation, strong in controllability of particle structure, and is suitable for preparation and industrial production of various nano-zeolite metal-organic framework compounds.
Description
Technical field
The present invention relates to the method that a kind of microreactor prepares nanometer class zeolite metallic organic framework compound, belong to the preparation technology of nano-particles field.
Background technology
Nano material refers to that particle diameter is that (1 ~ 100nm) ultrafine particle material has small-size effect and surface effects etc. to nanometer scale.Nanometer class zeolite metallic organic framework compound (ZIFs) is a series in the organometallics (MOF), to replace Si element and Al element in traditional zeolite molecular sieve with transition metal ions such as Zn/Cu, the derivative of imidazoles or imidazoles replaces the bridging oxygen in traditional zeolite molecular sieve, a kind zeolitic material that is connected and forms by the nitrogen-atoms on the imidazole ring.ZIFs has the high stability of inorganic zeolite and the porousness of a metal-organic complex concurrently, because its unique topological framework has huge potential application foreground in fields such as gas adsorption, catalysis, storage, optics and electromagnetism, thereby has been subject to extensive concern.Because the performance of ZIFs has extremely strong size and Structure Dependence, therefore the study hotspot for ZIFs mainly centers on how to regulate preparation process, obtains to have the more ZIFs of bigger serface, porosity, thermostability and structurally ordered property characteristics.
At present, the method of synthetic ZIFs mainly is solvent-thermal method (US2007/0202038A, CN102335626A), Liquid Phase Diffusion method (Chem Eur J, 2007,13,4146), template (J Am Chem Soc, 2004,126,13218), dynamic crystallization method (CN102220626A) etc., but these methods all in various degree have that severe reaction conditions, reaction process are loaded down with trivial details, contaminate environment and particle structure be difficult to the problems such as stable regulation and control.
The invention provides a kind of novel method of utilizing the efficient synthesis of nano class of microreactor zeolite imidazoles frame structure material (ZIFs).This microreactor is to be made up by porous-film to form, and the surface of film has aperture ratio than the micropore of homogeneous, and the liquid of film one side is by behind the micropore, with certain flow rate at the face flowing fluid, under the effect of shearing force, can form the microfacies contact conditions.The class zeolite metallic organic framework structured material of microreactor of the present invention preparation has that specific surface area is large, good dispersity, porosity advantages of higher.This method is simple to operate, energy-conserving and environment-protective, and the particle structure controllability is strong, for nanometer ZIFs material preparation provides a kind of simple and effective new way.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing microreactor to prepare nanometer class zeolite metallic organic framework compound.
According to technical scheme provided by the invention, a kind of microreactor prepares the method for nanometer class zeolite metallic organic framework compound, adopts following processing step:
(1) solution allocation: at first metal precursor is dissolved in and is mixed with the metal precursor solution A that concentration is 0.5 ~ 1mo/L in the solvent, organic ligand is dissolved in is mixed with the organic ligand solution B that concentration is 0.5 ~ 4mol/L in the solvent;
(2) mix: the both sides that metal precursor solution A and organic ligand solution B placed respectively microporous membrane, the temperature of two kinds of solution of control is 30 ~ 40 ℃, the pressure difference of film both sides is 0.02 ~ 0.08MPa, the metal precursor solution A is seen through mould uniformly enter in the organic ligand solution B, obtain the white size liquid suspension;
(3) aftertreatment: get that step (2) gained white size liquid suspension is centrifugal through 10000 ~ 12000r/min, methanol wash 2 times, obtain product nanometer class zeolite metallic organic framework compound at 80 ~ 100 ℃ of lower dry 10 ~ 12h.
Described metal precursor is zinc nitrate or cupric nitrate.Organic ligand is glyoxal ethyline or 2-ethyl imidazol(e) or imidazoles.Described organic solvent is methyl alcohol or deionized water.Described microporous membrane is that the aperture is that 0.01 ~ 10 μ m, molecular weight cut-off are 5000 ~ 50000 microporous membranes.The kit form of described microporous membrane is a kind of in flat sheet membrane, rolled film, tubular membrane or the hollow-fibre membrane.The material of described microporous membrane is polyethersulfone, polysulfones or polyvinylidene difluoride (PVDF).
