CN103521191B - A kind of preparation method of titanium dioxide/chitosan/oxigraphene graphene composite material and application - Google Patents
A kind of preparation method of titanium dioxide/chitosan/oxigraphene graphene composite material and application Download PDFInfo
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- CN103521191B CN103521191B CN201310480329.8A CN201310480329A CN103521191B CN 103521191 B CN103521191 B CN 103521191B CN 201310480329 A CN201310480329 A CN 201310480329A CN 103521191 B CN103521191 B CN 103521191B
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Abstract
The present invention relates to a kind of titanium dioxide/chitosan/oxigraphene graphene composite material, its concrete steps prepared are: graphite oxide is scattered in obtained dispersion liquid in spirit of vinegar, adds Chitosan powder, add titanium dioxide after stirring in dispersion liquid, continue to stir, form glue; Glue is added drop-wise in sodium hydroxide solution, after leaving standstill 4-12h, is washed till neutrality and obtains plural gel.Obtained material can be applicable to process the heavy metal arsenic in waste water, and this material can repeatedly use.Composite material and preparation method thereof of the present invention is simple, good to the removal effect of arsenic, is easy to Separation of Solid and Liquid, is a kind of material of simple, efficient, environmental protection, has good application prospect.
Description
Technical field
The invention belongs to environment new material and water-treatment technology field, be specifically related to a kind of preparation method and application of titanium dioxide/chitosan/oxigraphene graphene composite material.
Background technology
Arsenic is a kind of ubiquitous poisonous material, mainly with inorganic salts anion, as arsenate (AsO
4 3-) and arsenite (AsO
3 3-) form be present in natural stream networks, this two classes arsenide enters in human body by modes such as respiratory tract, food or skin contacts.If people drink or contact high arsenic water for a long time, the various pathology of health and canceration can be caused.Due to natural and artificial reason, there is serious arsenic pollution problem in many countries in the world, up-to-date report display, northern China vast rural area drinking water also exists very serious arsenic and pollutes, and it is that many places become one of the main inducing in " cancer village " that arsenic pollutes.
Dearsenicating method traditional so far, as the application such as the precipitation method, ion-exchange, membrane separating method, bioanalysis and absorption method are comparatively wide, wherein absorption method cost is low, technique is simple, efficiency is high, is ideal dearsenicating method.But it is not high that conventional adsorbent all also exists recycling rate of waterused, be difficult to Separation of Solid and Liquid and the problems such as other heavy metal pollutions may be introduced.
Shitosan is considered to a kind of good organic-biological adsorbent, nontoxic, wide material sources, but the stability of shitosan is not strong, thus limits it and further applies; Titanium dioxide is high to arsenious photochemical catalytic oxidation efficiency, and advantages of good adsorption effect, stability is strong, but titanium dioxide granule is little, bad mechanical strength, is difficult to realize Separation of Solid and Liquid, thus limits it directly as the application of adsorbent; Graphene is due to the physicochemical properties of its excellence, obtain in each field and paid close attention to widely, the character such as the specific area that wherein Graphene is huge and excellent mechanical strength can be used in the research and development of sorbing material, but because graphene oxide is hydrophilic, be easy in the solution reunite, also limit its range of application; So the advantageous property of various material being combined into composite is a kind of desirable solution.
Summary of the invention
The object of the present invention is to provide one be easy to preparation and Separation of Solid and Liquid, pollution-free, low consumed NEW TYPE OF COMPOSITE remove arsenic adsorbent material.
The present invention mainly make use of on the basis of shitosan plastic, successfully with the addition of titanium dioxide and graphene oxide synusia; Make use of the catalytic oxidation of titanium dioxide, the performance of arsenic-adsorbing, in addition, graphene oxide add the mechanical performance that greatly strengthen hydrogel.The concrete preparation method of this composite first adopts the hummers method of improvement to prepare graphite oxide, the graphite oxide of 0.05-0.1g being scattered in 50mL volume fraction is afterwards in the spirit of vinegar of 5%-8%, in dispersion liquid, Chitosan powder is added under normal temperature, Keep agitation 3-5h, then under 40 DEG C of-60 DEG C of constant temperatures, slowly titanium dioxide is added, Keep agitation reaction 1-3h, makes it to form glue; Again completely reacted glue is slowly added drop-wise in 0.1M sodium hydroxide solution through syringe afterwards, leave standstill 4-12h, filter after colloid-stabilised, spend deionized water 3-5 time, be placed in freeze drier dry, obtain the light grey solid particulate composite that particle diameter is 1-2mm.
