CN104226253B - 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
- CN104226253B CN104226253B CN201410536845.2A CN201410536845A CN104226253B CN 104226253 B CN104226253 B CN 104226253B CN 201410536845 A CN201410536845 A CN 201410536845A CN 104226253 B CN104226253 B CN 104226253B
- Authority
- CN
- China
- Prior art keywords
- tio
- graphene oxide
- iii
- composite
- tio2
- 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.)
- Expired - Fee Related
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 separating with technical field of analysis and detection and in particular to a kind of GO-TiO2Composite and its preparation
Method and in separation/enrichment environment water sample and bed mud heavy metal Cu (II), Pb (II) and rare-earth elements La (III), Ce
(III), the application in Eu (III), Dy (III) and Yb (III).
Background technology
Heavy metal pollution has serious threat to ecological environment, is progressively accumulated by biological chain and the mankind can be produced necessarily
Toxic and side effect.For example, copper is the element beneficial to human body, but exceed a certain amount of after, anaemia, lesions of liver and kidney and stomach can be caused
Disorder etc..Lead poisoning occurs stomachache, headache, spasm, anaemia, chronic nephritis, cerebral nerve maincenter disorder symptoms.The mankind pass through
Empty gas and water, food and medical medicine etc. absorb rare earth element, and Long Term Contact rare earth element may to liver, kidney, lung and
Sclerotin produces harmful effect and causes immunity degradation.Therefore, set up and develop heavy metal and dilute in effective determination of the environment sample
The method of Soil unit cellulose content has great importance.
Existing instrument is directly measured has following difficulty during actual sample：On the one hand, it is limited to analyte in sample
In content, if content be less than instrument detection limit; accurate result could not be drawn；On the other hand, if the matrix of sample complicated,
Physically or chemically state is not suitable for Direct Analysis, equally limits instrument application.Therefore, typically require before measurement and carry out sample
Product pre-treatment.
In sample pre-treatments, compared to the separation and concentration technologies such as coprecipitation, liquid-liquid extraction, Micro-column solid phase extraction technology
（SPE）Have the advantages that simple to operate, enrichment times are high, reduce analyte loss and the possibility of pollution and cost is relatively low,
It is widely used in separation/enriching heavy metal and rare earth element.In microtrabeculae SPE technology, fill out column material and improving analytical performance
Aspect plays the effect of key.Preferably sorbing material should possess object is had suitable affinity, preferably selectively and
The properties such as high-adsorption-capacity.Wherein, carbon-based material have that adsorption capacity is big, chemical stability and heat endurance is good and cost relatively
Low advantage, extensively being applied in SPE.For example, 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 Acta1998,368, 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 Toxicology2010,48,
2401-2406.）, Graphene（Wang, Y. K.; Gao, S. T.; Zang, X. H.; Li, J. C.; Ma, J.
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.）It is used successfully as the separation of SPE material and enrichment target analytes Deng carbon-based material.
Graphene oxide（GO）As a kind of new carbon, there is the unique advantage of separating and enriching trace metal ion.
First, GO maintains the basic skeleton structure of Graphene, has very big surface area, in theory up to 2630 m2g-1.Compared to
Fullerene and CNT, the two dimensional surface of GO provides more multiple binding sites.Secondly, GO aspect contains substantial amounts of oxygen-containing group
（Carboxyl, hydroxyl and epoxy radicals）, it is easier to be combined with metal ion compared with Graphene, and it is modified.These properties make
GO has the characteristics that chemism is high and adsorption capacity is big.In addition, GO can be aoxidized by graphite and be prepared, with commercialization
SPE material is compared, and cost is relatively low.
Although GO has above advantage, directly use it for online SPE and there is difficulty, because GO has good water
Dissolubility and dispersiveness, in solid-liquid two-phase column operation, then the problems such as the loss of inevitable material and post pressure are big.In order to solve
Problem above, fabricated in situ nano-TiO on GO2And the ratio of the two is optimized, it is prepared for having GO and TiO concurrently2Excellent
The GO-TiO of optimum energy2Composite, and it is used successfully to the heavy metal in separation/enrichment environment water sample and bed mud and rare earth unit
Element.
