CN109485095A - One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed - Google Patents

One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed Download PDF

Info

Publication number
CN109485095A
CN109485095A CN201811395283.9A CN201811395283A CN109485095A CN 109485095 A CN109485095 A CN 109485095A CN 201811395283 A CN201811395283 A CN 201811395283A CN 109485095 A CN109485095 A CN 109485095A
Authority
CN
China
Prior art keywords
preparation
crystalline material
metal salt
node
crystalline
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.)
Pending
Application number
CN201811395283.9A
Other languages
Chinese (zh)
Inventor
邓鹤翔
刘琦
宋银银
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University WHU
Original Assignee
Wuhan University WHU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuhan University WHU filed Critical Wuhan University WHU
Priority to CN201811395283.9A priority Critical patent/CN109485095A/en
Publication of CN109485095A publication Critical patent/CN109485095A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention provides one kind by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed, the mesopore orbit of the crystalline material is by 12 Zr6O8Node and 16 Cu3ON6Node composition, crystal structure contain the penetrating cellular structure of three-dimensional of long-range order.Compared with prior art, present invention gained crystalline material is raw materials used and synthesis cost is lower, has the three-dimensional open-framework of larger-size long-range order, the stability of crystalline material is preferable.

Description

One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and its preparation that multinode is constructed Method
Technical field
The invention belongs to mesoporous crystalline materials technical fields, in particular to a kind of containing by 12 Zr6O8Node and 16 Cu3ON6The crystalline material and preparation method thereof of node composition mesopore orbit.
Background technique
Mesopore orbit crystalline material is as a kind of novel porous materials, excellent cellular structure design and stabilization Property, gas absorption with separate, be catalyzed and in terms of biomolecule all with more important application (Science 2013,341,1230444；Chem.Soc.Rev.2012,41,1677.).Therefore, it is synthetically prepared New Type of Mesoporous duct crystal material Material has become heat subject.Existing synthesis preparation method tend to rely on organic ligand extension, and by organic ligand extension and Extension generally requires biggish cost and relatively complicated synthesis process, generally requires the ligand (Science that length is greater than 1nm 2012,336,1018；Angew.Chem.Int.Ed.2015,54,149.).Although having some researchs to report by mostly golden Belong to and multiple ligand constructs mesoporous material, but these structures or pore size is smaller or water stability is general (J.Am.Chem.Soc.2015,137,13456；J.Am.Chem.Soc.2017,139,7998.).But also it is same without research Shi Caiyong Zr and Cu construct material.This greatly limits the development of mesopore orbit crystalline material and its answering in multi-field With.
Summary of the invention
For deficiency existing for existing method, the invention proposes one kind containing by 12 Zr6O8Node and 16 Cu3ON6 Node forms the crystalline material of mesopore orbit, preparation method and applications.
In order to solve the above-mentioned technical problem, technical scheme is as follows:
One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials that multinode is constructed, the mesopore orbit of the crystalline material is by 12 A Zr6O8Node and 16 Cu3ON6Node composition, crystal structure contain the penetrating cellular structure of three-dimensional of long-range order.
Preferably, the Zr6O8Node is the structural unit being made of 6 Zr oxygen octahedras.
Preferably, the Cu3ON6Node is the structural unit being made of 3 Cu oxygen octahedras.
Preferably, the Zr6O8Node and Cu3ON6Node is used as [2c, 3c] connecting node in material crystal structure.
Preferably, the crystalline material includes a variety of nodes.
Preferably, the crystalline material intermediary hole pore size is 3.8nm.
The present invention also provides the preparation methods of above-mentioned crystalline material, comprising the following steps:
1) zirconium metal salt, copper metal salt, 4- pyrazole carboxylic acid, trifluoroacetic acid are added to equipped with N,N-dimethylformamide In glass reaction bottle, ultrasound clarifies reaction solution；
2) the glass reaction bottle of step 1) is put into 100 degrees Celsius of constant temperature ovens and is heated 10 hours, obtain sediment；
3) solution after step 2) reaction is centrifuged, separates original reaction dissolvent, obtains powdery product；
4) powdery product that step 3) obtains repeatedly is washed with N, dinethylformamide and acetone；
5) activation is dried using supercritical carbon dioxide in the powdery product after must washing step 4), obtains final Crystalline material.
Preferably, the zirconium metal salt is any one of the nitrate of zirconium, villaumite, sulfate, acetate, more preferably Ground is eight hydration zirconium oxychloride (ZrOCl2·8H2O)；The copper metal salt is in the nitrate of copper, villaumite, sulfate, acetate It is any, be more preferably Gerhardite (Cu (NO3)2·3H2O)。
Preferably, in mixed system obtained by step 1), zirconium metal salt concentrations are 3-5g/l, and copper metal salinity is 10- 15g/l, 4- pyrazole carboxylic acid are 2-4g/l, the concentration of trifluoroacetic acid is 15-20g/L.
Preferably, added zirconium metal salt in step 1), copper metal salt, 4- pyrazole carboxylic acid molar ratio be (10~15): (50 ~60): (20~30).
Preferably, the step 4) washing process is to be statically placed in powder in solvent for use 3-8 hours.
Preferably, activation is dried using supercritical carbon dioxide drying instrument in step 5).
Compared with prior art, the present invention has the advantage that and the utility model has the advantages that
1, organic ligand size used in crystalline material of the present invention is small (0.4nm), and synthesis cost is lower；
2, crystalline material of the present invention has three-dimensional meso-hole (3.8nm) cellular structure of larger-size long-range order, more piece Point constitutes [2c, 3c] connection；
3, the stability of crystalline material of the present invention is preferable.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention System.
Fig. 1 is the crystal structure schematic diagram of present invention gained crystalline material, in which: figure (A) is Zr6O8Node structure；(B) For Cu3ON6Node structure；It (C) is the crystal structure construction unit schematic diagram；(D) show for the mesopore orbit structure of the crystalline material It is intended to；It (E) is the crystal three dimensional structure diagram；(F) the topological structure schematic diagram simplified for the crystal；It (G) is crystal letter Frame (tilling) structural schematic diagram of change；
Fig. 2 is the crystal X-ray powder diffraction figure of 1 gained crystalline material of the embodiment of the present invention；
Fig. 3 is the nitrogen adsorption test result figure of the crystal of 1 gained crystalline material of the embodiment of the present invention, wherein figure (A) is The nitrogen adsorption curve of material；(A-1) pore-size distribution being fitted for material by nitrogen adsorption；It (B) is fitting specific surface The selected section of product；It (C) is specific surface area fitting result.
Specific embodiment
To keep the present invention easier to understand, specific embodiments of the present invention are further illustrated below.
Embodiment 1
1) by 43.5 milligram of eight hydration zirconium oxychloride (ZrOCl2·8H2O), 124.0 milligrams of Gerhardite (Cu (NO3)2·3H2O), 32.5 milligrams of 4- pyrazole carboxylic acids and 120 microlitres of trifluoroacetic acids are added to equipped with 10 milliliters of N, N- dimethyl methyl In the glass reaction bottle of amide, ultrasound clarifies reaction solution；
2) the glass reaction bottle of step 1) is put into 100 degrees Celsius of constant temperature ovens and is heated 10 hours；
3) it will be centrifuged by powder sample obtained in step 2), and separate original reaction dissolvent, obtain out powder product；
4) it will repeatedly be washed by powder obtained in step 3) using N, dinethylformamide and acetone.
5) activation is dried using supercritical carbon dioxide to get final products are arrived in powder obtained in step 4).
Fig. 2 is the crystal X-ray powder diffraction figure of gained crystalline material, and experimental result shows experimental patterns and crystal knot The map of structure simulation is consistent, shows the high crystalline and purity of material.
Fig. 3 is the nitrogen adsorption test result of the crystal of gained crystalline material, and nitrogen adsorption experiment is in gas absorption instrument Upper progress, test result can be used for the specific surface area analysis of material, the results showed that synthetic material specific surface area with higher, It is 2050m by the specific surface area that fitting obtains material with mesopore orbit2/g。
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention Protection scope within.