The hummers method improved described in said method is specially, and is added to by 1.5g graphite powder and H is housed
2sO
4/ H
3pO
4for in the beaker of 180ml/20ml, this system is placed in ice-water bath, then adds 9g potassium permanganate, after reaction 0.5-1h, is positioned in 50 DEG C of waters bath with thermostatic control and stirs 12 hours; After reactant cool to room temperature, add and fill 3mL30%H
2o
2200mL ice beaker in, fully after reaction with the metal screen filtration of 300 μm; Supernatant is outwelled by after the centrifugation of gained filtrate, after filter residue after centrifugal spends deionized water 1-3 time, again with centrifugation again after the washing of 5-10% watery hydrochloric acid, until supernatant is clarified and be can't detect sulfate ion, then use organic solvent washing 1-3 all over rear centrifugation; Obtain product and be placed in freeze drier drying.
Above-mentionedly prepare in graphite oxide that to wash organic solvent used can be ethanol, one in acetone.
As a total technical conceive, the present invention also provides a kind of application of above-mentioned composite, specifically described composite is used for the arsenic ion removed in waste water.
In above-mentioned application, composite is that often liter of arsenic-containing waste water adds 0.4-5g as addition during adsorbent, and the described pH for arsenic-containing waste water process controls at 5-7, and the concentration of arsenic ion is 500 μ g/L-10000 μ g/L, and temperature controls at 25 DEG C-35 DEG C.
Compared with prior art, the invention has the advantages that: the deficiency that the present invention is directed to existing dearsenicating method, by utilizing a kind of composite adsorbing material (hereinafter referred to as TCG) being easy to Separation of Solid and Liquid of respective advantage synthesis of three kinds of raw materials (shitosan, graphite oxide, titanium dioxide); Three kinds of raw material sources are extensive, and sintetics is environmentally friendly, can not cause secondary pollution; In whole preparation process, preparation method, synthesis condition are simple, do not need to add any catalyst and surfactant.As a comparison, titanium dioxide/aquagel (hereinafter referred to as TC) that we will not add graphene oxide and prepare, respectively with TC and composite of the present invention for adsorbent carries out adsorption experiment to the AS (III) of same initial concentration and AS (V) solution, we find that it improves about 150% to the clearance of AS in water (III) and AS (V) to product of the present invention compared with TC material; And prove through experiment, product of the present invention can arsenic ion on wash-out > 90% material under the condition of pH value > 9, and the product of visible this method has good removal effect to arsenic in water and can reuse.
In addition, the reaction of photochemical catalytic oxidation arsenic and arsenic-adsorbing can be carried out by composite provided by the invention under same device, has and has good actual application value and industrial prospect.
Detailed description of the invention
Specific embodiment is intended to be described in further detail instead of limitation of the invention further the present invention.
Embodiment 1
(1) preparation for titanium dioxide-shitosan-oxidized graphite composite material, comprises the steps:
The preparation of a, graphite oxide
1.5g graphite powder is added to H is housed
2sO
4/ H
3pO
4for in the beaker of 180ml/20ml, this system is placed in ice-water bath, then adds 9g potassium permanganate, after reaction 0.5-1h, is positioned over 50 DEG C of waters bath with thermostatic control and stirs 12 hours; After reactant cool to room temperature, add and fill 3mL30%H
2o
2200ml ice in, fully after reaction with the metal screen filtration of 300 μm; Filtrate is put into supercentrifuge centrifugation, take out and outwell supernatant; Spend deionized water filter residue 1-3 all over rear centrifugal, then by filter residue 5-10% salt acid elution, more repeatedly centrifugal, until supernatant is clarified and be can't detect sulfate ion, then use organic solvent washing 1-3 all over rear centrifugation; Obtain product dry in freeze drier.
The preparation of b, titanium dioxide/chitosan/oxidized graphite composite material
0.06g graphite oxide being dissolved in 50mL volume fraction is ultrasonic disperse 3h in the spirit of vinegar of 5%, in the dispersion liquid stirred, Chitosan powder is added under normal temperature, after stirring 4h, the anatase titanium dioxide that average grain diameter is less than 20nm is slowly added under 40-60 DEG C of constant temperature stirs, after reaction 1h, glue is poured into and is equipped with in the 10mL syringe of 18G1inch syringe needle, equably (keep 2 seconds one) be added drop-wise in the sodium hydroxide solution of 0.1M, leave standstill after 8 hours, take out after simple for micelle Separation of Solid and Liquid, after product washing is neutrality to filtrate, obtain through freeze drying.