It is with regard to Graphene-TiO that majority has been reported2The preparation of material and the application in terms of photocatalysis, synthetic graphite
Alkene-TiO2Numerous methods in, be mainly simply mixed-ultrasonic method, sol-gal process and hydro-thermal method, great majority are all by GO/
TiO2So that graphene oxide is reduced through high-temperature process and obtain Graphene-TiO2Material.The operation of mixing-ultrasonic method is upper simple, that is,
By the TiO preparing2After mixing with GO, carry out ultrasonically treated, but the chemical stability of material is bad, carry out on this basis adding
Heat treatment, can improve the chemical stability of material, but reduce the oxygen-containing base unit weight on GO.Using sol-gal process, GO and
TiO2Can be sufficiently mixed, but subsequently process through high-temperature calcination.With hydro-thermal method preparation, GO and TiO2Between there is chemistry the strongest
Active force, however, preparing at relatively high temperatures, GO is inevitably reduced, and reduces oxygen-containing base unit weight.Prepared by above method
Material reduce oxygen-containing group on GO, be unfavorable for being combined with metal ion.
Content of the invention
The present invention is directed to the deficiencies in the prior art, provides a kind of GO-TiO2The preparation method of composite and its
Application in enriching heavy metal ion, this preparation method modifies inorganic nano TiO on GO2, retain to greatest extent on GO
Oxygen-containing group, be beneficial to GO and act on as adsorbent and heavy metal ion；The present invention solves GO water solubility problems, widens new
Application in terms of material with carbon element graphene oxide trace metal ion in separation/enrichment environment sample.
A kind of graphene oxide-TiO2The preparation method of composite, comprises the following steps：
（1）Add graphene oxide into EtOH/H2In O, carry out ultrasonic disperse, form the suspension of graphene oxide, so
It is stirred under 80 °C of oil bath heatings afterwards；Wherein, EtOH and H2The volume ratio of O is 350：25；
（2）By Ti (BuO)4It is dissolved in EtOH/H2SO4In, then it is added dropwise to step（1）The suspension of graphene oxide
In, control Ti (BuO)4Consumption make graphene oxide and TiO2Mass ratio is 1：Stir under 1 ~ 9,80 °C of heating；Wherein, EtOH
And H2SO4Volume ratio be 25：0.375 ；
（3）By step（2）The product obtaining is centrifuged, milli-Q water, is dried, that is, obtains graphene oxide-TiO2
Composite.
Described step（1）In, ultrasonic time is 0.5 h ~ 1h.
Described step（2）In, mixing time is 12 h, and speed of agitator is 300 ~ 400 revs/min.
Described step（3）In, centrifugal rotational speed is 4000 revs/min, and baking temperature is 60 ~ 70 °C.
Described graphene oxide is prepared by the following preparation method：First by 2.5 g K2S2O8With 2.5 g P2O5Plus
Enter in the 12 mL concentrated sulfuric acids, be subsequently adding 3 g graphite dispersed with stirring uniformly, after 80 °C of heating response 4.5 h, stop stirring, cooling
Overnight, suction filtration, is washed to 40 °C of drying in vacuum drying chamber after neutrality；By the graphite dispersion of pre-oxidation in the dense sulphur of 120 mL
In acid, under ice bath, add 15 g KMnO4, control and add speed, make reacting liquid temperature≤20 °C, stir 7 days under 35 °C；So
After add 250 mL deionized waters, control temperature to be less than 50 °C, then be warming up to 98 °C of stirring 2 h, then reactant liquor is proceeded to burning
In cup, add 0.7 L deionized water terminating reaction；Add the H that 20 mL volume fractions are 30%2O2Solution, for by Gao Meng
Acid group and manganese dioxide are reduced to manganese ion, stand overnight after magnetic agitation 2h；After upper solution is outwelled, remaining solid is used
1.3 L volume fractions are 10% HCl solution washing, centrifugation, and then deionized water is washed till neutrality again；Freeze-drying obtains
Brown color graphene oxide solid.
