CN112958056A - Three-dimensional graphene oxide composite material and preparation method and application thereof - Google Patents
Three-dimensional graphene oxide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112958056A CN112958056A CN202110152073.2A CN202110152073A CN112958056A CN 112958056 A CN112958056 A CN 112958056A CN 202110152073 A CN202110152073 A CN 202110152073A CN 112958056 A CN112958056 A CN 112958056A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- composite material
- preparation
- dimensional graphene
- ions
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 rare earth ion Chemical class 0.000 claims abstract description 50
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 30
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 3
- 238000001338 self-assembly Methods 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000002156 adsorbate Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 32
- 238000004064 recycling Methods 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical group [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J20/20—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a three-dimensional graphene oxide composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1: preparing a graphene oxide solution by using crystalline flake graphite as a raw material; step 2: and (2) adding 2-aminobenzothiazole into the graphene oxide solution obtained in the step (1), stirring, ultrasonically mixing uniformly, then carrying out self-assembly reaction at high temperature and high pressure, and freeze-drying to obtain the composite material. The preparation method is simple, the interaction between the pi-pi action and the hydrogen bond of the 2-aminobenzothiazole and the graphene oxide at high temperature and high pressure is adopted, the agglomeration of the graphene oxide substrate is effectively avoided, a stable three-dimensional columnar structure is formed, the rare earth ion adsorption material has a good adsorption effect and good reusability on rare earth ions, the regeneration and recycling performance in the adsorption process can be realized, and the cost of the adsorption material can be greatly reduced. The composite material is expected to become an advanced adsorption material for enriching and recycling rare earth, which is widely applied.
Description
Technical Field
The invention relates to the technical field of graphene composite materials, in particular to a three-dimensional graphene oxide composite material and a preparation method and application thereof.
Background
The rare earth elements become a plurality of high-tech, traditional and future industry irreplaceable advanced materials such as super magnets, superconducting materials, chemical sensors, lasers, optical fibers, light emitting batteries, computer hard disks and the like due to unique magnetic, chemical, optical, catalytic and electrical properties of the rare earth elements. The tremendous development of emerging advanced technologies has led to an excessive demand for rare earths, and the limited resources have led to the expensive price of rare earths in the international market. In addition, such a situation causes more mining sites, and the mining of a large amount of rare earth elements causes a large amount of waste residues and waste water to be accumulated in the mining process, thereby seriously polluting the surrounding environment. If the wastewater is randomly discharged and not effectively recovered, a large amount of rare earth elements are lost and human health may be harmed. Therefore, further enrichment and recovery of valuable rare earth elements from aqueous solutions is indispensable in environmental and technical requirements. To solve these problems, various methods for separating and recovering rare earth from an aqueous solution have been proposed, including chemical precipitation, solvent extraction, ion exchange and electrochemical methods. However, most of these methods involve complicated procedures, high chemical toxicity, expensive energy consumption, and are effective only at high concentrations of rare earth ions. Therefore, it is very urgent and indispensable to develop an environment-friendly, low-cost technology for the sustainable supply of rare earth elements to enrich and recover rare earth elements. The adsorption method is simple and convenient to operate, flexible in design, non-toxic and easy to recover, and is generally regarded as an economic, environment-friendly and efficient rare earth ion recovery technology. Various adsorbents including clay, zeolite, activated carbon, chitosan, beta-cyclodextrin, silica, nanocomposite and the like have been widely used for the adsorption recovery of rare earth elements.
In order to further improve the separation and enrichment capacity of the adsorbent to rare earth elements, the research of an adsorption material which is simple to prepare, good in adsorption capacity, easy to recover and good in recycling performance is urgent.
Disclosure of Invention
The invention provides a three-dimensional graphene oxide composite material and a preparation method and application thereof, and aims to provide a composite material which is simple to prepare, good in adsorption capacity, easy to recover and good in recycling performance and a preparation method thereof, so that the rare earth ions in an aqueous solution can be effectively enriched and recovered.
In order to achieve the above object, the present invention provides a method for preparing a three-dimensional graphene oxide composite material, comprising the following steps:
step 1: preparing a graphene oxide solution by using crystalline flake graphite as a raw material;
step 2: and (2) adding 2-aminobenzothiazole into the graphene oxide solution obtained in the step (1), stirring, ultrasonically mixing uniformly, then carrying out self-assembly reaction at high temperature and high pressure, and freeze-drying to obtain the composite material.