The present invention has following advantage: nanoparticle provided by the invention has high specific surface area, narrow size distribution and little particle size, and its preparation technology is simple, and is easy to operate, and efficient is high, produces good reproducibility; Reaction conditions is gentle, pollutes little; Crystalline structure is controlled, complete in crystal formation, and the particle aperture is adjustable.In sum, product of the present invention has high specific surface area, the characteristics such as high thermostability and chemical stability.
Description of drawings
The class zeolite metallic organic framework compound electron scanning micrograph that Fig. 1 embodiment 2 makes.
Embodiment
Below be the embodiment that a kind of microreactor prepares the method for nanometer class zeolite metallic organic framework compound, but described embodiment is not construed as limiting the invention.
Embodiment 1
(1) solution allocation: respectively zinc nitrate and glyoxal ethyline are dissolved in methyl alcohol and are mixed with the organic ligand that metal precursor solution A that concentration is 0.5mol/L and concentration is 0.5mol/L and are dissolved in B.
(2) mix: it is 0.01 micron microfiltration membrane both sides that A solution and B solution are placed respectively the aperture, the pressure difference of controlling diaphragm both sides is 0.02MPa, making A solution see through uniformly film enters in the B solution, the control temperature of reaction is 30 ℃, used reactor kind is flat sheet membrane, and membrane material is polyethersulfone (PES).
(3) aftertreatment: with white size liquid suspension obtained above,, methanol wash centrifugal through 10000r/min 2 times obtains nanometer class zeolite metallic organic framework compound at 80 ℃ of lower dry 10h.
Recording its particle diameter is 32.44nm, and specific surface area is 980.4332m
2/ g.
Embodiment 2
(1) solution allocation: respectively zinc nitrate and 2-ethyl imidazol(e) are dissolved in deionized water and are mixed with the organic ligand that metal precursor solution A that concentration is 1mol/L and concentration is 4mol/L and are dissolved in B.
(2) mix: it is 50000 ultra-filtration membrane both sides that A solution and B solution are placed respectively molecular weight cut-off, the pressure difference of controlling diaphragm both sides is 0.08MPa, making A solution see through uniformly film enters in the B solution, the control temperature of reaction is 40 ℃, used reactor kind is rolled film, and membrane material is polysulfones (PS).
(3) aftertreatment: with white size liquid suspension obtained above,, methanol wash centrifugal through 12000r/min 2 times obtains nanometer class zeolite metallic organic framework compound at 100 ℃ of lower dry 12h.
Recording its particle diameter is 34.44nm, and specific surface area is 987.5348m
2/ g.
Embodiment 3
(1) solution allocation: respectively cupric nitrate and 2-ethyl imidazol(e) are dissolved in deionized water and are mixed with the organic ligand that metal precursor solution A that concentration is 1mol/L and concentration is 1mol/L and are dissolved in B.
(2) mix: it is 0.08 micron microfiltration membrane both sides that A solution and B solution are placed respectively the aperture, the pressure difference of controlling diaphragm both sides is 0.04MPa, making A solution see through uniformly film enters in the B solution, the control temperature of reaction is 35 ℃, used reactor kind is rolled film, and membrane material is polyvinylidene difluoride (PVDF) (PVDF).
(3) aftertreatment: with white size liquid suspension obtained above,, methanol wash centrifugal through 12000r/min 2 times obtains nanometer class zeolite metallic organic framework compound at 90 ℃ of lower dry 11h.
Recording its particle diameter is 33.56nm, and specific surface area is 1000.2225m
2/ g.
Embodiment 4
(1) solution allocation: respectively cupric nitrate and imidazoles are dissolved in methyl alcohol and are mixed with the organic ligand that metal precursor solution A that concentration is 0.6mol/L and concentration is 3mol/L and are dissolved in B.