A kind of graphene oxide-TiO being prepared by above-mentioned preparation method2Composite.
As graphene oxide and TiO2Mass ratio is 1：When 1, anatase type nano TiO2It is evenly distributed on graphene oxide layer
On face, TiO2Particle diameter is 10 ~ 15 nm.
One kind utilizes above-mentioned graphene oxide-TiO2The method of composite separation/enriching heavy metal ion, its feature exists
In：Weigh the graphene oxide-TiO of 30 ~ 50 mg first2Composite loads in PTFE microtrabeculae, and appropriate cotton is filled at post two ends
Prevent graphene oxide-TiO2Composite spills, tightening nuts；Then respectively with 0.5 mol L-1HNO3With 0.1 mol
L-1NH4Ac cleans and balances microtrabeculae successively, then to pH be 3-10, the solution containing heavy metal ion be enriched with, finally with rubbing
Your concentration is 0.3 ~ 1 mol L-1Salpeter solution eluted；Wherein, graphene oxide-TiO2Graphite oxide in composite
Alkene and TiO2Mass ratio is 1：1~9.
Described graphene oxide and TiO2Mass ratio is preferably 1：1.
Described heavy metal ion is Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III), Yb (III)
One or more of.
The different proportion GO-TiO of this method synthesis2Composite is used for being enriched with Cu (II), Pb as solid phase microtrabeculae material
(II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III), and compared for the TiO of preparation under similarity condition2Right
The adsorption effect of target analytes, final choice mass ratio is 1:1 GO-TiO2(1:1) composite is used for follow-up solid phase extraction
Take agent.Column operation step is as follows：Weigh 30 ~ 50 mg GO-TiO2(1:1) composite loads in PTFE microtrabeculae（20 mm×
2.0 mm i.d.）, a little cotton is filled at the two ends of post prevents material from spilling, and tightening nuts, with 0.5 mol L-1HNO3With
0.1 mol L-1NH4Ac cleans successively and balances microtrabeculae.Same method processes other ratios and fills out column material and TiO2.Solid phase extracts
Take microtrabeculae GO-TiO2(1:1) composite is to containing 0.18 ~ 0.5 g mL-1Cu(II)、Pb(II)、La(III)、Ce(III)、
The solution of Eu (III), Dy (III) and Yb (III) is enriched with, and is 0.3 ~ 1 mol L with 0.7mL molar concentration-1Nitric acid enter
Row wash-out, inductively coupled plasma atomic emission（ICP-OES）It is measured, the rate of recovery is more than 90%.Material can make repeatedly
With 90 times.
The main advantages of the present invention it is as follows：
（1）The present invention is prepared for GO-TiO using in-situ synthesis2Composite, and optimize material proportion, have selected
GO-TiO2(1:1) composite is as solid extracting agent, to Cu (II), Pb (II), La (III), Ce (III), Eu (III),
Dy (III) and Yb (III) has preferable Selective adsorption.
（2）The GO-TiO of the inventive method preparation2(1:1) composite have pH scope of application width, the rate of adsorption fast,
Adsorption capacity is big, higher selectivity, strong antijamming capability and the advantages of long service life.
（3）The GO-TiO of present invention preparation2(1:1) composite can be used for separation/enrichment environment water sample（Including high salt
Degree seawater）With the target analytes in bed mud, it is a kind of solid extracting agent that can be practical.
