CN105001245B - Metal organic framework material of Zn and preparation method and application of metal organic framework material of Zn - Google Patents
Metal organic framework material of Zn and preparation method and application of metal organic framework material of Zn Download PDFInfo
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- CN105001245B CN105001245B CN201510417125.9A CN201510417125A CN105001245B CN 105001245 B CN105001245 B CN 105001245B CN 201510417125 A CN201510417125 A CN 201510417125A CN 105001245 B CN105001245 B CN 105001245B
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000013110 organic ligand Substances 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910004039 HBF4 Inorganic materials 0.000 claims abstract description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 7
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 12
- 229910003460 diamond Inorganic materials 0.000 claims description 11
- 239000010432 diamond Substances 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000266 acriflavinium chloride Drugs 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- -1 Dimethylamine ion Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000009432 framing Methods 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 14
- BGLGAKMTYHWWKW-UHFFFAOYSA-N acridine yellow Chemical compound [H+].[Cl-].CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=CC2=C1 BGLGAKMTYHWWKW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 239000001045 blue dye Substances 0.000 description 4
- 238000002447 crystallographic data Methods 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 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
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to a metal organic framework material of Zn and a preparation method and application of the metal organic framework material of Zn. The chemical structure of the metal organic framework material of Zn is {[(CH3)2NH2]2Zn2L1.5Bpy}.2DMF, wherein L is an organic ligand 4,8-disulfonic-2,6-naphthalenedicarboxylic acid; Bpy is an auxiliary organic ligand 4,4'-dipyridyl; DMF is N,N-dimethylformamide. In a closed condition, thermal reaction is carried out on the organic ligand L 4,8-disulfonic-2,6-naphthalenedicarboxylic acid, the auxiliary organic ligand Bpy 4,4'-dipyridyl and zinc nitrate hexahydrate in a mixed solution of DMF (N,N-dimethylformamide) and HBF4 (tetrafluoroboric acid) to obtain crystals of the metal organic framework material. The metal organic framework material is charged negatively and can be used as a selective adsorption material of relatively small-sized cationic dyes methylene blue and acridine yellow.
Description
Technical field
The invention belongs to the technical field of crystalline material, technology is related to metal organic coordination polymer material, particularly one
Plant metal-organic framework materials, the preparation method and applications of Zn.
Background technology
Dye industry is one of serious industry of environmental pollution in chemical industry.According to statistics, during DYE PRODUCTION
The dyestuff of 1-2% is there are about, the dyestuff of 1-10% is there are about in dyeing course can be entered in environment with waste water, it is tight to environment structure
The threat of weight.Dyestuff as the stable organic compound of a class formation, with the characteristic such as antiacid, alkali resistant, anti-light, antimicrobial,
There is longer demurrage in the environment, therefore the negative effect of Dyes on Environment is not only in that its colourity and COD, is more right
The potential hazard of human health and growth and development of plants and animals.Therefore the dye that a kind of method efficiently, economic is removed in waste water is found
Material is significantly.
Metal-organic framework materials are tied with periodicity skeleton by what metal ion or ion cluster and organic ligand were constructed
One class novel porous materials of structure.Because it has porous, high specific surface area and aperture and hole surface property adjustable, metal
Organic framework material is considered a type of outstanding adsorbent and all has potential application, its selectivity in dyestuff in various fields
Research in terms of absorption, causes the extensive attention of domestic and international researcher.
The content of the invention
It is an object of the invention to provide a kind of metal-organic framework materials and preparation method and applications.
A kind of 3-dimensional metal organic framework material of the present invention, it is characterised in that chemical molecular formula is { [(CH3)2NH2]2Zn2L1.5Bpy } 2DMF, L be organic ligand 4,8- disulfonic acid base -2,6- naphthalene dicarboxylic acids;Bpy be ancillary organic ligands 4,4 '-
Bipyridyl;DMF is N,N-dimethylformamide.