Preferably, in the step 1, a graphene oxide solution of 3-12 mg/mL is prepared by using a modified Hummers method.
Preferably, in the step 2, the mass ratio of the graphene oxide to the 2-aminobenzothiazole is 1: 1-30: 1.
Preferably, in the step 2, the stirring time is 1-20 min, and the ultrasonic time is 5-60 min.
Preferably, in the step 2, the high-temperature and high-pressure conditions are provided by an oven and a high-temperature and high-pressure reaction kettle, the reaction temperature is 100-200 ℃, and the reaction time is 2-10 hours.
Preferably, in the step 2, after the reaction is completed, the reaction product is naturally cooled to room temperature, ultrapure water is added into the obtained composite material until the product concentration is 10-20 mg/mL, the composite material is transferred to a quick freezing machine at-50 ℃ for quick freezing, and finally the composite material is transferred to a vacuum freeze drying machine for drying.
The invention also provides the three-dimensional graphene oxide composite material prepared by the method.
The invention also provides an application of the three-dimensional graphene oxide composite material in efficient recovery of rare earth ions in an aqueous solution.
Preferably, the rare earth ions are corresponding chloride salts, and the concentration of the adsorbate is 1-100 mg/L.
Preferably, the rare earth ions include lanthanum ions, erbium ions, ytterbium ions, neodymium ions and yttrium ions.
The scheme of the invention has the following beneficial effects:
according to the invention, 2-aminobenzothiazole interacts with graphene oxide under high temperature and high pressure through pi-pi action and hydrogen bonds to generate the aerogel composite material with a three-dimensional structure, and the three-dimensional aerogel composite material is formed by utilizing the interpenetration action of organic molecules 2-aminobenzothiazole and the non-covalent bond acting force between the organic molecules and the graphene oxide. The composite material reserves rich oxygen-containing functional groups (carboxyl and hydroxyl) on the surface of graphene oxide and sulfur-nitrogen heteroatoms and amino on 2-aminobenzothiazole molecules as adsorption active sites for rare earth ions, and the adsorption recognition capability of the composite material for the rare earth ions is effectively improved by introducing the amino of 2-aminobenzothiazole and the nitrogen-sulfur heteroatoms on the surface of the graphene oxide.
The aerogel structure of the three-dimensional graphene oxide composite material can effectively avoid the agglomeration of a graphene oxide substrate, can realize the regeneration and recycling performance in the adsorption process, and can greatly reduce the cost of the adsorption material. The composite material is expected to become an advanced adsorption material for enriching and recycling rare earth, which is widely applied.
Drawings
FIG. 1 is a three-dimensional structure profile of a three-dimensional graphene oxide composite material according to the present invention (FIG. 1 a); comparison graph of adsorption capacity of the composite material on five rare earth ions of lanthanum, erbium, ytterbium, neodymium and yttrium (figure 1 b); 2-Aminobenzothiazole (ABT), Graphene Oxide (GO) and three-dimensional graphene oxide composite material (GO-ABT)15:1/120℃/6h) And a fourier transform infrared spectrum (fig. 1c) of the three-dimensional graphene oxide composite material after erbium ions are adsorbed;
fig. 2 is an X-ray photoelectron spectroscopy (XPS) of graphene oxide, a three-dimensional graphene oxide composite material, and a composite material after adsorption of erbium ions, respectively (fig. 2 a); a peak-splitting fitting graph (figure 2b) of nitrogen element (N) of the three-dimensional graphene oxide composite material before and after erbium ion adsorption; a peak-splitting fitting graph (fig. 2c) of oxygen element (O) of the three-dimensional graphene oxide composite material before and after erbium ion adsorption; a peak-splitting fitting graph (figure 2d) of the sulfur element (S) of the three-dimensional graphene oxide-aromatic heterocyclic compound composite material before and after erbium ion adsorption;
fig. 3 is a graph showing the recycling effect of the three-dimensional graphene oxide composite material according to the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Example 1
The preparation method of the three-dimensional graphene oxide composite material in the present example is as follows:
preparing a graphene oxide solution by using crystalline flake graphite as a raw material and adopting an improved Hummers method, and diluting the graphene oxide solution to 5mg/mL for later use.
50mg of 2-aminobenzothiazole were weighed out for further use.
And adding 10mL of graphene oxide solution into 2-aminobenzothiazole, stirring for 15min, and performing mixing ultrasonic treatment for 40min to obtain a uniformly mixed dispersion liquid.