(2) mix: it is 40000 ultra-filtration membrane both sides that A solution and B solution are placed respectively molecular weight cut-off, the pressure difference of controlling diaphragm both sides is 0.07MPa, making A solution see through uniformly film enters in the B solution, the control temperature of reaction is 30 ℃, used reactor kind is tubular membrane, and membrane material is polysulfones (PS).
(3) aftertreatment: with white size liquid suspension obtained above,, methanol wash centrifugal through 12000r/min 2 times obtains nanometer class zeolite metallic organic framework compound at 85 ℃ of lower dry 11.5h.
Recording its particle diameter is 31.57nm, and specific surface area is 1200.4562m
2/ g.
Embodiment 5
(1) solution allocation: respectively zinc nitrate and 2-ethyl imidazol(e) are dissolved in deionized water and are mixed with the organic ligand that metal precursor solution A that concentration is 0.9mol/L and concentration is 2mol/L and are dissolved in B.
(2) mix: it is 10 microns microfiltration membrane both sides that A solution and B solution are placed respectively the aperture, the pressure difference of controlling diaphragm both sides is 0.03MPa, making A solution see through uniformly film enters in the B solution, the control temperature of reaction is 30 ℃, used reactor kind is hollow-fibre membrane, and membrane material is polyethersulfone (PS).
(3) aftertreatment: with white size liquid suspension obtained above,, methanol wash centrifugal through 12000r/min 2 times obtains nanometer class zeolite metallic organic framework compound at 95 ℃ of lower dry 12h.
Recording its particle diameter is 30.66nm, and specific surface area is 1302.2379m
2/ g.
Embodiment 6
(1) solution allocation: respectively cupric nitrate and glyoxal ethyline are dissolved in methyl alcohol and are mixed with the organic ligand that metal precursor solution A that concentration is 0.8mol/L and concentration is 3mol/L and are dissolved in B.
(2) mix: it is 5000 ultra-filtration membrane both sides that A solution and B solution are placed respectively molecular weight cut-off, the pressure difference of controlling diaphragm both sides is 0.08MPa, making A solution see through uniformly film enters in the B solution, the control temperature of reaction is 40 ℃, used reactor kind is rolled film, and membrane material is polysulfones (PS).
(3) aftertreatment: with white size liquid suspension obtained above,, methanol wash centrifugal through 12000r/min 2 times obtains nanometer class zeolite metallic organic framework compound at 100 ℃ of lower dry 12h.
Recording its particle diameter is 35.78nm, and specific surface area is 1360.4356m
2/ g.
Claims (7)
1. a microreactor prepares the method for nanometer class zeolite metallic organic framework compound, it is characterized in that adopting following processing step:
(1) solution allocation: at first metal precursor is dissolved in and is mixed with the metal precursor solution A that concentration is 0.5 ~ 1mo/L in the solvent, organic ligand is dissolved in is mixed with the organic ligand solution B that concentration is 0.5 ~ 4mol/L in the solvent;
(2) mix: the both sides that metal precursor solution A and organic ligand solution B placed respectively microporous membrane, the temperature of two kinds of solution of control is 30 ~ 40 ℃, the pressure difference of film both sides is 0.02 ~ 0.08MPa, the metal precursor solution A is seen through mould uniformly enter in the organic ligand solution B, obtain the white size liquid suspension;
(3) aftertreatment: get that step (2) gained white size liquid suspension is centrifugal through 10000 ~ 12000r/min, methanol wash 2 times, obtain product nanometer class zeolite metallic organic framework compound at 80 ~ 100 ℃ of lower dry 10 ~ 12h.
2. microreactor prepares the method for nanometer class zeolite metallic organic framework compound as claimed in claim 1, and it is characterized in that: described metal precursor is zinc nitrate or cupric nitrate.