From the angle that skeleton connection is constructed, containing the zinc atom of two kinds of coordination modes in framing structure, Zn1 and Zn2 is designated as;
Dinuclear metal clustering architecture is formed by the way that three bridgings are bonded between adjacent Zn1 and Zn2, each bridging key is in L
Individual carboxyl, Zn1 is connected with an O of a carboxyl in L, and Zn2 is connected with another O of same carboxyl, three bridging keys
Carboxyl in three L;Simultaneously the 4th key in Zn1 is to be formed to be connected with the O in sulfonic group in the 4th L organic ligand
Key, the 5th in Zn1 key is the connecting key formed with the N Atomic coordinates in ancillary organic ligands Bpy;In Zn2 the 4th
Individual key is the connecting key formed with the N Atomic coordinates in another ancillary organic ligands Bpy.Zn1 is more relative to Zn2 from terms of form
Increased one with sulfonic group in L organic ligands in O formed connecting key.
The crystal structure of the 3-dimensional metal organic framework material belongs to anorthic system, and space group is P-1, and cell parameter is:α=67.834 °, β=81.604 °, γ=
74.195°。
The above-mentioned adjacent mutual bridging of two Zn1 and Zn2 atoms defines a dinuclear metal cluster, in each metal cluster
Three ligand Ls are connected respectively by other carboxyl from three neighbouring different metal clusters, form two-dimensional layered structure, wherein
Four metal clusters surround diamond structure by four ligand Ls, and multiple diamond structures side by side in a row, there is a multirow diamond structure, and two
The connection for defining duplicate rows structure is coordinated with the O atom on sulphur carboxyl in another row by Zn1 between row diamond structure, in two dimension
Layer structure carries out being coordinated the multiple structure for connecting and composing three-dimensional order between layers by Bpy.
(CH3)2NH2 +And DMF solvent molecule is for balancing charge and improves crystal structure.Can be from crystal structure
What data and charge balance drew.
See along vertical two-dimensional layered structure direction, metal cluster is connected to form the duct of rhombus with ligand L, duct size is aboutDuct is contained within maintaining the dimethylamine ion of charge balance.
The wherein chemical structural formula of organic ligand 4,8- disulfonic acid base -2,6 naphthalene dicarboxylic acid:
The synthetic method of metal-organic framework materials of the present invention, comprises the following steps:
Under sealing condition, organic ligand L (4,8- disulfonic acid base -2,6- naphthalene dicarboxylic acids), ancillary organic ligands Bpy (4,4 ' -
Bipyridyl) with zinc nitrate hexahydrate in DMF (N,N-dimethylformamide) and HBF4In the mixed solution of (Tetrafluoroboric acid), via
Thermal response obtains the crystal of metal-organic framework materials.
Wherein organic ligand L (4,8- disulfonic acid base -2,6 naphthalene dicarboxylic acid), ancillary organic ligands Bpy (4,4 '-bipyridyl)
It is (1~3) with the mol ratio of zinc nitrate hexahydrate:(1~3):1, the six directions zinc nitrate correspondence 0.5mL per 0.035 mM~
The DMF of 2mL, the HBF of 1~10 drop4, the wherein HBF of 1mL4About 40 drops, the temperature of the thermal response is 60
DEG C -120 DEG C, the response time is 20-50 hours.
This metal-organic framework materials carries negative charge, can be used for the small size dye of positive ion such as methylene blue and acriflavinium chloride
Selective absorption.
The metal-organic framework materials structure of the present invention is novel, the duct with suitable dimension, and skeleton carries negative charge, energy
Effective as selective absorption is carried out to the undersized dye of positive ion, is had in the organic dye molecule in selective absorption waste water
There is potential application.Preparation method process is simple of the present invention, easy to implement, yield are high, are conducive to large-scale popularization.
Description of the drawings
Fig. 1 is the schematic diagram of metallic atom coordination mode in the metal-organic framework materials;
Fig. 2 is the three dimensional structure diagram of the metal-organic framework materials.
Fig. 3 is absorption property figure of the metal-organic framework materials to methylene blue dye.
Fig. 4 is absorption property figure of the metal-organic framework materials to acridine yellow dye.