Brief description
Fig. 1 is the TiO prepared by embodiment 12The absorption figure to object ion under different pH；
Fig. 2 is the GO-TiO prepared by embodiment 12(1:9) the absorption figure to object ion under different pH；
Fig. 3 is the GO-TiO prepared by embodiment 12(1:3) the absorption figure to object ion under different pH；
Fig. 4 is the GO-TiO prepared by embodiment 12(1:1) the absorption figure to object ion under different pH；
The solid extracting agent GO-TiO that Fig. 5 is selected by embodiment 22(1:1) the FT-IR spectrogram of composite；
The solid extracting agent GO-TiO that Fig. 6 is selected by embodiment 22(1:1) thermogravimetric curve of composite；
The solid extracting agent GO-TiO that Fig. 7 is selected by embodiment 22(1:1) XRD of composite；
The solid extracting agent GO-TiO that Fig. 8 is selected by embodiment 22(1:1) transmission electron microscope picture of composite；Wherein,
Fig. 8（A）For under low multiplication factor（40000 x）Transmission electron microscope picture it can be seen that TiO2It is evenly distributed in GO aspect, particle diameter
Between 10-15 nm；Fig. 8（B）For under high-amplification-factor（400000 x）Transmission electron microscope picture, Fig. 8（B）And（A）Figure upper right
The bright TiO of angle SEAD chart2For Detitanium-ore-type, this is consistent with X-ray powder diffraction characterization result.
Specific embodiment
The present invention is prepared for composite GO-TiO2, and optimizing material proportion, the material that have selected best proportion is used for
Cu (II) in separation/enrichment environment sample, Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) trace
Secondary element, is expanded on further the present invention 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 present invention processed.
It is used in embodiment 1 and embodiment 4 measuring Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy
And the instrument of Yb (III) content composes direct-reading inductive etc. entirely for the Intrepid XSP Radial type of thermoelectricity department of the U.S. (III)
Emission spectrometer（ICP-OES）.
Embodiment 1：
Method with reference to improved Hummers prepares GO：By 2.5 g K2S2O8With 2.5 g P2O5It is added to 12 mL dense
In sulfuric acid, then by 3 g graphite dispersed with stirring wherein, it is heated to 80 °C, stop stirring after reaction 4.5 h, cool overnight, take out
Filter, is washed to 40 °C of drying in vacuum drying chamber after neutrality.By the graphite dispersion of pre-oxidation in the 120 mL concentrated sulfuric acids（98%,
Analysis is pure）In, add 15 g KMnO under ice bath4, control and add speed to make reaction temperature≤20 °C, stir 7 days under 35 °C.
Add 250 mL deionized waters, control temperature under 50 °C, then be warming up to 98 °C of stirring 2 h, then reactant liquor is proceeded to burning
In cup, add 0.7 L deionized water terminating reaction.Add 20 mL 30% H2O2（v/v）, for by MnO4 and titanium dioxide
Manganese is reduced to manganese ion, stands overnight after magnetic agitation 2h.After upper solution is outwelled, remaining solid 1.3 L 10% HCl
（v/v）Washed（Wash centrifugation with 35 ~ 40 mL10% HCl in centrifuge tube every time, after discarding upper strata centrifugate, again plus
Enter 10% HCl and carry out washing centrifugation, share and remove volume 1.3 L）, centrifugation, be then washed with deionized again solid to wash after
Deionized water be neutrality.Freeze-drying obtains brown color graphene oxide solid.Carry out ultrasonic stripping before synthetic composite material
From.
GO-TiO2The preparation of composite adopts in-situ synthesis, i.e. in-situ hydrolysis Ti (BuO)4, nucleating growth on GO
For TiO2.Synthetic schemes is specific as follows：120 mg GO are added to EtOH/H2O（350 mL/25 mL）In, ultrasonic disperse 0.5
H, then oil bath heating is to 80 °C；By Ti (BuO)4It is dissolved in EtOH/H2SO4（25 mL/0.375 mL）In, then it is added dropwise over
To in GO suspension.In 80 °C of lower stirring reaction 12 h.Carry out being centrifuged and washed with 500 mL deionized waters, by solid in true
It is dried under 60 °C in empty drying box.By changing GO and Ti (BuO)4Ratio synthesize different quality ratio GO-TiO2Compound
Material（GO:TiO2=1:9、1:3、1:1、3:1、9:1）.In addition, being added without GO to be prepared for TiO under the same terms2Material.