And (3) moving the mixed dispersion liquid to a high-temperature high-pressure reaction kettle, carrying out hydrothermal reaction for 4h at the temperature of 140 ℃, and naturally cooling to room temperature for later use.
And adding 20mL of ultrapure water into the obtained composite material, transferring the composite material to a quick freezer at the temperature of-50 ℃ for quick freezing, and finally transferring the composite material to a vacuum freeze dryer for drying to obtain the three-dimensional graphene oxide composite material.
Example 3
The preparation method of the three-dimensional graphene oxide composite material in the present example is as follows:
preparing a graphene oxide solution by using crystalline flake graphite as a raw material and adopting an improved Hummers method, and diluting the graphene oxide solution to 5mg/mL for later use.
5mg of 2-aminobenzothiazole were weighed out for further use.
And adding 10mL of graphene oxide solution into 2-aminobenzothiazole, stirring for 10min, and performing ultrasonic mixing for 20min to obtain a uniformly mixed dispersion liquid.
And (3) moving the mixed dispersion liquid to a high-temperature high-pressure reaction kettle, carrying out hydrothermal reaction for 4h at the temperature of 100 ℃, and naturally cooling to room temperature for later use.
And adding 20mL of ultrapure water into the obtained composite material, transferring the composite material to a quick freezer at the temperature of-50 ℃ for quick freezing, and finally transferring the composite material to a vacuum freeze dryer for drying to obtain the three-dimensional graphene oxide composite material.
Example 4
The preparation method of the three-dimensional graphene oxide composite material in the present example is as follows:
preparing a graphene oxide solution by using crystalline flake graphite as a raw material and adopting an improved Hummers method, and diluting the graphene oxide solution to 5mg/mL for later use.
3.33mg of 2-aminobenzothiazole were weighed out for further use.
And adding 10mL of graphene oxide solution into 2-aminobenzothiazole, stirring for 5min, and performing ultrasonic mixing for 15min to obtain a uniformly mixed dispersion liquid.
And (3) moving the mixed dispersion liquid to a high-temperature high-pressure reaction kettle, carrying out hydrothermal reaction for 3h at 160 ℃, and naturally cooling to room temperature for later use.
And adding 20mL of ultrapure water into the obtained composite material, transferring the composite material to a quick freezer at the temperature of-50 ℃ for quick freezing, and finally transferring the composite material to a vacuum freeze dryer for drying to obtain the three-dimensional graphene oxide composite material.
Example 5
The preparation method of the three-dimensional graphene oxide composite material in the present example is as follows:
preparing a graphene oxide solution by using crystalline flake graphite as a raw material and adopting an improved Hummers method, and diluting the graphene oxide solution to 5mg/mL for later use.
2.5mg of 2-aminobenzothiazole were weighed out for further use.
And adding 10mL of graphene oxide solution into 2-aminobenzothiazole, stirring for 5min, and performing ultrasonic mixing for 10min to obtain a uniformly mixed dispersion liquid.
And (4) moving the mixed dispersion liquid to a high-temperature high-pressure reaction kettle, carrying out hydrothermal reaction for 8h at the temperature of 120 ℃, and naturally cooling to room temperature for later use.
And adding 20mL of ultrapure water into the obtained composite material, transferring the composite material to a quick freezer at the temperature of-50 ℃ for quick freezing, and finally transferring the composite material to a vacuum freeze dryer for drying to obtain the three-dimensional graphene oxide composite material.
Example 6
The preparation method of the three-dimensional graphene oxide composite material in the present example is as follows:
preparing a graphene oxide solution by using crystalline flake graphite as a raw material and adopting an improved Hummers method, and diluting the graphene oxide solution to 5mg/mL for later use.
3.3mg of 2-aminobenzothiazole were weighed out for further use.
And adding 10mL of graphene oxide solution into 2-aminobenzothiazole, stirring for 5min, and performing ultrasonic mixing for 15min to obtain a uniformly mixed dispersion liquid.
And (4) moving the mixed dispersion liquid to a high-temperature high-pressure reaction kettle, carrying out hydrothermal reaction for 6h at the temperature of 120 ℃, and naturally cooling to room temperature for later use.
And adding 20mL of ultrapure water into the obtained composite material, transferring the composite material to a quick freezer at the temperature of-50 ℃ for quick freezing, and finally transferring the composite material to a vacuum freeze dryer for drying to obtain the three-dimensional graphene oxide composite material.
