CN104226253A - Graphene oxide-TiO2 composite material and preparation method and application thereof - Google Patents
Graphene oxide-TiO2 composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN104226253A CN104226253A CN201410536845.2A CN201410536845A CN104226253A CN 104226253 A CN104226253 A CN 104226253A CN 201410536845 A CN201410536845 A CN 201410536845A CN 104226253 A CN104226253 A CN 104226253A
- Authority
- CN
- China
- Prior art keywords
- tio
- graphene oxide
- composite
- iii
- preparation
- 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
Abstract
The invention discloses a graphene oxide (GO)-TiO2 composite material and preparation method and application thereof in terms of separation/enrichment of heavy metal ions. In situ synthesis of nanometer TiO2 on GO is achieved, the ratio of the GO to TiO2 is optimized so that the mass ratio of the GO to the TiO2 is 1: (1-9), the GO-TiO2 composite material with GO and TiO2 excellent properties can be prepared, and the GO-TiO2 composite material can be successfully applied to separation/enrichment of heavy metal and rare earth elements in environmental water samples and bottom mud. By means of the GO-TiO2 composite material and the preparation method and application thereof, the prepared GO-TiO2 (1: 1) composite material is wide in potential of hydrogen (pH) application range, high in adsorption rate, selectivity and anti-jamming capability, large in adsorption capacity and long in service life, and the composite material can be used for separation/enrichment of target analyte in environmental water samples and bottom mud and serves as a practical solid-phase extraction agent.
Description
?
Technical field
The invention belongs to separation and analysis detection technique field, be specifically related to a kind of GO-TiO
2composite and preparation method thereof with being separated/enrichment environment water sample and bed mud in heavy metal Cu (II), Pb (II) and rare-earth elements La (III), Ce (III), Eu (III), application in Dy (III) and Yb (III).
Background technology
Heavy metal pollution has serious threat to ecological environment, is progressively accumulated can produce certain toxic and side effect to the mankind by biological chain.Such as, copper is the element useful to human body, but exceed a certain amount of after, anaemia, lesions of liver and kidney and gastrointestinal disorder etc. can be caused.Lead poisoning there will be stomachache, headache, spasm, anaemia, chronic nephritis, the disorderly symptom of cerebral nerve maincenter.The mankind arrive rare earth element by picked-ups such as air, water, food and medical medicines, and Long Term Contact rare earth element may produce harmful effect to liver, kidney, lung and sclerotin and cause immunity degradation.Therefore, foundation and the effective method measuring heavy metal and ree content in environmental sample of development have great importance.
There is following difficulty when directly measuring actual sample in existing instrument: on the one hand, is limited to and analyzes thing content in the sample to which, if content is lower than the detection limit of instrument, can not draw accurate result; On the other hand, if the matrix complexity of sample, physics or chemical state are not suitable for Direct Analysis, instrument application is limited equally.Therefore, usually need before measurement to carry out sample pre-treatments.
In sample pre-treatments, beneficiation technologies is separated compared to coprecipitation, liquid-liquid extraction etc., Micro-column solid phase extraction technology (SPE) have simple to operate, enrichment times is high, reduce and analyze thing loss and the possibility polluted and the advantage such as cost is lower, is widely used in separation/enriching heavy metal and rare earth element.In microtrabeculae SPE technology, fill out column material improving in analytical performance and play a part key.Desirable sorbing material should possess has the character such as suitable affinity, preferably selective and high-adsorption-capacity to object.Wherein, carbon-based material has that adsorption capacity is large, chemical stability and Heat stability is good and the advantage such as cost is lower, in SPE, be able to extensive use.Such as, fullerene (Silva, M. M.; Arruda, M. A. Z.; Krug, F. J.; Oliveira, P. V.; Queiroz, Z. F.; Gallego, M.; Valcarcel, M., " On-line separation and preconcentration of cadmium, lead and nickel in a fullerene (C-60) minicolumn coupled to flow injection tungsten coil atomic absorption spectrometry ".
analytica Chimica Acta 1998, 368, 255-263.), CNT (Ozcan, S. G.; Satiroglu, N.; Soylak, M., " Column solid phase extraction of iron (III); copper (II), manganese (II) and lead (II) ions food and water samples on multi-walled carbon nanotubes ".
food and Chemical Toxicology 2010, 48, 2401-2406.), Graphene (Wang, Y. K.; Gao, S. T.; Zang, X. H.; Li, J. C.; Ma, J., " Graphene-based solid-phase extraction combined with flame atomic absorption spectrometry for a sensitive determination of trace amounts of lead in environmental water and vegetable samples ".
analytica Chimica Acta 2012, 716, 112-118.) etc. carbon-based material be used successfully as SPE material be separated and enrich target analysis thing.