Claims (10)

1. one kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials that multinode is constructed, it is characterised in that: the crystalline material it is mesoporous Duct is by 12 Zr6O8Node and 16 Cu3ON6Node composition.
2. crystalline material according to claim 1, it is characterised in that: the Zr6O8Node is by 6 Zr oxygen octahedras The structural unit of composition.
3. crystalline material according to claim 1, it is characterised in that: the Cu3ON6Node is by 3 Cu oxygen octahedras The structural unit of composition.
4. crystalline material according to claim 1, it is characterised in that: the crystalline material intermediary hole pore size is 3.8nm。
5. the preparation method of crystalline material as described in claim any one of 1-4, which comprises the following steps:
1) zirconium metal salt, copper metal salt, 4- pyrazole carboxylic acid, trifluoroacetic acid are added to the glass equipped with N,N-dimethylformamide In reaction bottle, ultrasound clarifies reaction solution；
2) the glass reaction bottle of step 1) is put into 100 degrees Celsius of constant temperature ovens and is heated 10 hours, obtain sediment；
3) solution after step 2) reaction is centrifuged, separates original reaction dissolvent, obtains powdery product；
4) powdery product that step 3) obtains repeatedly is washed with N, dinethylformamide and acetone；
5) activation is dried using supercritical carbon dioxide in the powdery product after must washing step 4), obtains final crystalline substance Body material.
6. preparation method according to claim 5, it is characterised in that: the zirconium metal salt is nitrate, villaumite, the sulphur of zirconium Any one of hydrochlorate, acetate；The copper metal salt is any one of the nitrate of copper, villaumite, sulfate, acetate.
7. preparation method according to claim 5, which is characterized in that in mixed system obtained by step 1), zirconium metal salt is dense Degree is 3-5g/L, and copper metal salinity is 10-15g/L, and 4- pyrazole carboxylic acid is 2-4g/L, the concentration of trifluoroacetic acid is 15-20g/ L。
8. preparation method according to claim 5, which is characterized in that added zirconium metal salt, copper metal salt, 4- in step 1) The molar ratio of pyrazole carboxylic acid is (10~15): (50~60): (20~30).
9. preparation method according to claim 5, it is characterised in that: the step 4) washing process is to be statically placed in powder 3-8 hours in solvent for use.
10. preparation method according to claim 5, it is characterised in that: step 5) uses supercritical carbon dioxide drying instrument Activation is dried.
CN201811395283.9A 2018-11-22 2018-11-22 One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed Pending CN109485095A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811395283.9A CN109485095A (en) 2018-11-22 2018-11-22 One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811395283.9A CN109485095A (en) 2018-11-22 2018-11-22 One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed

Publications (1)

Publication Number Publication Date
CN109485095A true CN109485095A (en) 2019-03-19

Family

ID=65697279

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811395283.9A Pending CN109485095A (en) 2018-11-22 2018-11-22 One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed

Country Status (1)

Country Link
CN (1) CN109485095A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116496506A (en) * 2023-04-21 2023-07-28 武汉大学 Preparation method and application of mesoporous crystalline material with super-large primary three-dimensional cage structure
CN117143350A (en) * 2023-08-29 2023-12-01 广东工业大学 Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851020A (en) * 2012-09-19 2013-01-02 复旦大学 Magnetic-chromatic synchronously-responsive self-assembled microporous material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851020A (en) * 2012-09-19 2013-01-02 复旦大学 Magnetic-chromatic synchronously-responsive self-assembled microporous material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QI LIU ET AL.: "Mesoporous Cages in Chemically Robust MOFs Created by a Large Number of Vertices with Reduced Connectivity", 《J. AM. CHEM. SOC.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116496506A (en) * 2023-04-21 2023-07-28 武汉大学 Preparation method and application of mesoporous crystalline material with super-large primary three-dimensional cage structure
CN116496506B (en) * 2023-04-21 2024-05-03 武汉大学 Preparation method and application of mesoporous crystalline material with super-large primary three-dimensional cage structure
CN117143350A (en) * 2023-08-29 2023-12-01 广东工业大学 Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone
CN117143350B (en) * 2023-08-29 2024-03-12 广东工业大学 Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone

Similar Documents

Publication Publication Date Title
CN106674537B (en) Method for quickly and efficiently synthesizing metal organic framework material UiO-66(Zr) without template agent and solvent
Hara et al. The effect of hydrothermal treatment on column performance for monolithic silica capillary columns
Szymańska et al. Low back-pressure hierarchically structured multichannel microfluidic bioreactors for rapid protein digestion–Proof of concept
CN109485095A (en) One kind is by Zr6O8And Cu3ON6The mesoporous crystalline materials and preparation method thereof that multinode is constructed
ES2579132A1 (en) Metal-organic gels and metal-organic aerogels built from nanofibers of coordination polymers (Machine-translation by Google Translate, not legally binding)
CN109942827A (en) A kind of method that covalent organic frame material is modified
Yu et al. A novel enzyme biosensor for glucose based on rhodanine derivative chemiluminescence system and mesoporous hollow silica microspheres receptor
Dong et al. Preparation of tubular hierarchically porous silicate cement compacts via a tert-butyl alcohol (TBA)-based freeze casting method
CN107576418B (en) Fluorescent nano thermometer based on DNA nano structure and preparation method thereof
CN108993419A (en) Method for preparing Ni-MOF adsorption material by ultrasonic-assisted solvothermal method and application
Jin et al. Biopolymer-assisted construction of porous SnO2 microspheres with enhanced sensing properties
Gao et al. Hierarchically mesoporous Ce-based MOFs with enhanced alkaline phosphatase-like activity for phosphorylated biomarker sensing
Fonseca et al. Rational synthesis of a hierarchical supramolecular porous material created via self-assembly of metal–organic framework nanosheets
CN104945655A (en) Synthesis method and application of molecularly imprinted mesoporous material
Sommerdijk et al. Lessons from nature—biomimetic approaches to minerals with complex structures
Sass et al. Electron spin echo modulation and electron spin resonance studies of cupric ions in H-ZSM-5, Na-ZSM-5, K-ZSM-5, and CA-ZSM-5 zeolites: analysis of carbon-13 electron spin echo modulation
CN108440767A (en) It is a kind of that nanometer Au is combined to the new method for preparing Au@MOF composite materials with porous MOF
CN108774323A (en) A kind of metal-organic framework materials and preparation method and applications of the Zr based on four tooth Carboxylic acid ligands
Zhao et al. Natural and artificial chiral-based systems for separation applications
Zhao et al. Aerogels
Yu et al. A fluorescence analysis model for assessing the water stability of porphyrinic metal− organic frameworks
Wang et al. Hierarchically Porous Covalent Organic Frameworks: Synthesis Methods and Applications
Zhang et al. Copper–carbon dot aerogel: a high-performance mimetic peroxidase and its application for versatile colorimetric bioassays
Zhang et al. Templated fabrication of biomorphic alumina-based ceramics with hierarchical structure
CN109592716A (en) One kind is by M3O13And Cu3ON6There are two types of the crystalline materials and preparation method thereof of mesopore orbit for the tool that multinode is constructed

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20190319

RJ01 Rejection of invention patent application after publication