CN103769051B - A kind of graphite oxide of transforming is to improve the method for its adsorb acidic dyestuff performance - Google Patents
A kind of graphite oxide of transforming is to improve the method for its adsorb acidic dyestuff performance Download PDFInfo
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- CN103769051B CN103769051B CN201410045613.7A CN201410045613A CN103769051B CN 103769051 B CN103769051 B CN 103769051B CN 201410045613 A CN201410045613 A CN 201410045613A CN 103769051 B CN103769051 B CN 103769051B
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Abstract
The invention provides a kind of graphite oxide of transforming to improve the method for its adsorb acidic dyestuff performance, it is characterized in that graphite oxide and Fe
3o
4-ZrO
2the ratio mixing of 1:1, through ultrasonic dispersed, after adding the ethylenediamine accounting for cumulative volume 6.7%, proceeds to autoclave, after reacting 15h, is cooled to room temperature, isolates solid product with magnet at 180 DEG C in mass ratio, namely obtains product after 70 DEG C of oven dry.The present invention strengthens the adsorption capacity of graphite oxide to electronegative acid dyes, expands graphite oxide and applies in improvement waste water from dyestuff field.
Description
Technical field
The present invention relates to a kind of remodeling method of graphite oxide, particularly relate to a kind of graphite oxide of transforming to improve the method for its adsorb acidic dyestuff performance.
Background technology
Graphite oxide is a kind of important graphite derived product, can obtain through simple processing from graphite, with low cost.It is a kind of multilayer material, surface has abundant functional group, as hydroxyl, epoxy radicals, carboxyl etc., there is the advantages such as specific area is large, ion-exchange capacity is strong, widen the application of graphite oxide for the graphite mineral resources making full use of China's abundant, improve graphite products added value significant, current focus has been become to the study on the modification of graphite oxide.
The main range of application of graphite oxide comprises: the sorbing material etc. of organic reaction catalyst, contaminant degradation material, pollutant efficiently.Wherein, graphite oxide as pollutant efficient adsorption material because of its height practicality paid close attention to widely.
In view of many-sided reason, current China water body environment safety is just tested, and wherein the threat that causes water environment of dyestuff is comparatively serious.Dye dosage is large, and discharge is wide, not only because of Color influences water quality, and mostly has bio-toxicity, even some little amount, carrys out extinction also can to aquatic biozone, can cause huge harm equally to human health.The high efficiency low cost sorbing material being suitable for large-scale application need be developed for this situation.Graphite oxide, as a kind of cheap sorbing material be conveniently easy to get, is developed its application of administering field at waste water from dyestuff and is had positive effect.
But current graphite oxide is subject to the restriction of himself character in waste water from dyestuff administering.This is because, graphite oxide is because its surface is with the abundant acidic functionality such as carboxyl, hydroxyl, its surface is electronegative, its isoelectric point is about 4, therefore, graphite oxide can only adsorb the basic-dyeable fibre of positively charged, and not good to electronegative acid dyes absorption property, and this seriously constrains graphite oxide in the application of administering waste water from dyestuff field.
Summary of the invention
The object of the present invention is to provide a kind of graphite oxide of transforming to improve the method for its adsorb acidic dyestuff performance.
The present invention is achieved like this.It comprises the following steps:
(1) take graphite as raw material, utilize logical improvement Hummer method synthesis graphite oxide (GO) known, namely GO refers to graphite oxide;
(2) with nanometer Fe
3o
4and ZrOCl
2for raw material, in the basic conditions with the precipitation method synthesizing magnetic zirconia (Fe of routine
3o
4-ZrO
2);
(3) by GO and Fe
3o
4-ZrO
2the ratio mixing of 1:1, through ultrasonic dispersed, after adding the ethylenediamine accounting for cumulative volume 6.7%, proceeds to autoclave, after reacting 15h, is cooled to room temperature, isolates solid product with magnet at 180 DEG C in mass ratio, namely obtains product after 70 DEG C of oven dry.