Graphene oxide (GO), as a kind of new carbon, has the unique advantage of separating and enriching trace metal ion.First, GO maintains the basic skeleton structure of Graphene, has very large surface area, can reach 2630 m in theory
2g
-1.Compared to fullerene and CNT, the two dimensional surface of GO provides more multiple binding sites.Secondly, GO aspect contains oxygen base (carboxyl, hydroxyl and epoxy radicals) containing a large amount of, and comparatively Graphene is easier to be combined with metal ion, and carries out modification to it.These character make GO have the advantages that chemism is high and adsorption capacity is large.In addition, GO can be undertaken being oxidized by graphite and prepare, and compared with commercial SPE material, cost is lower.
Although GO has above advantage, directly use it for online SPE and there is difficulty, because GO has well water-soluble and dispersed, in solid-liquid two-phase column operation, then the loss of inevitable material and the problem such as post pressure is large.In order to overcome the above problems, fabricated in situ nano-TiO on GO
2and the ratio of the two is optimized, prepare and had GO and TiO concurrently
2the GO-TiO of premium properties
2composite, and the heavy metal be used successfully in separation/enrichment environment water sample and bed mud and rare earth element.
It is about Graphene-TiO that majority has been reported
2the preparation of material and the application in photocatalysis, synthesizing graphite alkene-TiO
2numerous methods in, mainly contain simple mixing-ultrasonic method, sol-gal process and hydro-thermal method, great majority are all by GO/TiO
2through high-temperature process, graphene oxide is reduced and obtain Graphene-TiO
2material.The operation of mixing-ultrasonic method is upper simple, is about to the TiO prepared
2after mixing with GO, carry out ultrasonic process, but the chemical stability of material is bad, heats on this basis, the chemical stability of material can be improved, but reduce on GO containing oxygen base unit weight.Adopt sol-gal process, GO and TiO
2can fully mix, but follow-up through high-temperature calcination process.With hydro-thermal method preparation, GO and TiO
2between there is the strongest chemical interactions, but prepare at relatively high temperatures, GO is inevitably reduced, and reduces containing oxygen base unit weight.Material prepared by above method reduce on GO containing oxygen base, be unfavorable for being combined with metal ion.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of GO-TiO is provided
2the preparation method of composite and the application in enriching heavy metal ion thereof, this preparation method modifies inorganic nano TiO on GO
2, retain to greatest extent on GO containing oxygen base, be beneficial to GO as adsorbent and heavy metal ion effect; The invention solves GO water solubility problems, widen the application of new carbon graphene oxide in separation/enrichment environment sample in trace metal ion.
A kind of graphene oxide-TiO
2the preparation method of composite, comprises the following steps:
(1) graphene oxide is added EtOH/H
2in O, carry out ultrasonic disperse, form the suspension of graphene oxide, then stir under 80 ° of C oil bath heating; Wherein, EtOH and H
2the volume ratio of O is 350: 25;
(2) by Ti (BuO)
4be dissolved in EtOH/H
2sO
4in, then dropwise join in the suspension of step (1) graphene oxide, control Ti (BuO)
4consumption make graphene oxide and TiO
2mass ratio is 1:1 ~ 9,80 ° of lower stirrings of C heating; Wherein, EtOH and H
2sO
4volume ratio be 25: 0.375;
(3) product that step (2) obtains is carried out centrifugal, milli-Q water, dry, namely obtain graphene oxide-TiO
2composite.
In described step (1), ultrasonic time is 0.5 h ~ 1h.
In described step (2), mixing time is 12 h, and speed of agitator is 300 ~ 400 revs/min.
In described step (3), centrifugal rotational speed is 4000 revs/min, and baking temperature is 60 ~ 70 ° of C.
Described graphene oxide is obtained by following preparation method: first by 2.5 g K
2s
2o
8with 2.5 g P
2o
5add in the 12 mL concentrated sulfuric acids, then add 3 g graphite dispersed with stirring evenly, 80 ° of C stop stirring after adding thermal response 4.5 h, cool overnight, suction filtration, and after being washed to neutrality, in vacuum drying chamber, 40 ° of C are dried; By the graphite dispersion of pre-oxidation in the 120 mL concentrated sulfuric acids, under ice bath, add 15 g KMnO
4, control to add speed, make reacting liquid temperature≤20 ° C, stir 7 days under 35 ° of C; Then add 250 mL deionized waters, control temperature lower than 50 ° of C, then is warming up to 98 ° of C and stirs 2 h, then proceeds in beaker by reactant liquor, adds 0.7 L deionized water cessation reaction; Adding 20 mL volume fractions is the H of 30%
2o
2solution, for MnO4 and manganese dioxide are reduced to manganese ion, hold over night after magnetic agitation 2h; After upper solution is outwelled, remaining solid is the HCl solution washing, centrifugal of 10% by 1.3 L volume fractions, and then is washed till neutrality by deionized water; Freeze drying obtains brown color graphene oxide solid.
A kind of graphene oxide-TiO prepared by above-mentioned preparation method
2composite.
As graphene oxide and TiO
2when mass ratio is 1:1, anatase type nano TiO
2be evenly distributed in graphene oxide aspect, TiO
2particle diameter is 10 ~ 15 nm.