The three-dimensional graphene oxide composite material prepared in example 6 was used to adsorb rare earth ions in an aqueous solution, and lanthanum ions (La), erbium ions (Er), ytterbium ions (Yb), neodymium ions (Nd), and yttrium ions (Y) were selected to perform adsorption experiments, respectively. And analyzing the morphology, chemical composition and bonding mode of the material by adopting a scanning electron microscope, a Fourier infrared spectrum and an X-ray photoelectron spectrum. The adsorption results and the characterization of the materials are shown in FIGS. 1-2.
Fig. 1a shows that the three-dimensional graphene oxide composite material becomes a complete three-dimensional columnar structure after being dried, and a scanning electron microscope image shows that the structure of the composite material becomes a large unfolded sheet layer with few folds. From fig. 1b, the three-dimensional graphene oxide composite material has better adsorption capacity for several rare earth ions.
As can be seen from fig. 1C, the three-dimensional graphene oxide composite material is successfully synthesized, and due to pi-pi action and hydrogen bonding action between the 2-aminobenzothiazole and the functional group of the graphene oxide, compared with a characteristic absorption peak of pure graphene oxide, the hydroxyl (-OH) and carbonyl (-C ═ O) peaks of the three-dimensional graphene oxide composite material have obvious movement. Meanwhile, after the three-dimensional graphene oxide composite material adsorbs erbium ions (Er), hydroxyl (-OH) and carbonyl (-C ═ O) peaks obviously move to the low wave number direction, which shows that the composite material successfully adsorbs the erbium ions (Er).
Fig. 2 further shows the synthesis of the three-dimensional graphene oxide composite material and the adsorption of erbium ions (Er). From fig. 2a, the new combination energy of nitrogen (N) and sulfur (S) and the new combination energy of erbium (Er) after erbium ion adsorption of the composite material can be clearly seen. Respectively performing peak-splitting fitting on a nitrogen (N) element, an oxygen (O) element and a sulfur (S) element of the front-back three-dimensional graphene oxide-aromatic heterocyclic compound composite material for adsorbing erbium ions (see fig. 2 b-2 d). Performing peak-splitting fitting compared with nitrogen (N) element of the three-dimensional graphene oxide composite material before adsorption, and adsorbing erbium ions, as shown in figure 2b, -NH2And C-N ═ C peaks shift from 400.87 and 400.27eV to 400.68 and 399.76eV, respectively; the peak fitting plots of the oxygen (O) element before and after the adsorption of erbium ions showed that the carboxyl, hydroxyl and carbonyl peaks shifted from 533.52, 532.74 and 531.90eV to 533.53, 532.70 and 531.68eV, respectively (see fig. 2 c); fitting plots of the partial peaks of sulfur (S) before and after erbium ion adsorption showed that the C-S peak shifted from 164.61eV to 164,82eV (see fig. 2 d). These results indicate that the adsorption mechanism of the three-dimensional graphene oxide composite material to erbium ions is the complexation of free electrons of nitrogen, oxygen and sulfur of the composite material and erbium ions and the electrostatic attraction of carboxyl and erbium ions.
As can be seen from fig. 3, the three-dimensional graphene oxide composite material has an excellent recycling effect, and after 10 cycles of erbium ion adsorption-desorption, the adsorption rate of 100% and the elution rate of about 90% are still maintained.
The three-dimensional graphene oxide composite material prepared by the invention is simple to prepare, has a stable three-dimensional columnar structure, is good in reusability, has good adsorption performance on rare earth ions, and can realize effective adsorption and enrichment of the rare earth ions in an aqueous solution.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a three-dimensional graphene oxide composite material is characterized by comprising the following steps:
step 1: preparing a graphene oxide solution by using crystalline flake graphite as a raw material;
step 2: and (2) adding 2-aminobenzothiazole into the graphene oxide solution obtained in the step (1), stirring, ultrasonically mixing uniformly, then carrying out self-assembly reaction at high temperature and high pressure, and freeze-drying to obtain the composite material.
2. The method for preparing the three-dimensional graphene oxide composite material according to claim 1, wherein in the step 1, a modified Hummers method is adopted to prepare a 3-12 mg/mL graphene oxide solution.
3. The preparation method of the three-dimensional graphene oxide composite material according to claim 1, wherein in the step 2, the mass ratio of the graphene oxide to the 2-aminobenzothiazole is 1: 1-30: 1.