Embodiment 2：
Different proportion GO-TiO prepared by embodiment 12Composite and TiO2It is filled in respectively in SPE microtrabeculae,
Carry out extracting index experiment.
Weigh 50 mg GO-TiO2（1:9）、GO-TiO2（1:3）、GO-TiO2（1:1）、GO-TiO2（3:1）、GO-TiO2
（9:1）And TiO2Material is filled in microtrabeculae respectively, is contained using 2.5 mL under flow injection Dynamic Adsorption condition of different pH
Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III) are respectively 0.5 g mL-1Solution.Institute
It is 0.5 mL/min with flow velocity.
Experiment finds with GO-TiO2（3:1）And GO-TiO2（9:1）Big, operating difficulties pressed by microtrabeculae post for filler, not easy-to-use
In solid phase microtrabeculae filler.Fig. 1,2,3 and 4 are respectively TiO2Material, composite GO-TiO2（1:9）、GO-TiO2（1:3）、GO-
TiO2（1:1）With the absorption situation in the range of pH 1-10 to metal ion.As shown in Figure 1, TiO2Right in the range of pH 7-10
Target metal ions can achieve Absorption quantity；As shown in Figure 2, GO and TiO2Mass ratio is 1:9 composite GO-TiO2(1:
9) Absorption quantity analyte in the range of pH 4-10；GO and TiO2Mass ratio is 1:3 and 1:1 composite GO-TiO2(1:
3) （Fig. 3）、GO-TiO2(1:1) （Fig. 4）Can Absorption quantity metal ion in pH 3-10 scope.Following knot can be drawn
By：Compared to TiO2, composite GO-TiO2Low pH is shifted to the Absorption quantity of object ion, and in material, GO content is higher
Then the pH of Absorption quantity is lower, and in illustrative material, GO plays a key effect when retaining object ion.Excellent in view of GO uniqueness
Gesture, the composite GO-TiO that ratio containing GO is 50%2(1:1) as solid extracting agent, for target in environmental sample
Separation/the enrichment of ion.
Absorption quantity in described refers both to adsorption rate more than 90%.
Embodiment 3：
To the composite GO-TiO selecting in embodiment 22(1:1) carry out IR Characterization（FT-IR）, thermogravimetric analysis
（TGA/DTG）, X-ray powder diffraction characterize（XRD）And transmission electron microscope characterizes（TEM）It was demonstrated that material is successfully prepared.
Using FT-IR spectrometer to the composite GO-TiO selecting in embodiment 22(1:1) solid extracting agent is carried out
IR Characterization（As shown in Figure 5）, Fig. 5 is the material GO prepared by embodiment 1（Curve（A））、TiO2（Fig. 5（B））And GO-
TiO2(1:1) （Curve（C））IR Characterization collection of illustrative plates.In curve（A）In 1065,1229,1384,1627 and 1733
cm-1Be respectively C O C stretching vibration peak on GO, C OH vibration peak, O H deformation vibration in C OH, C=C stretching vibration and
C=O stretching vibration peak in COOH group, these different oxygen-containing group explanations are successfully prepared GO.In TiO2Infrared in figure, 1621
cm-1Locate as 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 Materials2012,205, 229-235.）.Composite wood
Material GO-TiO2(1:1) still remain GO and TiO2On characteristic peak, in 744 cm-1The new peak that place occurs is that C O Ti exists
798 cm-1The vibration peak at place（Sakthivel, S.; Kisch, H., "Daylight photocatalysis by
carbon-modified titanium dioxide".Angewandte Chemie-International Edition
2003,42(40), 4908-4911.）With being superimposed of Ti O Ti characteristic peak.In GO, TiO2And GO-TiO2(1:1) material
In, in 3409 cm-1It is relevant with the hydrone containing that wider O-H vibration peak in left and right.
