CN115504463B - Synthesis method and application of graphene oxide/silver molybdate composite macroscopic assembly - Google Patents
Synthesis method and application of graphene oxide/silver molybdate composite macroscopic assembly Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 121
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 67
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000002070 nanowire Substances 0.000 claims abstract description 29
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 19
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 19
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 19
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 239000010865 sewage Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- 239000002114 nanocomposite Substances 0.000 claims abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000001000 micrograph Methods 0.000 description 12
- 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 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
- 229940043267 rhodamine b Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012466 permeate Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
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- 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
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention discloses a synthesis method of a graphene oxide/silver molybdate composite macroscopic assembly body, wherein the assembly body is a binary nanocomposite, graphene oxide is coated on the surface of a silver molybdate nanowire, and the acting force between the silver molybdate nanowires is enhanced to enable the silver molybdate nanowire to be arranged to form the macroscopic assembly body; the synthesis method comprises the following steps: s1, dripping graphene oxide into a silver nitrate solution, and performing ultrasonic dispersion for 6-10 min to form a mixed solution; s2, adding an ammonium molybdate solution into the S1 to synthesize graphene oxide/silver molybdate precursors; s3, dropwise adding a dilute nitric acid solution into the S2 until the pH value is=2; and obtaining the assembly membrane material through hydrothermal reaction in a reaction kettle. The invention realizes the growth and macroscopic self-assembly of the silver molybdate nanowire in one step, and has simple and efficient synthesis process; the assembly has excellent mechanical properties, abundant porous structures and excellent selective adsorption characteristics of sulfur-containing and nitrogen-containing organic matters, is a separation membrane material with great potential, and has important application prospects in the fields of special dye recovery, sewage treatment and the like.
Description
Technical Field
The invention relates to the technical field of assembly materials, in particular to a synthetic method and application of a graphene oxide/silver molybdate composite macroscopic assembly body.
Background
In recent years, macroscopic self-assembly of nano-structures becomes a hot research field, and a series of novel macroscopic materials can be created by taking nano-structures as basic units by utilizing a self-assembly principle, so that the original characteristics of the nano-units are maintained, and a series of brand new functions are derived. Graphene two-dimensional nano materials such as graphene, graphene Oxide (GO) and the like become the most widely studied structural unit in the field of self-assembly due to unique two-dimensional structural characteristics and physical and chemical properties. The graphene and the derivative thereof which are chemically synthesized generally contain rich oxygen-containing functional groups such as hydroxyl, carboxyl and the like on the surface, so that the graphene and the derivative thereof stably exist in a high-concentration solution on the one hand, and a rich raw material is provided for macroscopic self-assembly; on the other hand, the oxygen-containing functional group and the benzene ring structure provide rich driving force for the self-assembly process, including hydrogen bonds, pi-pi stacking, hydrophobic effect and the like, and ensure the structural stability of the macroscopic assembly. In contrast, the general lack of functional groups on the surface of inorganic non-carbon nano-units results in weak inter-unit forces, which is a major reason to limit the large-scale macroscopic self-assembly of inorganic non-carbon nanowires. If the functional one-dimensional nanowire and the two-dimensional graphene can be assembled together, the application performance can be greatly improved. Therefore, developing self-assembled and high-performance one-dimensional/two-dimensional macroscopic assemblies is a hotspot in research in the current material science and separation fields.
Patent application publication No. CN102814124B reports a method for preparing graphene oxide-based porous membrane thin by using metal hydroxide nanowires and graphene oxide and related application, and Cu (OH) is synthesized first 2 Nanowires, positively charged by surface modification, and then positively charged Cu (OH) 2 The nanowires are dispersed in electronegative graphene oxide solution, and Cu (OH) is synthesized through a decompression filtration process 2 The nanowire/graphene oxide high-efficiency separation membrane. The graphene oxide-based porous membrane prepared by the method has separation performance similar to that of a graphene oxide nano separation membrane, and meanwhileThe method has good separation efficiency, the interception efficiency of rhodamine B is up to 87%, the interception efficiency of 5nm Au particles is up to 100%, the technology relates to multi-step synthesis, and the manufacturing process is complex.