4. The preparation method of the three-dimensional graphene oxide composite material according to claim 1, wherein in the step 2, the stirring time is 1-20 min, and the ultrasonic time is 5-60 min.
5. The preparation method of the three-dimensional graphene oxide composite material according to claim 1, wherein in the step 2, the high-temperature and high-pressure conditions are provided by an oven and a high-temperature and high-pressure reaction kettle, the reaction temperature is 100-200 ℃, and the reaction time is 2-10 hours.
6. The preparation method of the three-dimensional graphene oxide composite material according to claim 1, wherein in the step 2, after the reaction is completed, the material is naturally cooled to room temperature, ultrapure water is added into the obtained composite material until the product concentration is 10-20 mg/mL, the material is transferred to a freezer at-50 ℃ for quick freezing, and then the material is transferred to a vacuum freeze dryer for drying.
7. A three-dimensional graphene oxide composite material, wherein the composite material is prepared by the method according to any one of claims 1 to 6.
8. The application of the three-dimensional graphene oxide composite material prepared by the method of any one of claims 1 to 6 in efficient recovery of rare earth ions in an aqueous solution.
9. The use according to claim 8, wherein the rare earth ions are the corresponding chloride salts and the adsorbate concentration is 1-100 mg/L.
10. Use according to claim 8, wherein the rare earth ions comprise lanthanum ions, erbium ions, ytterbium ions, neodymium ions, yttrium ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110152073.2A CN112958056B (en) | 2021-02-03 | 2021-02-03 | Three-dimensional graphene oxide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110152073.2A CN112958056B (en) | 2021-02-03 | 2021-02-03 | Three-dimensional graphene oxide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112958056A true CN112958056A (en) | 2021-06-15 |
| CN112958056B CN112958056B (en) | 2022-04-15 |
Family
ID=76275037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110152073.2A Expired - Fee Related CN112958056B (en) | 2021-02-03 | 2021-02-03 | Three-dimensional graphene oxide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112958056B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102861559A (en) * | 2012-09-24 | 2013-01-09 | 浙江工商大学 | Production method of polyacrylonitrile chelating resin metal adsorbent |
| CN103301817A (en) * | 2013-05-03 | 2013-09-18 | 浙江工商大学 | Chelate fiber ABTF and synthetic method thereof |
| CN103392018A (en) * | 2011-02-22 | 2013-11-13 | 独立行政法人物质·材料研究机构 | Method for extraction and separation of lanthanoid elements and actinoid elements, and means for extraction and separation of lanthanoid elements and actinoid elements |
| CN103861565A (en) * | 2012-12-14 | 2014-06-18 | 吉首大学 | Preparation of linear amino modified graphene oxide adsorption material |
| CN104984728A (en) * | 2015-07-08 | 2015-10-21 | 常州大学 | Method for synthesizing nitrogen-doped graphene hydrogel in one step and using nitrogen-doped graphene hydrogel for electrically adsorbing heavy metal ions in water |
| CN105457601A (en) * | 2015-12-01 | 2016-04-06 | 济南大学 | Preparation and application of folic acid modified magnetic graphene oxide adsorbent |
| CN106179277A (en) * | 2016-08-31 | 2016-12-07 | 武汉大学 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
| CN106362697A (en) * | 2016-11-10 | 2017-02-01 | 过冬 | Heavy metal iron adsorption material modified by aminated graphene oxide |
| CN106693904A (en) * | 2016-12-26 | 2017-05-24 | 信阳师范学院华锐学院 | L-arginine/graphene oxide composite material, preparation method and application |
| CN108212117A (en) * | 2016-12-15 | 2018-06-29 | 南京理工大学 | A kind of preparation method of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material |
| CN108435134A (en) * | 2018-05-10 | 2018-08-24 | 中南大学 | The preparation and its application of egg white-graphene oxide self-assembled compound material |
-
2021
- 2021-02-03 CN CN202110152073.2A patent/CN112958056B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103392018A (en) * | 2011-02-22 | 2013-11-13 | 独立行政法人物质·材料研究机构 | Method for extraction and separation of lanthanoid elements and actinoid elements, and means for extraction and separation of lanthanoid elements and actinoid elements |
| CN102861559A (en) * | 2012-09-24 | 2013-01-09 | 浙江工商大学 | Production method of polyacrylonitrile chelating resin metal adsorbent |