One utilizes above-mentioned graphene oxide-TiO
2the method of composite separation/enriching heavy metal ion, is characterized in that: the graphene oxide-TiO first taking 30 ~ 50 mg
2composite loads in PTFE microtrabeculae, and post two ends are filled appropriate cotton and prevented graphene oxide-TiO
2composite spills, tightening nuts; Then 0.5 mol L is used respectively
-1hNO
3with 0.1 mol L
-1nH
4ac cleans successively and balances microtrabeculae, then is 3-10 to pH, carries out enrichment containing the solution of heavy metal ion, is finally 0.3 ~ 1 mol L by molar concentration
-1salpeter solution carry out wash-out; Wherein, graphene oxide-TiO
2graphene oxide and TiO in composite
2mass ratio is 1:1 ~ 9.
Described graphene oxide and TiO
2mass ratio is preferably 1:1.
Described heavy metal ion is one or more in Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III), Yb (III).
The different proportion GO-TiO of this method synthesis
2composite is used for enrichment Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) as solid phase microtrabeculae material, and the TiO prepared under compared for similarity condition
2to the adsorption effect of target analytes, final selection mass ratio is the GO-TiO of 1:1
2(1:1) composite is used for follow-up solid extracting agent.Column operation step is as follows: take 30 ~ 50 mg GO-TiO
2(1:1) composite loads in PTFE microtrabeculae (20 mm × 2.0 mm i.d.), and the two ends of post are filled a little cotton and prevented material from spilling, tightening nuts, with 0.5 mol L
-1hNO
3with 0.1 mol L
-1nH
4ac cleans successively and balances microtrabeculae.Other ratio of same method process fills out column material and TiO
2.SPE microtrabeculae GO-TiO
2(1:1) composite is to containing 0.18 ~ 0.5 μ g mL
-1the solution of Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) carries out enrichment, is 0.3 ~ 1 mol L by 0.7mL molar concentration
-1nitric acid carry out wash-out, inductively coupled plasma atomic emission (ICP-OES) measures, and the rate of recovery is more than 90%.Material can Reusability 90 times.
Major advantage of the present invention is as follows:
(1) the present invention GO-TiO that adopted in-situ synthesis to prepare
2composite, and optimize material proportion, have selected GO-TiO
2(1:1) composite is as solid extracting agent, has good Selective adsorption to Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III).
(2) GO-TiO for preparing of the inventive method
2(1:1) composite have that the pH scope of application is wide, the rate of adsorption is fast, adsorption capacity greatly, higher selective, antijamming capability strong and the advantage such as long service life.
(3) GO-TiO for preparing of the present invention
2(1:1) composite can, for separating of the target analytes in/enrichment environment water sample (comprising high salinity seawater) and bed mud, be a kind of solid extracting agent that can be practical.
Accompanying drawing explanation
The TiO of Fig. 1 prepared by embodiment 1
2to the absorption figure of object ion under different pH;
The GO-TiO of Fig. 2 prepared by embodiment 1
2(1:9) under different pH to the absorption figure of object ion;
The GO-TiO of Fig. 3 prepared by embodiment 1
2(1:3) under different pH to the absorption figure of object ion;
The GO-TiO of Fig. 4 prepared by embodiment 1
2(1:1) under different pH to the absorption figure of object ion;
The solid extracting agent GO-TiO that Fig. 5 selectes by embodiment 2
2(1:1) the FT-IR spectrogram of composite;
The solid extracting agent GO-TiO that Fig. 6 selectes by embodiment 2
2(1:1) thermogravimetric curve of composite;
The solid extracting agent GO-TiO that Fig. 7 selectes by embodiment 2
2(1:1) the XRD figure of composite;
The solid extracting agent GO-TiO that Fig. 8 selectes by embodiment 2
2(1:1) transmission electron microscope picture of composite; Wherein, Fig. 8 (A) is under low multiplication factor, (40000 transmission electron microscope pictures x), can see TiO
2be evenly distributed in GO aspect, particle diameter is between 10-15 nm; Fig. 8 (B) is under high-amplification-factor, (400000 transmission electron microscope pictures x), Fig. 8 (B) and (A) figure upper right corner SEAD figure shows TiO
2for Detitanium-ore-type, this is consistent with X-ray powder diffraction characterization result.
Detailed description of the invention
The present invention has prepared composite GO-TiO
2and optimize material proportion, the material that have selected best proportion, for separating of Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) trace element in/enrichment environment sample, sets forth the present invention further below in conjunction with case study on implementation.But these embodiments are only limitted to the present invention is described, can not limit the scope of the invention.
Be that direct-reading inductively-coupled plasma spectrometer (ICP-OES) composed entirely by the Intrepid XSP Radial type of thermoelectricity department of the U.S. for measuring the instrument of Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) content in embodiment 1 and embodiment 4.
Embodiment 1:
Method with reference to the Hummers improved prepares GO: by 2.5 g K
2s
2o
8with 2.5 g P
2o
5join in the 12 mL concentrated sulfuric acids, then by 3 g graphite dispersed with stirring wherein, be heated to 80 ° of C, stop stirring, cool overnight, suction filtration after reacting 4.5 h, after being washed to neutrality, in vacuum drying chamber, 40 ° of C are dried.By the graphite dispersion of pre-oxidation in the 120 mL concentrated sulfuric acids (98%, analyze pure), under ice bath, add 15 g KMnO
4, control to add speed and make reaction temperature≤20 ° C, stir 7 days under 35 ° of C.Add 250 mL deionized waters, control temperature under 50 ° of C, then is warming up to 98 ° of C and stirs 2 h, then proceeds in beaker by reactant liquor, adds 0.7 L deionized water cessation reaction.Add 20 mL 30% H
2o
2(v/v), for MnO4 and manganese dioxide are reduced to manganese ion, hold over night after magnetic agitation 2h.After upper solution is outwelled, remaining solid 1.3 L 10% HCl (v/v) carry out washing (to be washed centrifugal with 35 ~ 40 mL10% HCl at every turn in centrifuge tube, after discarding upper strata centrifugate, again adding 10% HCl, to carry out washing centrifugal, share and remove volume 1.3 L), centrifugal, and then the deionized water spent after deionized water solid to washing is for neutral.Freeze drying obtains brown color graphene oxide solid.Ultrasonic stripping is carried out before synthetic composite material.
GO-TiO
2the preparation of composite adopts in-situ synthesis, i.e. in-situ hydrolysis Ti (BuO)
4, on GO, nucleating growth is TiO
2.Synthetic schemes is specific as follows: 120 mg GO are joined EtOH/H
2o(350 mL/25 mL) in, ultrasonic disperse 0.5 h, then oil bath is heated to 80 ° of C; By Ti (BuO)
4be dissolved in EtOH/H
2sO
4in (25 mL/0.375 mL), then dropwise join in GO suspension.Stirring reaction 12 h under 80 ° of C.Carry out centrifugal and wash by 500 mL deionized waters, solid is dry under 60 ° of C in vacuum drying chamber.By changing GO and Ti (BuO)
4the GO-TiO of ratio of ratio synthesis different quality
2composite (GO:TiO
2=1:9,1:3,1:1,3:1,9:1).In addition, do not add GO and prepared TiO under the same terms
2material.
Embodiment 2:
Different proportion GO-TiO prepared by embodiment 1
2composite and TiO
2be filled in SPE microtrabeculae respectively, carry out the experiment of extraction index.
Take 50 mg GO-TiO
2(1:9), GO-TiO
2(1:3), GO-TiO
2(1:1), GO-TiO
2(3:1), GO-TiO
2(9:1) and TiO
2material is filled in microtrabeculae respectively, adopts 2.5 mL under flow injection Dynamic Adsorption condition of different pH to be respectively 0.5 μ g mL containing Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III)
-1solution.Flow velocity used is 0.5 mL/min.
Experiment finds with GO-TiO
2(3:1) and GO-TiO
2(9:1) the microtrabeculae post pressure for filler is large, and operating difficulties, is not easy for solid phase microtrabeculae filler.Fig. 1,2,3 and 4 is respectively TiO
2material, composite GO-TiO
2(1:9), GO-TiO
2(1:3), GO-TiO
2(1:1) with to the absorption situation of metal ion within the scope of pH 1-10.As shown in Figure 1, TiO
2absorption quantity can be realized to target metal ions within the scope of pH 7-10; As shown in Figure 2, GO and TiO
2mass ratio is the composite GO-TiO of 1:9
2(1:9) at pH 4-10 scope quantification adsorption analysis thing; GO and TiO
2mass ratio is the composite GO-TiO of 1:3 and 1:1
2(1:3) (Fig. 3), GO-TiO
2(1:1) (Fig. 4) can Absorption quantity metal ion in pH 3-10 scope.Can draw to draw a conclusion: compared to TiO
2, composite GO-TiO
2shift to low pH to the Absorption quantity of object ion, and in material, the pH of the higher then Absorption quantity of GO content is lower, in illustrative material, GO plays a key effect when retaining object ion.Considering the advantage of GO uniqueness, will be the composite GO-TiO of 50% containing GO ratio
2(1:1) as solid extracting agent, for the separation/enrichment of object ion in environmental sample.
Absorption quantity in described all refers to that adsorption rate is more than 90%.
Embodiment 3:
To composite GO-TiO selected in embodiment 2
2(1:1) carry out IR Characterization (FT-IR), thermogravimetric analysis (TGA/DTG), X-ray powder diffraction characterizes (XRD) and transmission electron microscope characterizes (TEM), confirm that material is successfully prepared.