Specific embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
By organic ligand L (0.035 mM), assistant ligand Bpy (0.035 mM) and zinc nitrate hexahydrate (0.035
MM) mix homogeneously in the DMF of 1mL, add 8 to drip HBF4, in enclosing bottle.At 100 DEG C via
Thermal response obtains the crystal of metal-organic framework materials for 48 hours.
Embodiment 2
By organic ligand L (0.035 mM), assistant ligand Bpy (0.019 mM) and zinc nitrate hexahydrate (0.035
MM) mix homogeneously in the DMF of 1mL, add 6 to drip HBF4, in enclosing bottle.At 100 DEG C via
Thermal response obtains the crystal of metal-organic framework materials for 48 hours.
Embodiment 3
By organic ligand L (0.035 mM), assistant ligand Bpy (0.019 mM) and zinc nitrate hexahydrate (0.035
MM) mix homogeneously in the DMF of 1.5mL, add 6 to drip HBF4, in enclosing bottle.The Jing at 100 DEG C
The crystal of metal-organic framework materials is obtained for 48 hours by thermal response.
Embodiment 4
By organic ligand L (0.035 mM) assistant ligand Bpy (0.019 mM) and zinc nitrate hexahydrate (0.035
MM) mix homogeneously in the DMF of 2mL, add 8 to drip HBF4, in enclosing bottle.At 120 DEG C via
Thermal response obtains the crystal of metal-organic framework materials for 24 hours.
The test result of the product obtained by above-described embodiment is identical, specifically sees below:
(1) crystal structure determination:
The monocrystalline of suitable size is chosen under the microscope, under 100K, using Agilent Technologies
SuperNova single crystal diffractometersThe Mo-K alpha rays of Jing graphite monochromator monochromatizations, withMode
Collect diffraction data.All diffraction datas carry out absorption correction using SADABS programs.Cell parameter is true using method of least square
It is fixed.Data convert and structure elucidation are completed respectively using SAINT and SHELXTL-97 programs.First with difference function method and a most young waiter in a wineshop or an inn
Multiplication determines whole non-hydrogen atom coordinates, and obtains hydrogen atom position with theoretical hydrogenation method, then with SHELXTL-97 to crystal
Structure carries out refine.Structure chart is shown in Fig. 1 and Fig. 2.Crystallographic data is shown in Table 1.
The crystallographic data of the metal-organic framework materials of table 1
The structure chart of Fig. 1 shows:The framework material has the zinc atom of two kinds of coordination modes, and Zn1 and Zn2 is designated as respectively.Zn1
The N Atomic coordinates in three O atoms and organic part Bpy altogether respectively and in three organic ligand L, wherein there is two O
Atom comes from the carboxyl in L, and sulfonic group of another O atom in L;Zn2 then with three O in three carboxyls
N atoms in atom and Bpy are coordinated.
The structure chart of Fig. 2 shows:The mutual bridging of Zn1 and Zn2 atoms defines the metal cluster of dinuclear, and metal cluster is connected by L
Connect and be expanded into two-dimensional layered structure.Three ligand Ls in each metal cluster pass through other carboxyl respectively with neighbouring three not
Same metal cluster connection, forms two-dimensional layered structure, wherein four metal clusters surround diamond structure by four ligand Ls, it is multiple
Diamond structure side by side in a row, there is multirow diamond structure, by Zn1 and sulphur carboxyl in another row between two row diamond structures
O atom coordination defines the connection of duplicate rows structure, carries out coordination by Bpy between layers in two-dimensional layered structure and connects and composes
The multiple structure of three-dimensional order.
(2) dye adsorption performance characterization:
Fig. 3 is the methylene blue dye Characterization of Adsorption of material of the present invention.In Fig. 3, at ambient temperature, over time
Increase, the methylene blue dye concentration in methanol solution is gradually lowered, and illustrates there is good absorption to methylene blue dye
Performance.
Fig. 4 is the dye adsorption performance characterization of acriflavinium chloride of material of the present invention.In Fig. 4, at ambient temperature, over time
Increase, the acridine yellow dye concentration in methanol solution is gradually lowered, and illustrates there is good absorption property to acridine yellow dye.