Fig. 6 thermogravimetric analysis（TGA, curve（A）For GO, curve（B）For GO-TiO2(1:1)）And differential thermal analysis（DTG, bent
Line（C）For GO, curve（D）For GO-TiO2(1:1)）Shown, for GO and composite GO-TiO2(1:1), 100oC with
Under, it is that solvent evaporation that remain in material or absorption is weightless；The losing 196 of the upper oxygen-containing group of GOoC about, with report
Result is consistent（McAllister, M. J.; 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 Materials2007,19
(18), 4396-4404.）；GO-TiO2(1:1) composite is 229oC about lose oxygen-containing group, increased 30 compared with GOoC
Left and right, this is likely due to TiO2Act on so as to stability increased with oxygen-containing group in GO（Lee, Y. C.; Yang, J.
W., "Self-assembled flower-like TiO2on exfoliated graphite oxide for heavy
metal removal".Journal of Industrial and Engineering Chemistry2012,18(3),
1178-1185.）.TGA/DTG curve shows GO and GO-TiO2(1:1) in, oxygen-containing group loses ratio and is respectively 35%, 17%, table
Bright composite GO-TiO2(1:1) in, GO mass is about 50%, and this is consistent with initial rate of charge.
Using powder x-ray diffraction（XRD）To the composite GO-TiO selecting in embodiment 22(1:1) solid phase extraction
Agent is taken to be characterized.Fig. 7 curve（A）It is the XRD of the GO of preparation in embodiment 1, its characteristic diffraction peak occurs in 2 θ angles and is
10.9o, its interlamellar spacing about 0.81 nm.Fig. 7 curve（B）It is the TiO of preparation in embodiment 12XRD, its 2 θ diffraction maximum
25.62o、37.98o、48.14o、54.12o/55.34o、62.56o/62.96oWith 68.8o/70.02oCorrespond to respectively（101）、
（004）、（200）、（105/211）、（213/204）With（116/220）Crystal face, consistent with Detitanium-ore-type（JCPDS no.00-
021-1272）.Fig. 7 curve（C）It is composite GO-TiO2(1:1) XRD is it can be seen that the characteristic diffraction peak of GO disappears
Lose, this is likely to and TiO2Special adsorption relevant（Zhang, X. Y.; Li, H. P.; Cui, X. L.; Lin, Y.
H., "Graphene/TiO2nanocomposites: synthesis, characterization and
application in hydrogen evolution from water photocatalytic splitting".Journal of Materials Chemistry2010,20(14), 2801-2806；Liu, J. C.; Bai, H.
W.; Wang, Y. J.; Liu, Z. Y.; Zhang, X. W.; Sun, D. D., "Self-Assembling TiO2
Nanorods on Large Graphene Oxide Sheets at a Two-Phase Interface and Their
Anti-Recombination in Photocatalytic Applications".Advanced Functional Materials2010,20(23), 4175-4181.）
Using transmission electron microscope（TEM）Observe the composite GO-TiO selecting in embodiment 22(1:1) solid phase
Extractant, such as Fig. 8（A）、（B）Shown,（A）In figure can be seen, TiO2It is evenly distributed in GO aspect, particle diameter is in 10-15
Between nm.（B）Figure and（A）The bright TiO of figure upper right corner SEAD chart2For Detitanium-ore-type, this and X-ray powder diffraction
Characterization result is consistent.
Embodiment 4：
The explanation of embodiment 3 result is successfully prepared composite GO-TiO2(1:1), further study its conduct in this
The adsorption capacity of solid extracting agent, the common coexisting ion disturbed condition of tolerance, service life and answering in actual environment sample
With.