Further improvement, GO and Fe in step (3)
3o
4-ZrO
2after the ratio of 1:1 mixes in mass ratio, the mixed solution that ultrasonic dispersed solution used is ethanol and deionized water is carried out to it, wherein ethanol: deionized water=1:4(volume ratio), the ultrasonic disperse time is no less than 30 minutes.
Technique effect of the present invention is: under high-temperature and high-pressure conditions, utilize hydro-thermal method by nano particle Fe
3o
4-ZrO
2be deposited on graphite oxide surface, obtain graphite oxide/Fe
3o
4-ZrO
2composite.Fe
3o
4-ZrO
2isoelectric point be about 6, higher than the isoelectric point of graphite oxide.Fe
3o
4-ZrO
2after graphite oxide compound, the isoelectric point relative Oxidation graphite of composite improves, thus strengthens graphite oxide to the adsorption capacity of electronegative acid dyes, expands graphite oxide and applies in improvement waste water from dyestuff field.
For checking correctional effect, with acid dyes amaranth for model pollutant, before and after inspection transformation, graphite oxide is to the absorption property of acid dyes.Result shows, the adsorption capacity of graphite oxide to acid dyes amaranth can be increased to original 2.8 times by the method, reaches 79 mg/g, apparently higher than the low cost amaranth adsorbent that some are common, if kohlrabi skin adsorbance is 31.15 mg/g, peanut shell adsorbance is 14.90 mg/g.
Method route of the present invention is simple in a word, with low cost; Greatly can improve the absorption property of graphite oxide to acid dyes; Improved graphite oxide material adsorbance is large, and has magnetic, and convenient recycling, is suitable for the deep purifying process of large volume waste water.
Accompanying drawing explanation
Fig. 1 is GO/ Fe prepared by embodiment 1
3o
4-ZrO
2transmission electron microscope (TEM) picture of composite.
Fig. 2 is that embodiment 1 prepares gained GO/ Fe
3o
4-ZrO
2composite and the front GO material of transformation are to the contrast of amaranth absorption property.
Fig. 3 is that pH value is to experimental example 1 gained GO/ Fe
3o
4-ZrO
2composite absorption amaranth affect variation diagram.
Detailed description of the invention
Embodiment 1
Take graphite as raw material, utilize the logical improvement Hummer method known to prepare graphite oxide (GO).
By 0.1g nanometer Fe
3o
4be dispersed in 80 ml ethanol, 20 ml water and 1 ml ammoniacal liquor, then add 0.03 g TEOS, stirred at ambient temperature 6h.Gained solid product is dispersed in the mixed solution of 0.3g CTAB, 80ml deionized water, 1.5ml ammoniacal liquor and 60ml ethanol, after Keep agitation 30min, adds 3.05g ZrOCl
2, by gained solid product acetone reflux 48h after completing, after drying, namely obtain Fe
3o
4-ZrO
2.
By 0.1 g GO and 0.1 g Fe
3o
4-ZrO
2mixing, is dispersed in the mixed solution of 15mL ethanol and 60mL deionized water composition, ultrasonic disperse 30 min, after adding 5 ml ethylenediamines, proceed to autoclave, react 15h at 180 DEG C after, be cooled to room temperature, isolate solid product with magnet, after 70 DEG C of oven dry, namely obtain product.
Carry out transmission electron microscope analysis to products obtained therefrom, result as shown in Figure 1.Improved graphite oxide (i.e. gained GO/ Fe
3o
4-ZrO
2composite) and the front GO material of transformation is to the structure of the contrast experiment of amaranth absorption property as shown in Figure 2, as shown in Figure 2, and improved GO/ Fe
3o
4-ZrO
2greatly improve before the absorption property of composite compares improvement, 79 mg/g can be reached.Also to gained GO/ Fe
3o
4-ZrO
2the adsorption capacity of composite under condition of different pH compares, and as shown in Figure 3, its adsorbance when pH equals 2 is high.
Embodiment 2
Take graphite as raw material, utilize the logical improvement Hummer method known to prepare graphite oxide (GO).
By 0.1g nanometer Fe
3o
4be dispersed in 80 ml ethanol, 20 ml water and 1 ml ammoniacal liquor, then add 0.03 g TEOS, stirred at ambient temperature 6h.Gained solid product is dispersed in the mixed solution of 0.3g CTAB, 80ml deionized water, 1.5ml ammoniacal liquor and 60ml ethanol, after Keep agitation 30min, adds 3.05g ZrOCl
2, by gained solid product acetone reflux 48h after completing, after drying, namely obtain Fe
3o
4-ZrO
2.
By 0.1 g GO and 0.1 g Fe
3o
4-ZrO
2mixing, is dispersed in the mixed solution of 15mL ethanol and 60mL deionized water composition, ultrasonic disperse 45 min, after adding 5 ml ethylenediamines, proceed to autoclave, react 15h at 180 DEG C after, be cooled to room temperature, isolate solid product with magnet, after 70 DEG C of oven dry, namely obtain product.
Claims (2)
1. transform graphite oxide to improve a method for its adsorb acidic dyestuff performance, it is characterized in that graphite oxide and Fe
3o
4-ZrO
2the ratio mixing of 1:1, through ultrasonic dispersed, after adding the ethylenediamine accounting for cumulative volume 6.7%, proceeds to autoclave, after reacting 15h, is cooled to room temperature, isolates solid product with magnet at 180 DEG C in mass ratio, namely obtains product after 70 DEG C of oven dry.
2. a kind of graphite oxide of transforming according to claim 1 is to improve the method for its adsorb acidic dyestuff performance, it is characterized in that graphite oxide and Fe
3o
4-ZrO
2after the ratio mixing of 1:1 in mass ratio, the mixed solution that ultrasonic dispersed solution used is ethanol and deionized water is carried out to it, wherein ethanol by volume: deionized water=1:4, the ultrasonic disperse time is no less than 30 minutes.
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| CN201410045613.7A CN103769051B (en) | 2014-02-08 | 2014-02-08 | A kind of graphite oxide of transforming is to improve the method for its adsorb acidic dyestuff performance |
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|---|---|---|---|
| CN201410045613.7A CN103769051B (en) | 2014-02-08 | 2014-02-08 | A kind of graphite oxide of transforming is to improve the method for its adsorb acidic dyestuff performance |
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|---|---|
| CN103769051A CN103769051A (en) | 2014-05-07 |
| CN103769051B true CN103769051B (en) | 2015-08-19 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011150329A2 (en) * | 2010-05-28 | 2011-12-01 | Board Of Regents, The University Of Texas System | Carbocatalysts for chemical transformations |
| CN102757041A (en) * | 2012-07-30 | 2012-10-31 | 哈尔滨工业大学 | Preparation method of graphene/metal oxide nanocomposite powder |
| CN103301812A (en) * | 2013-06-14 | 2013-09-18 | 湖北大学 | Magnetic core-shell microspheres, and preparation method and use thereof |
| CN103464096A (en) * | 2013-08-22 | 2013-12-25 | 青岛科技大学 | Adsorption material, preparation method of adsorption material and method for adsorbing weak acid brilliant blue G in water |
-
2014
- 2014-02-08 CN CN201410045613.7A patent/CN103769051B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011150329A2 (en) * | 2010-05-28 | 2011-12-01 | Board Of Regents, The University Of Texas System | Carbocatalysts for chemical transformations |
| CN102757041A (en) * | 2012-07-30 | 2012-10-31 | 哈尔滨工业大学 | Preparation method of graphene/metal oxide nanocomposite powder |
| CN103301812A (en) * | 2013-06-14 | 2013-09-18 | 湖北大学 | Magnetic core-shell microspheres, and preparation method and use thereof |
| CN103464096A (en) * | 2013-08-22 | 2013-12-25 | 青岛科技大学 | Adsorption material, preparation method of adsorption material and method for adsorbing weak acid brilliant blue G in water |
Non-Patent Citations (1)
| Title |
|---|
| 陈萍华等.磁性氧化锆/壳聚糖纳米复合材料吸附日落黄的性能研究.《南昌航空大学学报(自然科学版)》.2012,第26卷(第3期),第75页右栏结论部分. * |
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