| CN103861565A (en) * | 2012-12-14 | 2014-06-18 | 吉首大学 | Preparation of linear amino modified graphene oxide adsorption material |
| CN103301817A (en) * | 2013-05-03 | 2013-09-18 | 浙江工商大学 | Chelate fiber ABTF and synthetic method thereof |
| CN104984728A (en) * | 2015-07-08 | 2015-10-21 | 常州大学 | Method for synthesizing nitrogen-doped graphene hydrogel in one step and using nitrogen-doped graphene hydrogel for electrically adsorbing heavy metal ions in water |
| CN105457601A (en) * | 2015-12-01 | 2016-04-06 | 济南大学 | Preparation and application of folic acid modified magnetic graphene oxide adsorbent |
| CN106179277A (en) * | 2016-08-31 | 2016-12-07 | 武汉大学 | Sulfhydrylation graphene oxide/polyvinyl alcohol macropore composite balls adsorbent and its preparation method and application |
| CN106362697A (en) * | 2016-11-10 | 2017-02-01 | 过冬 | Heavy metal iron adsorption material modified by aminated graphene oxide |
| CN108212117A (en) * | 2016-12-15 | 2018-06-29 | 南京理工大学 | A kind of preparation method of three-dimensional graphene oxide/polyethyleneimine/carboxymethyl cellulose composite material |
| CN106693904A (en) * | 2016-12-26 | 2017-05-24 | 信阳师范学院华锐学院 | L-arginine/graphene oxide composite material, preparation method and application |
| CN108435134A (en) * | 2018-05-10 | 2018-08-24 | 中南大学 | The preparation and its application of egg white-graphene oxide self-assembled compound material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112958056B (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Carbonaceous materials as adsorbents for CO2 capture: synthesis and modification | |
| Liu et al. | Valorization of coffee grounds to biochar-derived adsorbents for CO2 adsorption | |
| Zhang et al. | Ultramicroporous carbons with extremely narrow pore size distribution via in-situ ionic activation for efficient gas-mixture separation | |
| CN109437202B (en) | Two-dimensional transition metal carbon (nitride) aerogel and preparation method and application thereof | |
| Ma et al. | High iodine adsorption by lignin-based hierarchically porous flower-like carbon nanosheets | |
| US20130041060A1 (en) | Porous Polymer and Synthetic Method Thereof | |
| Wang et al. | Mixed-matrix membranes consisting of Pebax and novel nitrogen-doped porous carbons for CO2 separation | |
| Liu et al. | Mercury adsorption from aqueous solution by regenerated activated carbon produced from depleted mercury-containing catalyst by microwave-assisted decontamination | |
| CN111482163B (en) | Preparation method of enhanced chitosan-based aerogel for adsorbing heavy metal ions | |
| CN111514868B (en) | Magnetic nano carbon, preparation method thereof and application thereof in removing micro plastic in water | |
| CN105417526A (en) | Three-dimensional graphene aerogel material for dye adsorption and preparation method thereof | |
| CN113117669A (en) | Cryptomelane type manganese dioxide oxidant with three-dimensional structure and preparation method and application thereof | |
| CN115779860A (en) | Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof | |
| CN110090624B (en) | Preparation method and application of magnetic covalent organic framework material | |
| CN112958056B (en) | Three-dimensional graphene oxide composite material and preparation method and application thereof | |
| Ao et al. | Polyethyleneimine incorporated chitosan/α-MnO2 nanorod honeycomb-like composite foams with remarkable elasticity and ultralight property for the effective removal of U (VI) from aqueous solution | |
| CN110711554A (en) | Preparation method and application of magnetic activated carbon | |
| Xie et al. | Synthesis of Spherical Composite CMC‐LTO‐EGDE‐ME for Lithium Recovery from Geothermal Water | |
| CN110339819A (en) | A kind of preparation and application of stalk cellulose/graphene oxide composite material | |
| Khan et al. | Highly porous polyaniline-or polypyrrole-derived carbons: Preparation, characterization, and applications in adsorption | |
| CN112934179B (en) | Graphene oxide-N-benzyloxycarbonyl glycine composite material and preparation method and application thereof | |
| Demir et al. | Enhanced water stability and high CO 2 storage capacity of a Lewis basic sites-containing zirconium metal–organic framework | |
| CN108311109A (en) | A kind of molasses adsorbing material and its preparation method and application | |
| CN110180510B (en) | Nano thin film and device for slowing down reservoir overturning phenomenon | |
| CN112547016B (en) | Graphene oxide composite material and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220415 |