Embodiment 1 extraction experiments show composite GO-TiO2(1:1) can Absorption quantity target in the range of pH 3-10
Ion, it is experiment condition that following experiment selects pH=5.
（1）Concentration is 10 g mL by experiment-1List mark ion in 2.0 mL min-1Pass through GO-TiO under flow velocity2(1:
1) fill out column material, and obtain composite GO-TiO with concentration of metal ions in ICP-OES detection efflux to adsorption saturation2
(1:1) the adsorption capacity difference to Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and Yb (III)
For 8.2,64.2,28.7,25.1,16.6,19.3 and 24.1 mg g-1.
（2）It is 0.18 g mL to concentration-1Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III) and
The solution of Yb (III) has carried out the experiment of common interference ion, 10000 mg L-1K+, 10000 mg L-1Na+, 5000 mg L-1Ca2+, 5000 mg L-1Mg2+, 10 mg L-1Al3+, 20 mg L-1Fe3+, 15000 mg L-1Cl-, 15000 mg L-1
NO3 -With 5000 mg L-1SO4 2-Absorption on object ion does not produce impact, with 1 mol L-1Nitric acid elutes, and its rate of recovery is equal
More than 90%.
（3）The 7 mL solution containing target analytes pass through microtrabeculae, then with 0.7 mL 1.0 mol L-1HNO3Carry out
Wash-out, and with 1 mL 0.1 mol L-1NH4Ac is balanced.Material can be at least using 90 times, and the rate of recovery does not substantially drop
Low.Show prepared GO-TiO2(1:1) composite has that good stability, capacity antacid be strong and long service life etc.
Advantage.
（4）By composite GO-TiO2(1:1) it is used for the analysis of target analytes in actual sample, sample includes East Lake
Water, Yangtze River Water（Wuhan, China）And seawater（Hangzhou Wan, China）And East Lake, the Changjiang river bed mud sample（Wuhan, China）.Water sample
, between 82.4-115.5%, bed mud recovery of standard addition is between 83.8-114.8% for recovery of standard addition.
Claims (1)
1. one kind utilizes graphene oxide-TiO2The method of composite separation/enriching heavy metal ion it is characterised in that：First
Weigh the graphene oxide-TiO of 30～50mg2Composite loads in PTFE microtrabeculae, and the anti-block of appropriate cotton is filled at post two ends
Graphite alkene-TiO2Composite spills, tightening nuts；Then use 0.5mol L respectively-1HNO3With 0.1mol L-1NH4Ac
Clean successively and balance microtrabeculae, then pH is 3-10, is enriched with containing the solution of heavy metal ion, with molar concentration be finally
0.3～1mol L-1Salpeter solution eluted；Wherein, graphene oxide-TiO2In composite graphene oxide and
TiO2Mass ratio is 1：1, anatase type nano TiO2It is evenly distributed in graphene oxide aspect, TiO2Particle diameter is 10～15nm；
Described heavy metal ion is one of Cu (II), Pb (II), La (III), Ce (III), Eu (III), Dy (III), Yb (III)
Or it is several；
Described graphene oxide-TiO2Composite is prepared by following preparation methods：
(1) add graphene oxide into EtOH/H2In O, carry out ultrasonic disperse, form the suspension of graphene oxide, then 80
It is stirred under DEG C oil bath heating；Wherein, EtOH and H2The volume ratio of O is 350：25；
(2) by Ti (BuO)4It is dissolved in EtOH/H2SO4In, then it is added dropwise in the suspension of step (1) graphene oxide, control
Ti (BuO) processed4Consumption make graphene oxide and TiO2Mass ratio is 1：Stir under 1,80 DEG C of heating；Wherein, EtOH and H2SO4
Volume ratio be 25：0.375；
(3) product obtaining step (2) is centrifuged, milli-Q water, is dried, that is, obtains graphene oxide-TiO2Composite wood
Material.