3. microreactor prepares the method for nanometer class zeolite metallic organic framework compound as claimed in claim 1, and it is characterized in that: described organic ligand is glyoxal ethyline or 2-ethyl imidazol(e) or imidazoles.
4. microreactor prepares the method for nanometer class zeolite metallic organic framework compound as claimed in claim 1, and it is characterized in that: described organic solvent is methyl alcohol or deionized water.
5. microreactor prepares the method for nanometer class zeolite metallic organic framework compound as claimed in claim 1, and it is characterized in that: described microporous membrane is that the aperture is that 0.01 ~ 10 μ m, molecular weight cut-off are 5000 ~ 50000 microporous membranes.
6. microreactor prepares the method for nanometer class zeolite metallic organic framework compound as claimed in claim 5, it is characterized in that: the kit form of described microporous membrane is a kind of in flat sheet membrane, rolled film, tubular membrane or the hollow-fibre membrane.
7. microreactor prepares the method for nanometer class zeolite metallic organic framework compound as claimed in claim 5, and it is characterized in that: the material of described microporous membrane is polyethersulfone, polysulfones or polyvinylidene difluoride (PVDF).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210539173.1A CN102993221B (en) | 2012-12-13 | 2012-12-13 | Method for preparing nano-zeolite metal-organic framework compounds by microreactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210539173.1A CN102993221B (en) | 2012-12-13 | 2012-12-13 | Method for preparing nano-zeolite metal-organic framework compounds by microreactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102993221A true CN102993221A (en) | 2013-03-27 |
| CN102993221B CN102993221B (en) | 2015-04-22 |
Family
ID=47922388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210539173.1A Expired - Fee Related CN102993221B (en) | 2012-12-13 | 2012-12-13 | Method for preparing nano-zeolite metal-organic framework compounds by microreactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993221B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464001A (en) * | 2013-08-05 | 2013-12-25 | 大连理工大学 | Preparation method of metal organic framework membrane for CO2 separation |
| CN104817577A (en) * | 2015-04-08 | 2015-08-05 | 广东工业大学 | Preparation method and catalysis applications of efficient and simple zeolite imidazole framework ZIF-8 crystals with different morphologies |
| CN104892404A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Micro-channel chemical preparation method of porous metal-organic framework material |
| CN105601652A (en) * | 2014-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | Method for preparing metal organic framework material |
| CN105622639A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing nanoscale Cu-based metal organic framework material |
| CN105622675A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for high-activity metal organic framework material |
| US9376453B2 (en) | 2014-01-03 | 2016-06-28 | National Central University | Preparation method of zeolitic imidazolate framework-90 in water-based system |
| CN106398686A (en) * | 2016-09-05 | 2017-02-15 | Tcl集团股份有限公司 | Quantum dot and preparation method thereof |
| CN106632055A (en) * | 2016-12-21 | 2017-05-10 | 湘潭大学 | Preparation method of zeolite-like imidazole framework material and application of zeolite-like imidazole framework material in cyclohexane oxidation reaction |
| CN108395542A (en) * | 2018-04-10 | 2018-08-14 | 武汉纺织大学 | A kind of MOFs nanocrystalline materials and preparation method thereof of porous membrane substrate regulation and control |
| CN109589890A (en) * | 2019-01-11 | 2019-04-09 | 北京机械设备研究所 | A kind of hydrogen peroxide synthesizer and method |
| CN110280193A (en) * | 2019-05-23 | 2019-09-27 | 中国药科大学 | A kind of device and method synthesizing class zeolitic imidazolate framework material |