Metal molybdates are of interest as an important inorganic material because of their great potential for use in various fields such as photoluminescence, optical fibers, and catalysts. In particular low-dimensional (1D) metal molybdates are widely used, e.g. Ag 2 Mo 3 O 10 ·1.8H 2 The silver O molybdate nanowire is simple in preparation process, can selectively adsorb sulfur-containing dye, and is an excellent material for preparing a selective separation membrane.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a synthesis method of a graphene oxide/silver molybdate composite macroscopic assembly body and application thereof, wherein the synthesis method simplifies the preparation process, improves the selective permeability and expands the application of the graphene oxide/silver molybdate composite macroscopic assembly body in the fields of filtering, adsorbing and treating industrial wastewater and the like.
The technical scheme adopted for solving the technical problems is as follows: a synthetic method of a graphene oxide/silver molybdate composite macroscopic assembly body comprises the steps that the composite macroscopic assembly body is a binary nanocomposite, a matrix material is a silver molybdate nanowire, and a reinforcing phase is graphene oxide; in the composite macroscopic assembly, graphene oxide is coated on the surface of silver molybdate nanowires, so that acting force among the silver molybdate nanowires is enhanced, and the silver molybdate nanowires are arranged to form the macroscopic assembly;
the synthesis method of the graphene oxide/silver molybdate composite macroscopic assembly comprises the following steps:
s1, preparing graphene oxide-silver nitrate solution: adding graphene oxide into a silver nitrate solution in a dropwise adding mode, and performing ultrasonic dispersion for 6-10 min to form a mixed solution;
s2, synthesizing graphene oxide/silver molybdate precursor: adding an ammonium molybdate solution into the mixed solution in the step S1, and synthesizing graphene oxide/silver molybdate precursors through simple solution reaction;
s3, synthesizing a graphene oxide/silver molybdate composite material: adding dilute nitric acid solution into the mixed product in the step S2 in a dropwise manner and measuring the pH value until the pH value reaches about 2; and adding the mixed liquid into a reaction kettle, and obtaining the self-assembled graphene oxide/silver molybdate material through hydrothermal reaction.
Further, in the macroscopic assembly, the volume percentage content of the graphene oxide is 0.5-12%.
Further, in the step S1, the volume ratio of the graphene oxide to the silver nitrate solution is 0.1-5: 10; wherein the concentration of the graphene oxide is 1-2mg/mL; the concentration of the silver nitrate solution is 2-3 mol/L.
Further, in the step S2, the volume ratio of the ammonium molybdate solution to the silver nitrate solution is 1.2-1.5:1, and the concentration of the ammonium molybdate solution is 0.5-1mol/L.
Further, in the step S3, the temperature of the hydrothermal reaction is 120 to 150 ℃, and the time of the hydrothermal reaction is 12 to 15 hours.
Further, in the step S3, the concentration of the dilute nitric acid solution is 0.5-6 mol/L.
The graphene oxide/silver molybdate composite macroscopic assembly can be used as a separation membrane material for filtering separation of soluble organic dye molecules in aqueous solution, special dye recovery and sewage treatment through excellent mechanical properties, abundant porous structures and excellent selective adsorption characteristics of sulfur-containing and nitrogen-containing organic matters.
Because silver ions in the silver molybdate are very easy to form N-Ag and S-Ag coordination bonds with sulfur-and nitrogen-containing organic substances, the sulfur-and nitrogen-containing organic substances can be selectively adsorbed; and the three-dimensional intercommunication porous structure of the graphene oxide/silver molybdate macroscopic assembly body allows water molecules to rapidly permeate, so that the graphene oxide/silver molybdate macroscopic assembly body has high selectivity and high membrane flux.