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 CN104226253A (en) | 2014-12-24 |
| CN104226253B true 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) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817069B (en) * | 2014-12-25 | 2017-03-01 | 华南师范大学 | A kind of preparation facilitiess of Graphene composite block material and its method |
| CN104607064A (en) * | 2015-01-11 | 2015-05-13 | 王丽莉 | Method for preparing polyvinylidene fluoride-graphene oxide composite hollow fiber membrane |
| 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 |
| CN108906059B (en) * | 2018-07-06 | 2021-04-23 | 内蒙古农业大学 | TiO 22Magnetic porous composite material and preparation method thereof |
| CN110102258B (en) * | 2019-05-15 | 2021-02-12 | 华北电力大学 | Synthetic method and application of three-dimensional manganese dioxide and graphene oxide composite adsorbent |
Citations (2)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (2)
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 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;Shaowei Su et al;《Talanta》;20131125;第119卷;第458-466页 * |
| Structure and photocatalytic properties of TiO2-Graphene Oxide intercalated composite;ZHANG Qiong et al;《Chinese Sci Bull》;20110131;第56卷(第3期);第331-339页 * |
| TiO2 Nanocrystals Grown on Graphene as Advanced Photocatalytic Hybrid Materials;Yongye Liang et al;《Nano Research》;20101231;第3卷(第10期);第701-705页及Electronic Supplementary Materical第1-4页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104226253A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226253B (en) | Graphene oxide-TiO2 composite material and preparation method and application thereof | |
| 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 | |
| Zhang et al. | Electrocatalytically active cobalt-based metal–organic framework with incorporated macroporous carbon composite for electrochemical applications | |
| Tan et al. | Enhanced adsorption of uranium (VI) using a three-dimensional layered double hydroxide/graphene hybrid material | |
| Gu et al. | Two-dimensional MAX-derived titanate nanostructures for efficient removal of Pb (II) | |
| Qu et al. | Highly efficient synthesis of graphene/MnO2 hybrids and their application for ultrafast oxidative decomposition of methylene blue | |
| Wang et al. | Extraction of neonicotinoid insecticides from environmental water samples with magnetic graphene nanoparticles as adsorbent followed by determination with HPLC | |
| Zhao et al. | A facile route to the synthesis copper oxide/reduced graphene oxide nanocomposites and electrochemical detection of catechol organic pollutant | |
| Wang et al. | Highly-dispersed Fe2O3@ C electrode materials for Pb2+ removal by capacitive deionization | |
| 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 | |
| CN108328706A (en) | A kind of MOF derives the preparation and application of porous carbon/graphene combination electrode material | |
| CN104003368A (en) | Porous phosphor-nitrogen-codoped carbon material and preparation method thereof | |
| CN105238927A (en) | Titanium-based lithium ion sieve adsorbent, precursor thereof, preparation methods and application | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| Zhang et al. | Effective removal of methyl blue by fine-structured strontium and barium phosphate nanorods | |
| CN104671234B (en) | A method of preparing graphene using stratiform template carbonization | |
| WO2023142668A1 (en) | Method for preparing nitrogen-doped carbon dot-reduced graphene oxide composite material and use thereof | |
| CN102649590B (en) | Method for preparing mesoporous material NiAl2O4 without specific surface active agent | |
| CN108704610A (en) | The Mg-Fe ball composite material and preparation method of magnetic carbon modification and application | |
| Ohashi et al. | Lithium adsorption from natural brine using surface-modified manganese oxide adsorbents | |
| Heidarimoghadam et al. | Graphene oxide for rapid determination of testosterone in the presence of cetyltrimethylammonium bromide in urine and blood plasma of athletes | |
| CN106430304A (en) | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution | |
| Luo et al. | MOF-derived porous CeO 2− x/C nanorods and their applications in uric acid biosensor | |
| Yang et al. | Layered MnO 2 nanosheet as a label-free nanoplatform for rapid detection of mercury (ii) |
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 |
Granted publication date: 20170215 Termination date: 20171013 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |