CN112547016A - Graphene oxide composite material and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of composite materials. An organic molecule 1, 3-bis [ tri (hydroxymethyl) methylamino ] propane rich in oxygen/nitrogen and graphene oxide are subjected to effective covalent coupling, and the graphene oxide composite material with a stable structure and good selectivity is prepared. The stable chemically bonded composite product is obtained by carrying out esterification and amidation reactions on graphene oxide and 1, 3-bis [ tri (hydroxymethyl) methylamino ] propane under the catalytic condition. The graphene oxide composite material has different adsorption capacities on various substances due to different adsorption mechanisms, shows adsorption selectivity on organic matters and adsorption rejection on certain metal ions, and can realize efficient adsorption of organic matters in an aqueous solution and effective separation of inorganic and organic pollutant mixtures; and the composite material has good recycling performance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a graphene oxide composite material and a preparation method and application thereof.
Background
Rare earth elements are essential in many advanced technology and energy applications, and the global demand for rare earth elements has proliferated over the past two decades. Because rare earth elements are geographically unevenly distributed, recovery of rare earth is one method of supplemental mining to maintain sustainable supply. However, the rare earth elements industrially separated from mineral ores require further purification, and the aqueous environment contains a large amount of other elements and contaminants, such as lead, copper, organic contaminants, etc., which generally interfere with the enrichment, recovery and detection of rare earth elements. Meanwhile, most organic compounds, such as phenol and derivatives thereof, are widely used in the pharmaceutical, textile, wood and other industries, and heavy metal ions and dyes are common elements in environmental pollutants. Studies have shown that many toxic metal ions, such as zinc, copper, nickel, mercury, cadmium, lead and chromium, are detected in industrial wastewater. In addition, due to their high biotoxicity, mutagenic and carcinogenic effects, the release of dyes into the environment without proper treatment poses serious problems, endangering humans, aquatic organisms and wild life. To solve these problems and minimize their hazards, water treatment is required, and existing water treatment methods include chemical processes, membrane separation, organic solvent extraction, ion exchange methods, sedimentation methods, and adsorption.
The adsorption method is one of the important methods for water treatment, has the characteristics of wide application range, good treatment effect, reusability of the adsorbent and the like, and is characterized by applying the appropriate adsorbent. The prior common adsorbent has small density of surface active sites, small adsorption activation energy in a heterogeneous system, slow reaction kinetics, unbalanced adsorption and low mass transfer rate of the surface of the adsorbent, and in recent years, various adsorbents such as clay mineral materials, carbon nanotubes, silicon dioxide, cellulose-graphene oxide aerogel, chitosan, titanium dioxide, beta-cyclodextrin and the like are widely used for adsorbing and separating various rare earth, heavy metals and organic substances.
Graphene oxide is rich in oxygen-containing functional groups and aromatic functional groups, and can interact with various particles through pi-pi stacking interaction, Lewis acid-base interaction, hydrogen bonds, electrostatic attraction and other intermolecular interactions. The graphene oxide has the advantages of high mechanical strength, large specific surface area, high chemical stability, high thermal stability and the like, and the graphene oxide material is widely applied to adsorption and separation of inorganic metal ions and organic pollutants in an aqueous solution. The functionalized graphene oxide has a wide application prospect in the field of adsorption separation by taking graphene oxide as a substrate material and chemically modifying the graphene oxide with novel molecules.
At present, researchers focus on efficient enrichment, selective separation and material recycling of substances in water treatment, and a three-dimensional composite material is mostly synthesized by a simple hydrothermal self-assembly method, but the three-dimensional material assembled by hydrothermal physics is loose and porous, has low selectivity and is easy to fall off, and the defects of complex operation, poor separation effect and low adsorption capacity exist in the adsorption separation process. Therefore, the search for an adsorbent with stable structure, good selective separation performance and good adsorption capacity is urgent.
Disclosure of Invention
The invention provides a graphene oxide composite material and a preparation method and application thereof, and aims to provide a composite material which is stable in structure, good in selectivity, good in separation performance and strong in adsorption capacity and a preparation method thereof, so that inorganic ions and organic pollutants in an aqueous solution can be effectively adsorbed and separated.
In order to achieve the above object, the present invention provides a method for preparing a graphene oxide composite material, comprising the steps of:
s1: preparing graphene oxide by taking crystalline flake graphite as a raw material, and freeze-drying to obtain dried graphene oxide;
s2: and (2) dissolving the graphene oxide obtained in the step (S1) by using anhydrous N, N-dimethylformamide to obtain a graphene oxide solution, then uniformly mixing the graphene oxide solution with 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, carrying out esterification and amidation reactions under the condition of an anhydrous catalyst, and drying to obtain the composite material.