The beneficial effects of the invention are as follows: compared with the prior art, the method for synthesizing the graphene oxide/silver molybdate composite macroscopic assembly body and the application thereof provided by the invention have the advantages that the graphene oxide/silver molybdate macroscopic assembly body material is synthesized by adopting a graphene oxide-assisted self-assembly method, the growth and macroscopic self-assembly of the silver molybdate nanowire are realized in one step, and the synthesis process is simple and efficient; the assembly has excellent mechanical properties, rich porous structures and excellent selective adsorption characteristics of sulfur-containing and nitrogen-containing organic matters, can directly realize the filtration and separation of soluble organic dye molecules in aqueous solution, is a separation membrane material with great potential, and has important application prospects in the fields of special dye recovery, sewage treatment and the like.
Drawings
Fig. 1 is a scanning electron microscope image of the graphene oxide/silver molybdate film material synthesized in example 1.
Fig. 2 is a scanning electron microscope image of the graphene oxide/silver molybdate film material synthesized in example 2.
Fig. 3 is a scanning electron microscope image of the graphene oxide/silver molybdate film material synthesized in example 3.
Fig. 4 is a scanning electron microscope image of the graphene oxide/silver molybdate film material synthesized in example 4.
FIG. 5 is a scanning electron microscope image of the silver molybdate film material synthesized in comparative example 1.
Fig. 6 is a scanning electron microscope image of the graphene oxide/silver molybdate film material synthesized in comparative example 2.
FIGS. 7, 8 and 9 are UV-visible absorption spectra of the assembled membrane material of example 5 applied to dye separation.
Detailed Description
The invention is further illustrated by the following specific examples. These examples are merely illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
The volume content of the graphene oxide is 0.5 percent
(1) Preparing graphene oxide-silver nitrate solution: adding 0.125mL of graphene oxide into 10mL of silver nitrate solution by using a pipette to form a mixed solution, wherein the concentration of the graphene oxide is 1mg/mL; the concentration of the silver nitrate solution is 2.5mol/L, and the dispersing conditions are as follows: ultrasonic treatment is carried out for 6-10 min.
(2) Synthesizing graphene oxide/silver molybdate precursor: 15ml of an ammonium molybdate solution was added to the mixed solution in the step (1), and the concentration of the ammonium molybdate solution was 0.5mol/L. Graphene oxide/silver molybdate precursors were synthesized by simple solution reaction.
(3) Synthesizing a graphene oxide/silver molybdate composite material: dilute nitric acid was added dropwise to the mixed product in step (2) and the pH was measured until ph=2. And adding the mixed liquid into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 12 hours to obtain the self-assembled graphene oxide/silver molybdate film material. The volume and film thickness of the final material can be controlled by adjusting the amount added to the reaction vessel.
The graphene oxide/silver molybdate film material synthesized by the method has the advantages that the film thickness is 2-3mm, the shape of an assembly is regular, the formability is good, the strength is high, and the loosening is not easy to occur. The scanning electron microscope image is shown in fig. 1, and it can be seen that the silver molybdate nanowires are orderly arranged due to the induction of the graphene oxide.
Example 2
The volume content of the graphene oxide is 2%
(1) Preparing graphene oxide-silver nitrate solution: adding 0.5mL of graphene oxide into 10mL of silver nitrate solution by using a pipette to form a mixed solution, wherein the concentration of the graphene oxide is 1mg/mL; the concentration of the silver nitrate solution is 2.5mol/L, and the dispersing conditions are as follows: ultrasonic treatment is carried out for 6-10 min.
(2) Synthesizing graphene oxide/silver molybdate precursor: 15ml of an ammonium molybdate solution was added to the mixed solution in the step (1), and the concentration of the ammonium molybdate solution was 0.5mol/L. Graphene oxide/silver molybdate precursors were synthesized by simple solution reaction.