Claims (6)
1. a kind of metal-organic framework materials of Zn, it is characterised in that chemical molecular formula is { [(CH3)2NH2]2Zn2L1.5Bpy}·
2DMF, L be organic ligand 4,8- disulfonic acid base -2,6- naphthalene dicarboxylic acids;
Bpy is ancillary organic ligands 4,4 '-bipyridyl;DMF is N,N-dimethylformamide;
Crystal structure belongs to anorthic system, and space group is P-1, and cell parameter is: α=67.834 °, β=81.604 °, γ=74.195 °.
2. according to claim 1 a kind of Zn metal-organic framework materials, it is characterised in that from the angle constructed of skeleton connection
Degree, containing the zinc atom of two kinds of coordination modes in framing structure, is designated as Zn1 and Zn2;Pass through three between adjacent Zn1 and Zn2
The bonded formation cagelike structure of bridging, each bridging key is a carboxyl in L, an O of a carboxyl in Zn1 and L
Connection, Zn2 is connected with another O of same carboxyl, the carboxyl of three bridging keys in three L;While the 4th in Zn1
Individual key is to form connecting key with the O in sulfonic group in the 4th L organic ligand, and the 5th in Zn1 key is organic with auxiliary
The connecting key that N Atomic coordinates in part Bpy are formed;The 4th key in Zn2 be with another ancillary organic ligands Bpy
The connecting key that N Atomic coordinates are formed.
3. according to claim 2 a kind of Zn metal-organic framework materials, it is characterised in that two adjacent Zn1 and Zn2 are former
Sub mutually bridging defines a metal cluster of dinuclear, three in each metal cluster ligand L by other carboxyl respectively with
Three neighbouring different metal cluster connections, form two-dimensional layered structure, wherein four metal clusters surround Pedicellus et Pericarpium Trapae by four ligand Ls
Shape structure, multiple diamond structures side by side in a row, there is multirow diamond structure, by Zn1 and another row between two row diamond structures
O atom coordination on middle sulphur carboxyl defines the connection of duplicate rows structure, is carried out by Bpy between layers in two-dimensional layered structure
Coordination connects and composes the multiple structure of three-dimensional order.
4. according to claim 3 a kind of Zn metal-organic framework materials, it is characterised in that along vertical two-dimensional layered structure side
To seeing, metal cluster is connected to form the duct of rhombus with ligand L, and duct size is aboutDuct is contained within maintaining charge balance
Dimethylamine ion.
5. the method for preparing the metal-organic framework materials of any Zn of claim 1-4, it is characterised in that including following
Step:Under sealing condition, organic ligand L (4,8- disulfonic acid base -2,6- naphthalene dicarboxylic acids), ancillary organic ligands Bpy (4,4 '-connection
Pyridine) with zinc nitrate hexahydrate in DMF (N,N-dimethylformamide) and HBF4In the mixed solution of (Tetrafluoroboric acid), via heat
Reaction obtains the crystal of metal-organic framework materials;
Wherein organic ligand L (4,8- disulfonic acid base -2,6 naphthalene dicarboxylic acid), ancillary organic ligands Bpy (4,4 '-bipyridyl) and six
The mol ratio of nitric hydrate zinc is (1~3):(1~3):1, the six directions zinc nitrate correspondence 0.5mL~2mL's per 0.035 mM
DMF, the HBF of 1~10 drop4, the wherein HBF of 1mL4About 40 drops, the temperature of the thermal response is 60 DEG C-
120 DEG C, the response time is 20-50 hours.
6. the metal-organic framework materials of the Zn described in any one of claim 1-4 are in methylene blue and the selectivity of acriflavinium chloride
Application in terms of absorption.
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CN106693935A (en) * | 2016-12-28 | 2017-05-24 | 福建工程学院 | Method for preparing magnetic carbon material from core-shell metal organic framework |
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CN109351334A (en) * | 2018-09-12 | 2019-02-19 | 内蒙古大学 | A kind of methylene blue adsorption number material and its preparation method and application that water is stable |
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