Adopt FT-IR spectrometer to composite GO-TiO selected in embodiment 2
2(1:1) solid extracting agent carries out IR Characterization (as shown in Figure 5), the material GO(curve (A) of Fig. 5 prepared by embodiment 1), TiO
2(Fig. 5 (B)) and GO-TiO
2(1:1) the IR Characterization collection of illustrative plates of (curve (C)).1065,1229,1384,1627 and 1733 cm in curve (A)
-1be respectively C=O stretching vibration peak in O – H deformation vibration in the C – O – C stretching vibration peak on GO, C – OH vibration peak, C – OH, C=C stretching vibration and – COOH group, these different explanations containing oxygen base have successfully prepared GO.At TiO
2in infrared figure, 1621 cm
-1place is the – OH vibration peak on its surface, 1000,574 cm
-1the peak that left and right occurs is Ti – O – Ti characteristic peak (Hou, C. Y.; Zhang, Q. H.; Li, Y. G.; Wang, H. Z., " P25-graphene hydrogels:Room-temperature synthesis and application for removal of methylene blue from aqueous solution ".
journal of Hazardous Materials 2012, 205, 229-235.).Composite GO-TiO
2(1:1) still GO and TiO is remained
2on characteristic peak, at 744 cm
-1the new peak that place occurs is that C – O – Ti is at 798 cm
-1vibration peak (Sakthivel, the S. at place; Kisch, H., " Daylight photocatalysis by carbon-modified titanium dioxide ".
angewandte Chemie-International Edition 2003, 42(40), 4908-4911.) with the superposing of Ti – O – Ti characteristic peak.At GO, TiO
2and GO-TiO
2(1:1) in material, at 3409 cm
-1left and right occurs that wider O-H vibration peak is relevant with the hydrone contained.
(TGA, curve (A) is GO, and curve (B) is GO-TiO in Fig. 6 thermogravimetric analysis
2(1:1)) and differential thermal analysis (DTG, curve (C) is GO, and curve (D) is GO-TiO
2(1:1)), for GO and composite GO-TiO
2(1:1), 100
obelow C, for solvent evaporation that is residual in material or absorption is weightless; Upper the losing 196 containing oxygen base of GO
oabout C, (McAllister, M. J. consistent with the result reported; Li, J. L.; Adamson, D. H.; Schniepp, H. C.; Abdala, A. A.; Liu, J.; Herrera-Alonso, M.; Milius, D. L.; Car, R.; Prud'homme, R. K.; Aksay, I. A., " Single sheet functionalized graphene by oxidation and thermal expansion of graphite ".
chemistry of Materials 2007, 19(18), 4396-4404.); GO-TiO
2(1:1) composite is 229
oabout C loses containing oxygen base, and comparatively GO adds 30
oabout C, this may be due to TiO
2contain the effect of oxygen base with in GO, make its stability increase (Lee, Y. C. to some extent; Yang, J. W., " Self-assembled flower-like TiO
2on exfoliated graphite oxide for heavy metal removal ".
journal of Industrial and Engineering Chemistry 2012, 18(3), 1178-1185.).TGA/DTG curve display GO and GO-TiO
2(1:1) lose ratio containing oxygen base in and be respectively 35%, 17%, show composite GO-TiO
2(1:1) in, GO quality is about 50%, and this is consistent with initial rate of charge.
Utilize powder x-ray diffraction (XRD) to composite GO-TiO selected in embodiment 2
2(1:1) solid extracting agent characterizes.Fig. 7 curve (A) is the XRD figure of the GO of preparation in embodiment 1, and it is 10.9 that its characteristic diffraction peak appears at 2 θ angles
o, about 0.81 nm of its interlamellar spacing.Fig. 7 curve (B) is the TiO of preparation in embodiment 1
2xRD figure, its 2 θ diffraction maximum 25.62
o, 37.98
o, 48.14
o, 54.12
o/ 55.34
o, 62.56
o/ 62.96
owith 68.8
o/ 70.02
ocorresponding (101), (004), (200), (105/211), (213/204) and (116/220) crystal face respectively, consistent with Detitanium-ore-type (JCPDS no.00-021-1272).Fig. 7 curve (C) is composite GO-TiO
2(1:1) XRD figure, can find out, the characteristic diffraction peak of GO disappears, this probably with TiO
2relevant (Zhang, the X. Y. of special adsorption; Li, H. P.; Cui, X. L.; Lin, Y. H., " Graphene/TiO
2nanocomposites:synthesis, characterization and application in hydrogen evolution from water photocatalytic splitting ".
journal of Materials Chemistry 2010, 20(14), 2801-2806; Liu, J. C.; Bai, H. W.; Wang, Y. J.; Liu, Z. Y.; Zhang, X. W.; Sun, D. D., " Self-Assembling TiO
2nanorods on Large Graphene Oxide Sheets at a Two-Phase Interface and Their Anti-Recombination in Photocatalytic Applications ".
advanced Functional Materials 2010, 20(23), 4175-4181.)