(3) Synthesizing a graphene oxide/silver molybdate composite material: dilute nitric acid was added dropwise to the mixed product in step (2) and the pH was measured until ph=2. And adding the mixed liquid into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 12 hours to obtain the self-assembled graphene oxide/silver molybdate film material. The volume and film thickness of the final material can be controlled by adjusting the amount added to the reaction vessel.
The graphene oxide/silver molybdate film material synthesized by the method has the advantages that the film thickness is 2-3mm, the shape of an assembly is regular, the formability is good, the strength is high, and the loosening is not easy to occur. The scanning electron microscope image is shown in fig. 2, and it can be seen that the silver molybdate nanowires are orderly arranged due to the induction of the graphene oxide.
Example 3
The volume content of the graphene oxide is 4%
(1) Preparing graphene oxide-silver nitrate solution: adding 1mL of graphene oxide into 10mL of silver nitrate solution by using a pipette to form a mixed solution, wherein the concentration of the graphene oxide is 1mg/mL; the concentration of the silver nitrate solution is 2.5mol/L, and the dispersing conditions are as follows: ultrasonic treatment is carried out for 6-10 min.
(2) Synthesizing graphene oxide/silver molybdate precursor: 15ml of an ammonium molybdate solution was added to the mixed solution in the step (1), and the concentration of the ammonium molybdate solution was 0.5mol/L. Graphene oxide/silver molybdate precursors were synthesized by simple solution reaction.
(3) Synthesizing a graphene oxide/silver molybdate composite material: dilute nitric acid was added dropwise to the mixed product in step (2) and the pH was measured until ph=2. And adding the mixed liquid into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 12 hours to obtain the self-assembled graphene oxide/silver molybdate film material. The volume and film thickness of the final material can be controlled by adjusting the amount added to the reaction vessel.
The graphene oxide/silver molybdate film material synthesized by the method has the advantages that the film thickness is 2-3mm, the shape of an assembly body is regular, the formability is good, the strength is high, and the loosening is not easy to occur. The scanning electron microscope image is shown in fig. 3, and the whole ordered arrangement of the silver molybdate nanowires can be seen.
Example 4
The volume content of the graphene oxide is 12%
(1) Preparing graphene oxide-silver nitrate solution: adding 3mL of graphene oxide into 10mL of silver nitrate solution by using a pipette to form a mixed solution, wherein the concentration of the graphene oxide is 1mg/mL; the concentration of the silver nitrate solution is 2.5mol/L, and the dispersing conditions are as follows: ultrasonic treatment is carried out for 6-10 min.
(2) Synthesizing graphene oxide/silver molybdate precursor: 15ml of an ammonium molybdate solution was added to the mixed solution in the step (1), and the concentration of the ammonium molybdate solution was 0.5mol/L. Graphene oxide/silver molybdate precursors were synthesized by simple solution reaction.
(3) Synthesizing a graphene oxide/silver molybdate composite material: dilute nitric acid was added dropwise to the mixed product in step (2) and the pH was measured until ph=2. And adding the mixed liquid into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 12 hours to obtain the self-assembled graphene oxide/silver molybdate film material. The volume and film thickness of the final material can be controlled by adjusting the amount added to the reaction vessel.
The graphene oxide/silver molybdate film material synthesized by the method has the advantages that the film thickness is 2-3mm, the assembly body is regular in shape, deep in color, good in formability, high in strength and not easy to loosen. The scanning electron microscope image is shown in fig. 4, and it can be seen that the silver molybdate nanowires are wrapped into strips by the graphene oxide, and are obviously arranged in an integral and orderly manner, thus greatly helping to improve the film strength.