| CN111387178A (en) * | 2020-03-17 | 2020-07-10 | 南京启佑生物科技有限公司 | Method for preparing metal organic framework-pesticide nano composite preparation by adopting microreactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101404646A (en) * | 2007-10-02 | 2009-04-08 | 艾科星科技公司 | Systems & methods for proxy resolution of domain name service (DNS) requests |
| CN102220626A (en) * | 2011-05-25 | 2011-10-19 | 大连理工大学 | Nano zeolitic imidazolate frameworks crystal preparation method through dynamic crystallization |
| CN102335626A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing micro/nano zeolitic imidazolate frameworks (ZIFs) |
| CN102731538A (en) * | 2012-06-07 | 2012-10-17 | 中国石油大学(华东) | Preparation method of nanometer-to-micrometer scale zeolitic imidazolate frameworks (ZIFs) |
-
2012
- 2012-12-13 CN CN201210539173.1A patent/CN102993221B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101404646A (en) * | 2007-10-02 | 2009-04-08 | 艾科星科技公司 | Systems & methods for proxy resolution of domain name service (DNS) requests |
| CN102220626A (en) * | 2011-05-25 | 2011-10-19 | 大连理工大学 | Nano zeolitic imidazolate frameworks crystal preparation method through dynamic crystallization |
| CN102335626A (en) * | 2011-07-20 | 2012-02-01 | 中国科学院化学研究所 | Method for synthesizing micro/nano zeolitic imidazolate frameworks (ZIFs) |
| CN102731538A (en) * | 2012-06-07 | 2012-10-17 | 中国石油大学(华东) | Preparation method of nanometer-to-micrometer scale zeolitic imidazolate frameworks (ZIFs) |
Non-Patent Citations (6)
| Title |
|---|
| CHRISTOPHER J.ADAMS ET AL: "Coordination chemistry in the solid state: synthesis and interconversion of pyrazolium salts, pyrazole complexes, and pyrazolate MOFs", 《DALTON TRANS.》 * |
| 孙余凭等: "膜法富氧气及UF 膜法CuO用于异丙苯氧化反应的研究", 《化学反应工程与工艺》 * |
| 尹燕亓: "UF膜法CuO及富氧气用于异丙苯氧化反应的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 张春芳等: "超滤膜法CuO-ZnO 复合催化剂的制备及催化性能", 《化工进展》 * |
| 许炯: "UF膜法纳米金属氧化物催化剂制备及其对异丙苯氧化反应的催化性能研究", 《中国优秀硕士学位论文全文数据库》 * |
| 许炯等: "膜法 C u O 的制备及其对异丙苯氧化反应的催化作用", 《江南大学学报（自然科学版）》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464001B (en) * | 2013-08-05 | 2016-03-09 | 大连理工大学 | A kind of for CO 2the preparation method of the metal organic framework film be separated |
| CN103464001A (en) * | 2013-08-05 | 2013-12-25 | 大连理工大学 | Preparation method of metal organic framework membrane for CO2 separation |
| US9376453B2 (en) | 2014-01-03 | 2016-06-28 | National Central University | Preparation method of zeolitic imidazolate framework-90 in water-based system |
| CN104892404A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Micro-channel chemical preparation method of porous metal-organic framework material |
| CN105622675B (en) * | 2014-10-28 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of preparation method of high activity metal organic framework material |
| CN105601652A (en) * | 2014-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | Method for preparing metal organic framework material |
| CN105622639A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing nanoscale Cu-based metal organic framework material |
| CN105622675A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for high-activity metal organic framework material |
| CN105601652B (en) * | 2014-10-28 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method for preparing metal-organic framework materials |
| CN104817577A (en) * | 2015-04-08 | 2015-08-05 | 广东工业大学 | Preparation method and catalysis applications of efficient and simple zeolite imidazole framework ZIF-8 crystals with different morphologies |
| CN106398686A (en) * | 2016-09-05 | 2017-02-15 | Tcl集团股份有限公司 | Quantum dot and preparation method thereof |
| CN106632055A (en) * | 2016-12-21 | 2017-05-10 | 湘潭大学 | Preparation method of zeolite-like imidazole framework material and application of zeolite-like imidazole framework material in cyclohexane oxidation reaction |
| CN106632055B (en) * | 2016-12-21 | 2021-03-30 | 湘潭大学 | Preparation method of zeolite-like imidazole framework material and application of zeolite-like imidazole framework material in cyclohexane oxidation reaction |