Transmission electron microscope (TEM) is adopted to observe composite GO-TiO selected in embodiment 2
2(1:1) solid extracting agent, as shown in Fig. 8 (A), (B), can see, TiO in (A) figure
2be evenly distributed in GO aspect, particle diameter is between 10-15 nm.(B) figure and (A) figure upper right corner SEAD figure shows TiO
2for Detitanium-ore-type, this is consistent with X-ray powder diffraction characterization result.
Embodiment 4:
Embodiment 3 result illustrates successfully has prepared composite GO-TiO
2(1:1), further study its adsorption capacity as solid extracting agent in this, tolerate common coexisting ion disturbed condition, service life and the application in actual environment sample.
Embodiment 1 extraction experiments shows composite GO-TiO
2(1:1) can Absorption quantity object ion within the scope of pH 3-10, experimental selection pH=5 is below experiment condition.
(1) concentration is 10 μ g mL by experiment
-1list mark ion at 2.0 mL min
-1gO-TiO is passed through under flow velocity
2(1:1) fill out column material, and it is saturated to adsorbing to detect concentration of metal ions in efflux with ICP-OES, obtains composite GO-TiO
2(1:1) 8.2,64.2,28.7,25.1,16.6,19.3 and 24.1 mg g are respectively to the adsorption capacity of Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III)
-1.
(2) be 0.18 μ g mL to concentration
-1the solution of Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) has carried out the experiment of common interference ion, 10000 mg L
-1k
+, 10000 mg L
-1na
+, 5000 mg L
-1ca
2+, 5000 mg L
-1mg
2+, 10 mg L
-1al
3+, 20 mg L
-1fe
3+, 15000 mg L
-1cl
-, 15000 mg L
-1nO
3 -with 5000 mg L
-1sO
4 2-the absorption of object ion is not had an impact, with 1 mol L
-1nitric acid wash-out, its rate of recovery is all more than 90%.
(3) the 7 mL solution containing target analytes, by microtrabeculae, then use 0.7 mL 1.0 mol L
-1hNO
3carry out wash-out, and with 1 mL 0.1 mol L
-1nH
4ac balances.Material can at least use 90 times, and the rate of recovery does not obviously reduce.Show prepared GO-TiO
2(1:1) composite has the advantages such as the strong and long service life of good stability, capacity antacid.
(4) by composite GO-TiO
2(1:1) for the analysis of target analytes in actual sample, sample comprises East Lake Water, Wuhan, Yangtze River Water (Wuhan, China) and seawater (Hangzhou Wan, China) and East Lake, the Changjiang river bed mud sample (Wuhan, Chinese).Water sample recovery of standard addition is between 82.4-115.5%, and bed mud recovery of standard addition is between 83.8-114.8%.
Claims (10)
1. a graphene oxide-TiO
2the preparation method of composite, is characterized in that, comprises the following steps:
(1) graphene oxide is added EtOH/H
2in O, carry out ultrasonic disperse, form the suspension of graphene oxide, then stir under 80 ° of C oil bath heating; Wherein, EtOH and H
2the volume ratio of O is 350: 25;
(2) by Ti (BuO)
4be dissolved in EtOH/H
2sO
4in, then dropwise join in the suspension of step (1) graphene oxide, control Ti (BuO)
4consumption make graphene oxide and TiO
2mass ratio is 1:1 ~ 9,80 ° of lower stirrings of C heating; Wherein, EtOH and H
2sO
4volume ratio be 25: 0.375;
(3) product that step (2) obtains is carried out centrifugal, milli-Q water, dry, namely obtain graphene oxide-TiO
2composite.
2. preparation method according to claim 1, is characterized in that: in described step (1), and ultrasonic time is 0.5 h ~ 1h.
3. preparation method according to claim 1, is characterized in that: in described step (2), and heating mixing time is 12 h, and speed of agitator is 300 ~ 400 revs/min.
4. preparation method according to claim 1, is characterized in that: in described step (3), and centrifugal rotational speed is 4000 revs/min, and baking temperature is 60 ~ 70 ° of C.
5. preparation method according to claim 1, is characterized in that: described graphene oxide is obtained by following preparation method: first by 2.5 g K
2s
2o
8with 2.5 g P
2o
5add in the 12 mL concentrated sulfuric acids, then add 3 g graphite dispersed with stirring evenly, 80 ° of C stop stirring after adding thermal response 4.5 h, cool overnight, suction filtration, and after being washed to neutrality, in vacuum drying chamber, 40 ° of C are dried; By the graphite dispersion of pre-oxidation in the 120 mL concentrated sulfuric acids, under ice bath, add 15 g KMnO
4, control to add speed, make reacting liquid temperature≤20 ° C, stir 7 days under 35 ° of C; Then add 250 mL deionized waters, control temperature lower than 50 ° of C, then is warming up to 98 ° of C and stirs 2 h, then proceeds in beaker by reactant liquor, adds 0.7 L deionized water cessation reaction; Adding 20 mL volume fractions is the H of 30%
2o
2solution, for MnO4 and manganese dioxide are reduced to manganese ion, hold over night after magnetic agitation 2h; After upper solution is outwelled, remaining solid is the HCl solution washing, centrifugal of 10% by 1.3 L volume fractions, and then is washed till neutrality by deionized water; Freeze drying obtains brown color graphene oxide solid.