Preferably, in S1, crystalline flake graphite is used as a raw material, and a modified Hummers method is used to prepare graphene oxide.
Preferably, in S2, the concentration of the graphene oxide solution is 2.5-75 mg/mL, and the mass ratio of the graphene oxide to the 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane is 1: 1-1: 10.
Preferably, in the step S2, the mass ratio of the catalyst to the graphene oxide is 1: 5-20, the catalyst adopts N, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine in combination, and the mass ratio of the N, N' -dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 5: 1-1: 5.
Preferably, in the step S2, the reaction equipment adopts a moisture-proof reflux device, the reaction temperature is 150-180 ℃, and the reaction time is 4-12 h.
Preferably, in S2, the reaction is performed under magnetic stirring all the time, after the reaction is completed, the reaction is naturally cooled to room temperature, the obtained product is vacuum filtered, the filter residue is repeatedly washed with ethanol and deionized water in sequence, and the filter residue is collected and dried after impurities are removed.
The invention also provides a graphene oxide composite material prepared by the preparation method.
The invention also provides application of the graphene oxide composite material in selective adsorption and separation of inorganic ions and organic pollutants in an aqueous solution.
Preferably, the inorganic ions comprise chloride, sulfate and nitrate, the organic pollutants comprise tert-butyl hydroquinone, m-nitrophenol, p-nitrophenol, alizarin red S and neutral red, and the concentration of the adsorbate is 10-100 mg/L.
Preferably, the inorganic ions include rare earth ions and heavy metal ions.
The scheme of the invention has the following beneficial effects:
according to the invention, the graphene oxide and 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane are subjected to esterification and amidation reactions under the condition of a catalyst, secondary amine and abundant hydroxyl on the 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane and abundant carboxyl on the graphene oxide are subjected to amidation and esterification to synthesize a composite material with a stable structure, and the composite material is bonded to a certain extent, so that different substances show different adsorption capacities due to different adsorption mechanisms, and the composite material has excellent selective adsorption and enrichment performances on different substances, and effective adsorption and separation are realized.
The graphene oxide composite adsorbent provided by the invention only has an adsorption effect on heavy metals and organic pollutants, but hardly has an adsorption capacity on rare earth ions, so that the graphene oxide composite adsorbent can be applied to separation of heavy metals and organic pollutants from rare earth ions. Meanwhile, the graphene oxide composite adsorbent provided by the invention shows obvious difference in adsorption capacity to heavy metals and organic pollutants, is beneficial to practical application in separation of inorganic and organic pollutant mixtures, and has high efficiency in adsorption of organic pollutants. And the composite material can realize good recycling performance, and can greatly reduce the cost of the adsorbent.
Drawings
FIG. 1 shows the comparison of the adsorption capacities of the graphene oxide composite material of the present invention on rare earth ions (lanthanum and erbium), heavy metal ions (copper and lead), organic phenols (tert-butyl hydroquinone, m-nitrophenol and p-nitrophenol), and dyes (alizarin red S and neutral red)FIG. 1 (a); 1, 3-bis [ tris (hydroxymethyl) methylamino]Propane (BTP), Graphene Oxide (GO), graphene oxide composite (GO-BTP), and post-adsorption graphene oxide composite (GO-BTP-n, n = Pb)2+NR, PNP) fourier transform infrared spectrogram (fig. 1 b);
fig. 2 is an X-ray photoelectron spectroscopy (XPS) spectrum of graphene oxide, a graphene oxide composite material and a composite material after adsorption of lead ions, respectively (fig. 2 a); a peak fitting plot of the oxygen element (O) of graphene oxide (fig. 2 b); a peak fitting graph of oxygen element (O) of the graphene oxide composite material (fig. 2 c); a peak fitting graph of nitrogen element (N) of the graphene oxide composite material (fig. 2 d);
FIG. 3 is a fitting graph of the peak separation of the oxygen element (O) of the graphene oxide composite material after adsorption of lead ions, p-nitrophenol and neutral red (FIGS. 3a-3 c); a peak fitting plot of carbon element (C) of the graphene oxide composite (fig. 3 d); and respectively adsorbing the paranitrophenol and the neutral red carbon element (C) of the oxidized graphene composite material, and fitting the peak (fig. 3e and 3 f).
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 graphene oxide composite material in the present example is as follows:
s1, preparing graphene oxide by using crystalline flake graphite as a raw material through a modified Hummers method, and freeze-drying the graphene oxide for later use;
s2, measuring 60 mL of anhydrous N, N-dimethylformamide treated by a molecular sieve into a 250 mL round-bottom flask, adding graphene oxide obtained by 1 g S1, performing ultrasonic treatment for 30 min, stirring in a proper amount to fully dissolve the graphene oxide, and sealing for later use;
weighing 2 g of 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, 0.1 g N, N' -dicyclohexylcarbodiimide and 0.1 g of 4-dimethylaminopyridine in turn in the round-bottom flask, sealing, carrying out ultrasonic treatment for 30 minutes, and stirring and mixing uniformly to obtain a mixed reaction solution;
transferring the mixed reaction liquid into a moisture-proof reflux device, heating to 160 ℃, and heating for reflux reaction for 8 hours under continuous magnetic stirring;
and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the obtained product, repeatedly washing the filter residue with 60 mL of ethanol for 6 times, repeatedly washing the filter residue with deionized water for 6 times, removing impurities, collecting the filter residue, and drying to obtain the graphene oxide composite material.
Example 2
The preparation method of the graphene oxide composite material in the present example is as follows:
s1, preparing graphene oxide by using crystalline flake graphite as a raw material through a modified Hummers method, and freeze-drying the graphene oxide for later use;
s2, measuring 90 mL of anhydrous N, N-dimethylformamide treated by a molecular sieve into a 250 mL round-bottom flask, adding 1.5 g S1-obtained graphene oxide into the flask, carrying out ultrasonic treatment for 30 min, stirring the mixture in a proper amount to fully dissolve the graphene oxide, and sealing the mixture for later use;
sequentially weighing 3 g of 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, 0.15 g N, N' -dicyclohexylcarbodiimide and 0.15 g of 4-dimethylaminopyridine in the round-bottom flask, sealing, carrying out ultrasonic treatment for 30 minutes, and stirring and mixing uniformly to obtain a mixed reaction solution;
transferring the mixed reaction liquid into a moisture-proof reflux device, heating to 160 ℃, and heating for reflux reaction for 10 hours under continuous magnetic stirring;
and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the obtained product, repeatedly washing the filter residue with 70 mL of ethanol for 7 times, repeatedly washing the filter residue with deionized water for 7 times, removing impurities, collecting the filter residue, and drying to obtain the graphene oxide composite material.
Example 3
The preparation method of the graphene oxide composite material in the present example is as follows:
s1, preparing graphene oxide by using crystalline flake graphite as a raw material through a modified Hummers method, and freeze-drying the graphene oxide for later use;
s2, weighing 30 mL of anhydrous N, N-dimethylformamide treated by a molecular sieve into a 250 mL round-bottom flask, adding 22.5 g S1-obtained graphene oxide into the flask, performing ultrasonic treatment for 30 min, stirring the mixture in a proper amount to fully dissolve the graphene oxide, and sealing the mixture for later use;
weighing 22.5 g of 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, 1.8 g of 1.8 g N, N' -dicyclohexylcarbodiimide and 2.7 g of 4-dimethylaminopyridine in sequence in the round-bottom flask, sealing, carrying out ultrasonic treatment for 30 minutes, and stirring and mixing uniformly to obtain a mixed reaction solution;
transferring the mixed reaction liquid into a moisture-proof reflux device, heating to 180 ℃, and heating and refluxing for reaction for 12 hours under continuous magnetic stirring;
and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration on the obtained product, repeatedly washing the filter residue with 80 mL of ethanol for 8 times, repeatedly washing the filter residue with deionized water for 8 times, removing impurities, collecting the filter residue, and drying to obtain the graphene oxide composite material.
The graphene oxide composite material prepared in example 1 is used to adsorb inorganic ions and organic pollutants in an aqueous solution, and lanthanum ions (La), erbium ions (Er), copper ions (Cu), lead ions (Pb), tert-butyl hydroquinone (TBHQ), m-nitrophenol (MNP), p-nitrophenol (PNP), alizarin red s (ars), and Neutral Red (NR) are selected to respectively perform adsorption experiments. Fourier infrared spectrum and X-ray photoelectron spectrum are adopted to analyze the chemical composition and bonding mode of the material. The adsorption results and the characterization of the materials are shown in FIGS. 1-3.
As can be seen from fig. 1a, the graphene oxide composite material has an obvious adsorption effect only on heavy metals and organic pollutants, but has almost no adsorption capacity on rare earth ions, and thus can be applied to separation of heavy metals and organic pollutants from rare earth ions. Meanwhile, the composite material shows obvious difference in the adsorption capacity to heavy metals and organic pollutants, is beneficial to the practical application of the composite material in the separation of inorganic and organic pollutant mixtures, and has higher efficiency in the adsorption of the organic pollutants.
As can be seen from fig. 1b, the synthesis of the graphene oxide composite material is successful, and due to the esterification and amidation between the 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane molecule and the graphene oxide functional group, a new distinct absorption peak appears compared with the characteristic absorption peak of pure graphene oxide. Meanwhile, the graphene oxide composite material has new characteristic peaks after adsorbing p-nitrophenol, neutral red and lead ions respectively, and the composite material has better adsorption to the p-nitrophenol, the neutral red and the lead ions.
It can be further seen from fig. 2 that esterification and amidation of the graphene oxide composite was successful. From fig. 2a, the binding energy of nitrogen (N) newly appeared in the composite material and the binding energy of lead (Pb) newly appeared after adsorption of lead ions are clearly seen. Respectively, peak fitting is performed on the oxygen (O) element of the graphene oxide composite material, as shown in fig. 2b and 2c, and comparison shows that a new ester group peak appears at 532.22 eV in the composite material, and in addition, peak fitting is performed on the nitrogen (N) element of the graphene oxide composite material, as shown in fig. 2d, nitrogen of the composite material is found to exist in the form of amide, which indicates successful esterification and amidation of the graphene oxide composite material.
It can be seen from fig. 3 that the composite material has different adsorption mechanisms for inorganic ions and organic substances. Compared with a peak-splitting fitting graph of an oxygen (O) element of the graphene oxide composite material before adsorption, after lead ions are adsorbed, as shown in FIG. 3a, a new peak of a-Pb-O bond appears at 530.7 eV, and peaks of carboxyl, carbonyl and ester groups move from 532.92, 531.82 and 532.22 eV to 533.3, 531.37 and 532.36 eV respectively, which shows that the adsorption mechanism of the graphene oxide composite material on the lead ions is the complexation of lead ions and free electrons of a small amount of oxygen in the composite material. After the graphene oxide composite material adsorbs the paranitrophenol and the neutral red, the adsorption mechanism of the graphene oxide composite material on the paranitrophenol and the neutral red is pi-pi effect, hydrophobic effect and hydrogen bond effect through peak fitting (see fig. 3 b-3 f) of oxygen (O) element and carbon (C) element(s).
The graphene oxide composite material prepared by the invention has the advantages of stable structure, good reusability, good adsorption selectivity on organic matters and adsorption rejection on certain metal ions, and can realize high-efficiency adsorption of organic matters in an aqueous solution and effective separation of inorganic and organic pollutant mixtures.
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. The preparation method of the graphene oxide composite material is characterized by comprising the following steps:
s1: preparing graphene oxide by taking crystalline flake graphite as a raw material, and freeze-drying to obtain dried graphene oxide;
s2: dissolving the graphene oxide obtained in the step S1 in anhydrous N, N-dimethylformamide to obtain a graphene oxide solution, adding 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane, uniformly mixing, performing esterification and amidation reactions under the condition of an anhydrous catalyst, and drying to obtain the composite material.
2. The method for preparing a graphene oxide composite material according to claim 1, wherein in S1, the graphene oxide is prepared by a modified Hummers method using flake graphite as a raw material.
3. The method for preparing the graphene oxide composite material according to claim 1, wherein in S2, the concentration of the graphene oxide solution is 2.5-75 mg/mL, and the mass ratio of the graphene oxide to 1, 3-bis [ tris (hydroxymethyl) methylamino ] propane is 1: 1-1: 10.
4. The preparation method of the graphene oxide composite material according to claim 1, wherein in S2, the mass ratio of the catalyst to the graphene oxide is 1: 5-20, the catalyst is N, N '-dicyclohexylcarbodiimide combined with 4-dimethylaminopyridine, and the mass ratio of the N, N' -dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 5: 1-1: 5.
5. The preparation method of the graphene oxide composite material according to claim 1, wherein in the step S2, a moisture-proof reflux device is adopted as reaction equipment, the reaction temperature is 150-180 ℃, and the reaction time is 4-12 h.
6. The preparation method of the graphene oxide composite material according to claim 1, wherein in the step S2, the reaction is always performed under magnetic stirring, the reaction product is naturally cooled to room temperature after the reaction is completed, the obtained product is subjected to vacuum filtration, the filter residue is repeatedly washed with ethanol and deionized water in sequence, impurities are removed, and the filter residue is collected and dried.
7. A graphene oxide composite material characterized by being produced by the production method according to any one of claims 1 to 6.
8. Use of the graphene oxide composite material of claim 7 in selective adsorption separation of inorganic ions and organic contaminants in an aqueous solution.
9. Use according to claim 8, wherein the inorganic ions comprise chloride, sulphate, nitrate; the organic pollutants comprise tert-butyl hydroquinone, m-nitrophenol, p-nitrophenol, alizarin red S and neutral red; the concentration of the adsorbate is 10-100 mg/L.
10. Use according to claim 8, wherein the inorganic ions comprise rare earth ions and heavy metal ions.
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| CN116059974A (en) * | 2023-03-24 | 2023-05-05 | 中南大学 | Thiophene-2-carboxylic acid modified silica gel composite material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423072A (en) * | 2016-09-21 | 2017-02-22 | 广东环境保护工程职业学院 | Graphene oxide-sulfhydryl compound composite capable of adsorbing heavy metal ions and preparation method of graphene oxide-sulfhydryl compound composite |
| CN107141226A (en) * | 2017-06-15 | 2017-09-08 | 温州大学 | The method that six arm initiators or eight arm initiators are synthesized based on 1,3 2 [three (methylol) methylaminos] propane |
| WO2017183745A1 (en) * | 2016-04-20 | 2017-10-26 | 고려대학교 산학협력단 | Carbon dioxide adsorbent with improved long-term adsorption performance through amine cross-linking and core-shell structure, and preparation method therefor |
| CN107497404A (en) * | 2017-10-18 | 2017-12-22 | 中南林业科技大学 | A kind of preparation method of modified graphene oxide sorbing material |
| CN107840971A (en) * | 2017-10-27 | 2018-03-27 | 华南理工大学 | It is a kind of that from adhering to, wearable power is quick to sense composite aquogel and preparation method thereof |
| CN107930607A (en) * | 2017-11-23 | 2018-04-20 | 湖南大学 | A kind of method that tetracycline and Ciprofloxacin single and binary-combined contamination water body are handled using modified graphene oxide |
| 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 |
| CN110937598A (en) * | 2019-11-08 | 2020-03-31 | 宁波锋成先进能源材料研究院 | Modified graphene oxide and preparation method and application thereof |
| CN111004390A (en) * | 2018-10-08 | 2020-04-14 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
| US20200149178A1 (en) * | 2018-11-13 | 2020-05-14 | Nanjing Graphene Research Institute Corporation | Method for forming electroplated copper on surface of non-metal material by graphene-based ink |
-
2020
- 2020-11-06 CN CN202011228065.3A patent/CN112547016B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017183745A1 (en) * | 2016-04-20 | 2017-10-26 | 고려대학교 산학협력단 | Carbon dioxide adsorbent with improved long-term adsorption performance through amine cross-linking and core-shell structure, and preparation method therefor |
| CN106423072A (en) * | 2016-09-21 | 2017-02-22 | 广东环境保护工程职业学院 | Graphene oxide-sulfhydryl compound composite capable of adsorbing heavy metal ions and preparation method of graphene oxide-sulfhydryl compound composite |
| CN107141226A (en) * | 2017-06-15 | 2017-09-08 | 温州大学 | The method that six arm initiators or eight arm initiators are synthesized based on 1,3 2 [three (methylol) methylaminos] propane |
| CN107497404A (en) * | 2017-10-18 | 2017-12-22 | 中南林业科技大学 | A kind of preparation method of modified graphene oxide sorbing material |
| CN107840971A (en) * | 2017-10-27 | 2018-03-27 | 华南理工大学 | It is a kind of that from adhering to, wearable power is quick to sense composite aquogel and preparation method thereof |
| CN107930607A (en) * | 2017-11-23 | 2018-04-20 | 湖南大学 | A kind of method that tetracycline and Ciprofloxacin single and binary-combined contamination water body are handled using modified graphene oxide |
| 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 |
| CN111004390A (en) * | 2018-10-08 | 2020-04-14 | 惠州学院 | Preparation method of graphene/polyaniline composite material |
| US20200149178A1 (en) * | 2018-11-13 | 2020-05-14 | Nanjing Graphene Research Institute Corporation | Method for forming electroplated copper on surface of non-metal material by graphene-based ink |
| CN110937598A (en) * | 2019-11-08 | 2020-03-31 | 宁波锋成先进能源材料研究院 | Modified graphene oxide and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAORU ZHAO ET AL.: "Behavior and mechanism of graphene oxide-tris(4-aminophenyl)amine composites in adsorption of rare earth elements", 《JOURNAL OF RARE EARTHS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116059974A (en) * | 2023-03-24 | 2023-05-05 | 中南大学 | Thiophene-2-carboxylic acid modified silica gel composite material and preparation method and application thereof |
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