| CN108395542A (en) * | 2018-04-10 | 2018-08-14 | 武汉纺织大学 | A kind of MOFs nanocrystalline materials and preparation method thereof of porous membrane substrate regulation and control |
| CN108395542B (en) * | 2018-04-10 | 2020-12-18 | 武汉纺织大学 | MOFs nanocrystalline material regulated and controlled by porous membrane substrate and preparation method thereof |
| CN109589890A (en) * | 2019-01-11 | 2019-04-09 | 北京机械设备研究所 | A kind of hydrogen peroxide synthesizer and method |
| CN110280193A (en) * | 2019-05-23 | 2019-09-27 | 中国药科大学 | A kind of device and method synthesizing class zeolitic imidazolate framework material |
| CN111387178A (en) * | 2020-03-17 | 2020-07-10 | 南京启佑生物科技有限公司 | Method for preparing metal organic framework-pesticide nano composite preparation by adopting microreactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102993221B (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102993221B (en) | Method for preparing nano-zeolite metal-organic framework compounds by microreactor | |
| Zhao et al. | Metal-organic framework based membranes for selective separation of target ions | |
| Faustini et al. | Microfluidic approach toward continuous and ultrafast synthesis of metal–organic framework crystals and hetero structures in confined microdroplets | |
| Wang et al. | Nanoreactor Based on Macroporous Single Crystals of Metal‐Organic Framework | |
| Chen et al. | Synthesis of monodisperse mesoporous titania beads with controllable diameter, high surface areas, and variable pore diameters (14− 23 nm) | |
| CN107497377A (en) | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere | |
| CN103881278B (en) | The preparation method of a kind of graphene oxide-water-soluble polymers three-dimensional porous nano matrix material | |
| CN110105580B (en) | Hierarchical pore zeolite imidazole ester framework material and preparation method thereof | |
| CN102580565B (en) | Preparation method for high-performance metal organic framework film | |
| CN104448381B (en) | The preparation and its application of imidazoles functionalized ordered mesoporous phenolic resin material | |
| CN108976433B (en) | Method for preparing metal organic framework nanosheet by liquid phase stripping method | |
| CN108129670B (en) | Preparation method of gradient porous metal organic framework ZIF-8 | |
| CN102976412B (en) | Method for preparing mesoporous LaFeO3 by taking mesoporous carbon and mesoporous silicon dioxide as hard templates | |
| Guo et al. | Synthesis of 3D-ordered macro/microporous yolk–shelled nanoreactor with spatially separated functionalities for cascade reaction | |
| CN111282405A (en) | Modified metal organic framework nanosheet and preparation method thereof | |
| CN109012224A (en) | The method that a kind of nanometer of confinement growth in situ prepares ZIF-8@graphene oxide hybridized film | |
| CN103059066A (en) | Method of rapidly preparing metal organic framework material thin-film from hydroxide nanowires and organic ligands under normal temperature | |
| CN105731424A (en) | Preparation method and application of nitrogen-doped nanoscale hollow carbon ball material | |
| CN106694050A (en) | Preparation method of visible-light-induced photocatalyst with core-shell structure | |
| CN111387178A (en) | Method for preparing metal organic framework-pesticide nano composite preparation by adopting microreactor | |
| CN103566772B (en) | Porous polymer polymeric hollow fibre tube-surface prepares method and the application of metal organic framework thin film | |
| Yang et al. | A cellulose monolith supported metal/organic framework as a hierarchical porous material for a flow reaction | |
| CN106674290A (en) | Preparation method of monodispersed cobalt and nickel composite MOF-74 | |
| Xiao et al. | Construction of a functionalized hierarchical pore metal–organic framework via a palladium-reduction induced strategy | |
| Xu et al. | Facile synthesis of mesoporous reduced graphene oxide microspheres with well-distributed Fe2O3 nanoparticles for photochemical catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150422 Termination date: 20151213 |
|
| EXPY | Termination of patent right or utility model |