6. a graphene oxide-TiO
2composite, is characterized in that: prepared by the preparation method described in any one of claim 1 ~ 5.
7. graphene oxide-TiO according to claim 6
2composite, is characterized in that: as graphene oxide and TiO
2when mass ratio is 1:1, anatase type nano TiO
2be evenly distributed in graphene oxide aspect, TiO
2particle diameter is 10 ~ 15 nm.
8. one kind utilizes the graphene oxide-TiO described in claim 6 or 7
2the method of composite separation/enriching heavy metal ion, is characterized in that: the graphene oxide-TiO first taking 30 ~ 50 mg
2composite loads in PTFE microtrabeculae, and post two ends are filled appropriate cotton and prevented graphene oxide-TiO
2composite spills, tightening nuts; Then 0.5 mol L is used respectively
-1hNO
3with 0.1 mol L
-1nH
4ac cleans successively and balances microtrabeculae, then is 3-10 to pH, carries out enrichment containing the solution of heavy metal ion, is finally 0.3 ~ 1 mol L by molar concentration
-1salpeter solution carry out wash-out; Wherein, graphene oxide-TiO
2graphene oxide and TiO in composite
2mass ratio is 1:1 ~ 9.
9. the method for separation according to claim 8/enriching heavy metal ion, is characterized in that: described graphene oxide and TiO
2mass ratio is 1:1.
10. the method for separation/enriching heavy metal ion according to claim 8 or claim 9, is characterized in that: described heavy metal ion is one or more in Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III), Yb (III).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410536845.2A CN104226253B (en) | 2014-10-13 | 2014-10-13 | Graphene oxide-TiO2 composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410536845.2A CN104226253B (en) | 2014-10-13 | 2014-10-13 | Graphene oxide-TiO2 composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104226253A true CN104226253A (en) | 2014-12-24 |
| CN104226253B CN104226253B (en) | 2017-02-15 |
Family
ID=52215678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410536845.2A Expired - Fee Related CN104226253B (en) | 2014-10-13 | 2014-10-13 | Graphene oxide-TiO2 composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104226253B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607064A (en) * | 2015-01-11 | 2015-05-13 | 王丽莉 | Method for preparing polyvinylidene fluoride-graphene oxide composite hollow fiber membrane |
| CN104817069A (en) * | 2014-12-25 | 2015-08-05 | 华南师范大学 | Preparation device and method of composite graphene block material |
| CN105107476A (en) * | 2015-08-26 | 2015-12-02 | 南昌航空大学 | Preparation method of self-cleaning intelligent adsorbing material |
| CN105355320A (en) * | 2015-10-23 | 2016-02-24 | 河北麦森钛白粉有限公司 | Production technology of nanoscale conductive titanium dioxide |
| CN106179302A (en) * | 2016-07-14 | 2016-12-07 | 华北电力大学（保定） | A kind of catalysis material and the method preparing catalysis material |
| CN107469772A (en) * | 2017-10-13 | 2017-12-15 | 山东理工大学 | A kind of method of heavy metal classes incretion interferent in removal reverse osmosis concentrated water |
| CN108906059A (en) * | 2018-07-06 | 2018-11-30 | 内蒙古农业大学 | A kind of TiO2Base magnetic porous composite material and preparation method thereof |
| CN110102258A (en) * | 2019-05-15 | 2019-08-09 | 华北电力大学 | The synthetic method and application of three-dimensional manganese dioxide and graphene oxide compound adsorbent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
| KR20130044987A (en) * | 2011-10-25 | 2013-05-03 | 울산대학교 산학협력단 | Composition for air purification comprising photocatalysts of graphene oxide-tio2 |
-
2014
- 2014-10-13 CN CN201410536845.2A patent/CN104226253B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
| KR20130044987A (en) * | 2011-10-25 | 2013-05-03 | 울산대학교 산학협력단 | Composition for air purification comprising photocatalysts of graphene oxide-tio2 |
Non-Patent Citations (3)
| Title |
|---|
| SHAOWEI SU ET AL: "Determination of trace/ultratrace rare earth elements in environmental samples by ICP-MS after magnetic solid phase extraction with Fe3O4@SiO2@polyaniline-graphene oxide composite", 《TALANTA》 * |
| YONGYE LIANG ET AL: "TiO2 Nanocrystals Grown on Graphene as Advanced Photocatalytic Hybrid Materials", 《NANO RESEARCH》 * |
| ZHANG QIONG ET AL: "Structure and photocatalytic properties of TiO2-Graphene Oxide intercalated composite", 《CHINESE SCI BULL》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817069A (en) * | 2014-12-25 | 2015-08-05 | 华南师范大学 | Preparation device and method of composite graphene block material |
| CN104607064A (en) * | 2015-01-11 | 2015-05-13 | 王丽莉 | Method for preparing polyvinylidene fluoride-graphene oxide composite hollow fiber membrane |
| CN105107476A (en) * | 2015-08-26 | 2015-12-02 | 南昌航空大学 | Preparation method of self-cleaning intelligent adsorbing material |