Example 5 (formulation of 0.5% graphene oxide was used here)
The application of the graphene oxide/silver molybdate composite macroscopic assembly in dye separation can selectively adsorb sulfur-containing and nitrogen-containing organic substances because silver ions in the silver molybdate are extremely easy to form N-Ag and S-Ag coordination bonds with the sulfur-containing and nitrogen-containing organic substances; and the three-dimensional intercommunication porous structure of the graphene oxide/silver molybdate macroscopic assembly body allows water molecules to rapidly permeate, so that the graphene oxide/silver molybdate macroscopic assembly body has high selectivity and high membrane flux. The methylene blue filtration experiment shows that after being filtered by the silver molybdate film, the blue methylene blue solution becomes colorless and transparent, which indicates that the assembly only allows water molecules to permeate, and the methylene blue molecules are intercepted efficiently. As shown in fig. 7, the uv-vis absorption spectrum showed that the absorbance of the solution decreased from 1.72 to almost 0 before and after filtration, which further confirmed that the assembly could completely separate water molecules and methylene blue molecules. After filtration through the silver molybdate film, the red rhodamine B solution still maintains a red appearance, indicating that water molecules and rhodamine B molecules permeate the assembly simultaneously. As shown in fig. 8, the uv-vis absorption spectrum confirmed that the absorbance decreased from 1.76 to 1.64 before and after filtration, indicating that most rhodamine B molecules penetrated the film. When the mixed dye was filtered, the solution changed from violet to red, which indicated that only rhodamine B penetrated the assembly and methylene blue was intercepted by the assembly, as shown by the ultraviolet absorption spectrum in fig. 9, the characteristic absorption peak of methylene blue almost disappeared after filtration, and the absorption peak of rhodamine B slightly decreased, which also confirmed that the assembly intercepted methylene blue, allowing rhodamine B to freely penetrate, thereby achieving efficient separation of methylene blue and rhodamine B.
Comparative example 1
The graphene oxide content is 0:
(1) Adding 0.5mol/L ammonium molybdate solution into 2.5mol/L silver nitrate solution, wherein the volume ratio of the ammonium molybdate solution to the silver nitrate solution is 3:2, and synthesizing the silver molybdate precursor through simple solution reaction.
(2) Synthesis of silver molybdate material: dilute nitric acid was added dropwise to the mixed product in step (1) and the pH was measured until ph=2. And adding the mixed liquid into a reaction kettle, and carrying out hydrothermal reaction for 12 hours at 140 ℃ to obtain the silver molybdate film material. The amount added to the reactor can be adjusted to control the volume and film thickness of the final material.
The graphene oxide/silver molybdate film material synthesized by the method has irregular assembly body shape with the film thickness of 2-3mm, is easy to crack, has low probability of self-assembly forming by hydrothermal reaction and low integral loose strength, and is not suitable for subsequent practical application. The scanning electron microscope image is shown in fig. 5, so that the scattering disorder of the nanowires can be observed directly, and the self-assembly forming is not facilitated due to no rules.
Comparative example 2
The content of graphene oxide is 20%
(1) Preparing graphene oxide-silver nitrate solution: adding 5mL of graphene oxide into 10mL of silver nitrate solution by using a pipette to form a mixed solution, wherein the concentration of the graphene oxide is 1-2mg/mL; the concentration of the silver nitrate solution is 2-3mol/L, and the dispersing conditions are as follows: ultrasonic treatment is carried out for 6-10 min.
(2) Synthesizing graphene oxide/silver molybdate precursor: 15ml of an ammonium molybdate solution was added to the mixed solution in the step (1), and the concentration of the ammonium molybdate solution was 0.5 to 1mol/L. Graphene oxide/silver molybdate precursors were synthesized by simple solution reaction.
(3) Synthesizing a graphene oxide/silver molybdate composite material: adding dilute nitric acid dropwise to the mixed product in step (2) and measuring the pH value until the pH is about 2. And adding the mixed liquid into a reaction kettle, and carrying out hydrothermal reaction at 140 ℃ for 12 hours to obtain the self-assembled graphene oxide/silver molybdate film material. The volume and film thickness of the final material can be controlled by adjusting the amount added to the reaction vessel.
The graphene oxide/silver molybdate film material synthesized by the method has the advantages that the film thickness is 2-3mm, the graphene oxide content is high, the color of the assembled film is deep, the whole assembled body is loose in structure and difficult to form, the shape of the assembled body is irregular, and the strength is low. The scanning electron microscope image is shown in fig. 6, and it can be seen that the silver molybdate nanowires are largely wrapped by graphene oxide, and the overall morphology tends to be unstable.
In comparative example 1, only a loose solid precipitate was obtained without adding graphene oxide, and no regular macroscopic assembly was formed. In the above examples 1 to 4, a small amount of graphene oxide was added, and the graphene oxide induced the silver molybdate nanowires to undergo macroscopic self-assembly, so that a regular macroscopic assembly material could be obtained, and the size and thickness of the assembly could be controlled, and the assembly had excellent mechanical properties. The SEM test results in fig. 1-4 show that the assembly is formed by stacking one-dimensional silver molybdate, and graphene oxide is wrapped on the surface of the silver molybdate nanowires to act as a bridging agent, so that acting force among the silver molybdate nanowires is enhanced.
The above embodiments are only for illustrating the present invention, not for limiting the present invention, and various changes and modifications may be made by one of ordinary skill in the relevant art without departing from the spirit and scope of the present invention, and therefore, all equivalent technical solutions are also within the scope of the present invention, and the scope of the present invention is defined by the claims.
Claims (3)
1. A method for synthesizing a graphene oxide/silver molybdate composite macroscopic assembly body is characterized by comprising the following steps: the composite macroscopic assembly body is a binary nanocomposite, the matrix material is silver molybdate nanowires, and the reinforcing phase is graphene oxide; in the composite macroscopic assembly, graphene oxide is coated on the surface of silver molybdate nanowires, so that acting force among the silver molybdate nanowires is enhanced, and the silver molybdate nanowires are arranged to form the macroscopic assembly; in the macroscopic assembly, the volume percentage of the graphene oxide is 0.5-12%;
the synthesis method of the graphene oxide/silver molybdate composite macroscopic assembly comprises the following steps:
s1, preparing graphene oxide-silver nitrate solution: adding graphene oxide into a silver nitrate solution in a dropwise adding mode, and performing ultrasonic dispersion for 6-10 min to form a mixed solution; the volume ratio of the graphene oxide to the silver nitrate solution is 0.1-5: 10; wherein the concentration of the graphene oxide is 1-2mg/mL; the concentration of the silver nitrate solution is 2-3 mol/L;
s2, synthesizing graphene oxide/silver molybdate precursor: adding an ammonium molybdate solution into the mixed solution in the step S1, and synthesizing graphene oxide/silver molybdate precursors through simple solution reaction; the volume ratio of the ammonium molybdate solution to the silver nitrate solution is 1.2-1.5:1, and the concentration of the ammonium molybdate solution is 0.5-1 mol/L;
s3, synthesizing a graphene oxide/silver molybdate composite material: adding dilute nitric acid solution into the mixed product in the step S2 in a dropwise manner and measuring the pH value until the pH value reaches 2; transferring the mixed liquid into a reaction kettle, and obtaining a self-assembled graphene oxide/silver molybdate material through hydrothermal reaction; the temperature of the hydrothermal reaction is 120-150 ℃, and the time of the hydrothermal reaction is 12-15 hours.
2. The method for synthesizing the graphene oxide/silver molybdate composite macroscopic assembly body according to claim 1, wherein the method comprises the following steps: in the step S3, the concentration of the dilute nitric acid solution is 0.5-6 mol/L.
3. Use of a graphene oxide/silver molybdate composite macroscopic assembly according to any of claims 1 to 2, characterized in that: the graphene oxide/silver molybdate composite macroscopic assembly body can be used as a separation membrane material for filtering separation of soluble organic dye molecules in aqueous solution, special dye recovery and sewage treatment through excellent mechanical properties, rich porous structures and excellent selective adsorption characteristics of sulfur-containing and nitrogen-containing organic matters.
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