(2) mensuration of composite absorption property.
With composite material adsorbent of the present invention, removal experiment is carried out to trivalent arsenic ion and pentavalent arsenic ion.Getting 50mL initial concentration is 1 × 10
4the AS (III) of μ g/L and AS (V) solution, temperature 30 DEG C, when pH is 6.5, the adsorbance of 0.25g composite to AS (III) and AS (V) is respectively 6124.3 μ g/g and 8317.2 μ g/g.
Embodiment 2
Composite adsorbing material of the present invention (being called for short TCG) is tested with the removal that the titanium dioxide/shitosan sorbing material (being called for short TC) not adding graphite oxide carries out arsenic ion under the same conditions as example 1, it is 6256.3 μ g/g that measurement obtains the adsorbance of TCG product to AS (III), and the adsorbance of TCG product to AS (V) is 8149.2 μ g/g.The adsorbance of TC material to AS (III) is 4082.7 μ g/g, and the adsorbance of TC material to AS (V) is 5546.3 μ g/g.
Claims (4)
1. a titanium dioxide/chitosan/oxigraphene graphene composite material preparation method, it is characterized in that preparation method is as follows: the graphite oxide of 0.05-0.1g being scattered in 50mL volume fraction is in the spirit of vinegar of 5%-8%, in dispersion liquid, Chitosan powder is added under normal temperature, make feed components titanium dioxide, shitosan, graphite oxide dosage than being (0.3-0.5): 1:(0.05-0.1), and Keep agitation 3-5h; Under 40 DEG C of-60 DEG C of constant temperatures, slowly add titanium dioxide, Keep agitation reaction 1-3h, makes it to form glue; Glue is added drop-wise in the sodium hydroxide solution of 0.1M, after leaving standstill 4-12h, made micelle is taken out and is washed till neutrality, obtain composite through freeze drying.
2. according to a kind of described in claim 1 preparation method of titanium dioxide/chitosan/oxigraphene graphene composite material, it is characterized in that, titanium dioxide is anatase titanium dioxide, and average grain diameter is less than 20 nanometers.
3. a kind of application of titanium dioxide/chitosan/oxigraphene graphene composite material that obtains of preparation method described in any one of claim 1 to 2, is characterized in that, described composite is used for the process of arsenic-containing waste water.
4. according to the application described in claim 3, it is characterized in that, described composite is that often liter of arsenic-containing waste water adds 0.4-5g as addition during adsorbent, the described pH for arsenic-containing waste water process controls at 5-7, the concentration of arsenic ion is 500 μ g/L-10000 μ g/L, and temperature controls at 25 DEG C-35 DEG C.
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| CN105642246A (en) * | 2016-03-25 | 2016-06-08 | 郑州大学 | Graphene oxide/chitosan porous composite microspheres and preparation method as well as application thereof |
| CN105771915A (en) * | 2016-03-30 | 2016-07-20 | 安徽大学 | Preparation method for circulation adsorbent graphene/molybdenum disulfide/chitosan compound aquogel |
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| CN106362805B (en) * | 2016-08-26 | 2018-11-13 | 湖南大学 | Titanium dioxide/graphene/molecular imprinting composite material and its preparation method and application |
| CN108262020A (en) * | 2016-12-30 | 2018-07-10 | 海门市源美美术图案设计有限公司 | Biomass modified graphite oxide and the application in terms of uranium improvement |
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| CN108745420A (en) * | 2018-04-24 | 2018-11-06 | 曹俊峰 | A kind of nano titanium dioxide photocatalyst of degradable Phenol for Waste Water pollutant |
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| CN109126647B (en) * | 2018-09-08 | 2020-11-03 | 特勃尔润滑技术(江苏)有限公司 | Preparation method of graphene oxide-sodium alginate gel spheres |
| CN110550693A (en) * | 2019-08-30 | 2019-12-10 | 大连理工大学 | Preparation method and application of ZnO-GO/chitin aerogel composite material |
| CN112495435B (en) * | 2020-11-23 | 2023-05-16 | 北京联合大学 | Chitosan-based graphene/TiO 2 Composite microsphere and preparation method thereof |
| CN112916045A (en) * | 2021-01-31 | 2021-06-08 | 胡国强 | Load ZnO-TiO2Preparation method of magnetic graphene oxide/chitosan composite material |
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