| CN105107476B (en) * | 2015-08-26 | 2017-07-14 | 南昌航空大学 | A kind of preparation method of the intelligent sorbing material of automatically cleaning |
| CN105355320A (en) * | 2015-10-23 | 2016-02-24 | 河北麦森钛白粉有限公司 | Production technology of nanoscale conductive titanium dioxide |
| CN106179302A (en) * | 2016-07-14 | 2016-12-07 | 华北电力大学（保定） | A kind of catalysis material and the method preparing catalysis material |
| CN107469772A (en) * | 2017-10-13 | 2017-12-15 | 山东理工大学 | A kind of method of heavy metal classes incretion interferent in removal reverse osmosis concentrated water |
| CN108906059A (en) * | 2018-07-06 | 2018-11-30 | 内蒙古农业大学 | A kind of TiO2Base magnetic porous composite material and preparation method thereof |
| CN108906059B (en) * | 2018-07-06 | 2021-04-23 | 内蒙古农业大学 | TiO 22Magnetic porous composite material and preparation method thereof |
| CN110102258A (en) * | 2019-05-15 | 2019-08-09 | 华北电力大学 | The synthetic method and application of three-dimensional manganese dioxide and graphene oxide compound adsorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104226253B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226253B (en) | Graphene oxide-TiO2 composite material and preparation method and application thereof | |
| Wang et al. | Extraction of neonicotinoid insecticides from environmental water samples with magnetic graphene nanoparticles as adsorbent followed by determination with HPLC | |
| Cai et al. | Fabrication of a phosphorylated graphene oxide–chitosan composite for highly effective and selective capture of U (VI) | |
| Zhou et al. | Pseudocapacitive deionization of uranium (VI) with WO3/C electrode | |
| Yao et al. | In-situ reduction synthesis of manganese dioxide@ polypyrrole core/shell nanomaterial for highly efficient enrichment of U (VI) and Eu (III) | |
| Li et al. | In situ fabrication of Mn3O4 decorated graphene oxide as a synergistic catalyst for degradation of methylene blue | |
| Wu et al. | Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples | |
| Liu et al. | Hemimicelles/admicelles supported on magnetic graphene sheets for enhanced magnetic solid-phase extraction | |
| Gupta et al. | Chromium removal by combining the magnetic properties of iron oxide with adsorption properties of carbon nanotubes | |
| Han et al. | Facile and tunable fabrication of Fe3O4/graphene oxide nanocomposites and their application in the magnetic solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples | |
| Zhang et al. | Graphene oxide–TiO 2 composite as a novel adsorbent for the preconcentration of heavy metals and rare earth elements in environmental samples followed by on-line inductively coupled plasma optical emission spectrometry detection | |
| Yang et al. | In situ controllable synthesis of magnetic Prussian blue/graphene oxide nanocomposites for removal of radioactive cesium in water | |
| Ryu et al. | Recovery of lithium in seawater using a titanium intercalated lithium manganese oxide composite | |
| Zhang et al. | Magnetic hollow carbon nanospheres for removal of chromium ions | |
| Zhao et al. | A facile route to the synthesis copper oxide/reduced graphene oxide nanocomposites and electrochemical detection of catechol organic pollutant | |
| Shi et al. | Enrichment and detection of small molecules using magnetic graphene as an adsorbent and a novel matrix of MALDI-TOF-MS | |
| Jiang et al. | Realization of super high adsorption capability of 2D δ-MnO2/GO through intra-particle diffusion | |
| Sun et al. | Magnetically separable porous graphitic carbon with large surface area as excellent adsorbents for metal ions and dye | |
| Cheng et al. | Self-assembly of 2D-metal–organic framework/graphene oxide membranes as highly efficient adsorbents for the removal of Cs+ from aqueous solutions | |
| Zhao et al. | Solid-phase microextraction with a novel graphene-coated fiber coupled with high-performance liquid chromatography for the determination of some carbamates in water samples | |
| CN108328706A (en) | A kind of MOF derives the preparation and application of porous carbon/graphene combination electrode material | |
| Li et al. | Diglycolamide-grafted Fe3O4/polydopamine nanomaterial as a novel magnetic adsorbent for preconcentration of rare earth elements in water samples prior to inductively coupled plasma optical emission spectrometry determination | |
| Thapa et al. | Bisphosphonate modified mesoporous silicon for scandium adsorption | |
| Heidarimoghadam et al. | Graphene oxide for rapid determination of testosterone in the presence of cetyltrimethylammonium bromide in urine and blood plasma of athletes | |
| Ohashi et al. | Lithium adsorption from natural brine using surface-modified manganese oxide adsorbents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| 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: 20170215 Termination date: 20171013 |