CN102716746A - Recyclable and reusable organic dye photocatalyst and preparation method thereof - Google Patents

Recyclable and reusable organic dye photocatalyst and preparation method thereof Download PDF

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CN102716746A
CN102716746A CN2012101891610A CN201210189161A CN102716746A CN 102716746 A CN102716746 A CN 102716746A CN 2012101891610 A CN2012101891610 A CN 2012101891610A CN 201210189161 A CN201210189161 A CN 201210189161A CN 102716746 A CN102716746 A CN 102716746A
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graphene
titanium dioxide
preparation
photochemical catalyst
solution
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CN102716746B (en
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林岳
耿志刚
宋雨晴
曾杰
潘楠
王晓平
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Abstract

The invention provides a preparation method for a recyclable and reusable organic dye photocatalyst composite. The preparation method includes a) mixing graphene oxide liquor, titanium isopropoxide sulfuric acid and alcohol together to obtain mixed liquor; b) heating the mixed liquor and enabling the mixed liquor to react to obtain a graphene and titanium oxide composite; and c) mixing, heating and enabling the graphene and titanium oxide composite, liquor containing Fe2+ and Fe3+ and liquor containing OH- to react to obtain a graphene, titanium dioxide and ferroferric oxide photocatalyst. The invention further provides the photocatalyst composite which comprises a graphene layer, a titanium dioxide granular layer and a ferroferric oxide layer. The titanium dioxide granular layer is positioned on the graphene layer, and the ferroferric oxide layer is positioned on the titanium dioxide granular layer. The photocatalyst composite is fine in structural stability, and has high degradation rate after being used for degrading organic dye for multiple times.

Description

A kind of recovery, reused organic dyestuff photochemical catalyst and preparation method thereof of being easy to
Technical field
The present invention relates to the nano composite material technical field, relate in particular to a kind of recovery, reused organic dyestuff photochemical catalyst and preparation method thereof of being easy to.
Background technology
Energy resources, cultivated land resource and water resource also are called the three big grand strategy resources that support China's sustainable development of socio-economy.Along with the quickening of global economy, industrial development and the aggravation of mankind's activity, water pollution problems is serious day by day, has become the global crisis of face of mankind.The discharging of industrial wastewater becomes the main source that water pollutes.
Along with developing rapidly of dyestuff textile industry, dye species and quantity constantly increase, and a large amount of waste water from dyestuff all will discharge every year in synthetic dyestuffs factory and printing and dyeing mill, and the emphasis that waste water from dyestuff has become industrial wastewater dyes one of source.According to national incomplete statistics, have 17% ~ 20% to come from waste water from dyestuff in the industrial wastewater.Be only China 2010 and just produced about 1,500,000 tons of organic dyestuff, the utilization rate of these organic dyestuff is extremely low, and often unprocessedly just directly is discharged in the environment, and this will directly influence public health and destroy environment.Therefore, how to handle organic dyestuff, become the focus of people's research to reduce its harm.
Mainly develop at present and two kinds of modes of handling organic dyestuff: absorbing dye and degradation of dye.For the mode of absorbing dye, owing to exist adsorption capacity low with reason such as reclaimer operation complicacy, its application has received than limitations.And for the mode of degrading, people once used TiO 2, semi-conducting material photocatalytically degradating organic dye such as ZnO or CdS, develop the magnetic material-TiO that various structures subsequently again 2Compound, the compound of this kind structure can reclaim compound through the magnetic way of recycling behind degradating organic dye.But magnetic material-TiO 2There is a problem in compound, and promptly the compound of this kind structure is in the process of degradating organic dye, and the magnetic material in the compound is reduced, then magnetic material-TiO 2Composite structure is destroyed, thereby the compound that reclaims reduces, if with the magnetic material-TiO that reclaims 2Compound is degradating organic dye once more, and the degradation rate of organic dyestuff can obviously descend.Therefore, because photochemical catalyst magnetic material-TiO 2Composite structure stable bad, its repeatedly the degradating organic dye degradation rate obviously slow down.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of and is easy to reclaim, the preparation method of reused organic dyestuff photochemical catalyst.
In view of this, the invention provides a kind ofly be easy to reclaim, the preparation method of reused organic dyestuff photocatalyst composite, may further comprise the steps:
A) graphene oxide solution, isopropyl titanate, sulfuric acid and alcohol are mixed, obtain mixed liquor;
B), obtain Graphene-titanium dioxide compound with the heating of said mixed liquor and react;
C) with said Graphene-titanium dioxide compound, contain Fe 2+And Fe 3+Solution with contain OH -Solution mix, heat and react, obtain photocatalyst composite.
Preferably, said step a) is specially:
With proportioning is graphene oxide solution, isopropyl titanate, sulfuric acid and the alcohol mixing of 4 ~ 10mL:40 ~ 100 μ L:110 ~ 250 μ L:20 ~ 200mL, obtains mixed liquor, and the concentration of said graphene oxide solution is 0.5mg/mL.
Preferably, heating described in the step b) is divided into heating for the first time and heating for the second time.
Preferably, the temperature of the said heating first time is 60 ℃ ~ 100 ℃, and the time of the said heating first time is 4h ~ 30h.
Preferably, the temperature of the said heating second time is 150 ℃ ~ 240 ℃, and the time of the said heating second time is 4h ~ 30h.
Preferably, said Fe 2+And Fe 3+Mol ratio be (1.4 ~ 2.6): (2.4 ~ 3.6).
Preferably, the said Fe that contains 2+And Fe 3+Solution be FeCl 2H 2O and FeCl 3H 2The aqueous solution of O.
Preferably, the temperature that heats described in the step c) is 50 ℃ ~ 100 ℃.
The time of preferably, heating described in the step c) is 2h ~ 10h.
The present invention also provides a kind of and has been easy to reclaim, reused organic dyestuff photocatalyst composite, comprising: graphene layer, titanium dioxide granule layer and magnetite layer; Said titanium dioxide granule layer is positioned on the graphene layer, and said magnetite layer is positioned on the said titanium dioxide granule layer.
Compared with prior art, the present invention's a kind of Graphene-titanium dioxide-tri-iron tetroxide photocatalyst composite that adopted method for preparing.On the one hand, because Graphene has the characteristic that absorbs electronics, the light induced electron that titanium dioxide produces under illumination condition is transferred to Graphene, has stoped the compound of light induced electron and photohole, the OH in then more photohole and the organic dyestuff -Generate hydroxyl radical free radical, hydroxyl radical free radical has extremely strong oxidisability, effectively degradating organic dye; Because the light induced electron overwhelming majority is transferred to Graphene, the light induced electron that is transferred to the tri-iron tetroxide surface is less, has avoided the Fe in the tri-iron tetroxide simultaneously 3+Be reduced into Fe 2+, the stability of Graphene-titanium dioxide-tri-iron tetroxide compound photochemical catalyst is guaranteed; On the other hand, the tri-iron tetroxide that exists in the photochemical catalyst of the present invention is easy to magnetic and reclaims and do not change, and is stable better after therefore photochemical catalyst provided by the invention is repeatedly degraded-reclaimed-degrade-reclaim, and still has higher degradation rate.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the Graphene-titanium dioxide-tri-iron tetroxide photochemical catalyst of the embodiment of the invention 1 preparation;
Fig. 2 is the X ray diffracting spectrum of the Graphene-titanium dioxide-tri-iron tetroxide photochemical catalyst of the embodiment of the invention 1 preparation;
Fig. 3 is the degradation rate curve map of Graphene-titanium dioxide-5 degradating organic dyes of tri-iron tetroxide photochemical catalyst of the embodiment of the invention 1 preparation;
Fig. 4 is the degradation rate curve map of the different pH rhodamine B of the Graphene-titanium dioxide-tri-iron tetroxide photocatalyst for degrading solution of the embodiment of the invention 1 preparation;
Fig. 5 is the change procedure curve map of the mixed solution of blue, the orange and rhodamine B of Graphene-titanium dioxide-tri-iron tetroxide photocatalyst for degrading acid of the embodiment of the invention 1 preparation;
Fig. 6 is the change procedure curve map of Graphene under solar light irradiation-titanium dioxide tri-iron tetroxide photocatalyst for degrading rhodamine B solution;
Fig. 7 is the transmission electron microscope photo of photochemical catalyst a ~ f;
Fig. 8 is the electronic energy spectrum of photochemical catalyst a ~ f;
Fig. 9 is the rate profile of titanium dioxide, Graphene-titanium dioxide and photochemical catalyst a ~ f degradating organic dye.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind ofly be easy to reclaim, the preparation method of reused organic dyestuff photocatalyst composite, may further comprise the steps:
A) graphene oxide solution, isopropyl titanate, sulfuric acid and alcohol are mixed, obtain mixed liquor;
B), obtain Graphene-titanium dioxide compound with the heating of said mixed liquor and react;
C) with Graphene-titanium dioxide compound, contain Fe 2+And Fe 3+Solution with contain OH -Solution mix, heat and react, obtain photocatalyst composite.
Step a) is to prepare the process of mixed liquor, and the proportion optimization of said graphene oxide solution, sulfuric acid, isopropyl titanate and alcohol is 4 ~ 10mL:40 ~ 100 μ L:110 ~ 250 μ L:20 ~ 200mL.Said graphene oxide solution is preferably the graphene oxide that adopts the preparation of hummer method, and the concentration of said graphene oxide solution is preferably 0.5mg/mL.After obtaining mixed liquor, step b) is the process of preparation photochemical catalyst predecessor Graphene-titanium dioxide compound, with said mixed liquor heating and react, obtains Graphene-titanium dioxide compound.
In the process of preparation Graphene-titanium dioxide compound, under heating condition, the water reaction in isopropyl titanate and the mixed liquor obtains titanium dioxide; In order to make the graphene oxide sufficient reacting; As preferred version; Heating in the step b) specifically is divided into heating for the first time and heating for the second time, and the temperature of the said heating first time is preferably 60 ℃ ~ 100 ℃, more preferably 80 ℃; The time of the said heating first time is preferably 4h ~ 30h, more preferably 12h; The said heating second time is preferably carried out in autoclave, and the temperature of the said heating second time is preferably 150 ℃ ~ 240 ℃, and more preferably 200 ℃, the time of the said heating second time is preferably 4h ~ 30h, more preferably 12h.After twice heating, graphene oxide is reduced, and obtains Graphene.Sulfuric acid in the mixed liquor makes the titanium dioxide of generation be grown in the Graphene surface, is grown in the Graphene surface in order to make more titanium dioxide, and said sulfuric acid is preferably the concentrated sulfuric acid, and said alcohol is preferably absolute alcohol.
Step c) is the process that is generated Graphene-titanium dioxide-tri-iron tetroxide compound by Graphene-titanium dioxide compound, and Graphene-titanium dioxide compound as predecessor, is added and contains Fe 2+And Fe 3+Solution with contain OH -Solution, reaction as follows takes place:
8OH -+Fe 2++2Fe 3+＝Fe 3O 4↓+4H 2O；
The tri-iron tetroxide that generates is grown in Graphene-titanium dioxide compound surface, promptly obtains Graphene-titanium dioxide-tri-iron tetroxide compound.The said Fe that contains 2+And Fe 3+Solution be preferably FeCl 2H 2O and FeCl 3H 2The aqueous solution of O.Said Fe 2+And Fe 3+Mol ratio be preferably (1.4 ~ 2.6): (2.4 ~ 3.6).The temperature of above-mentioned heating is preferably 50 ~ 100 ℃, more preferably 60 ~ 90 ℃.The time of above-mentioned heating is preferably 2 ~ 10h, more preferably 2.5h ~ 5h.The said OH that contains -Solution be preferably the ammoniacal liquor of 1.5mol/L.
The present invention also provides a kind of and has been easy to reclaim, reused organic dyestuff photocatalyst composite, comprising: graphene layer, titanium dioxide granule layer and magnetite layer; Said titanium dioxide granule layer is positioned on the graphene layer, and said magnetite layer is positioned on the said titanium dioxide granule layer.
Graphene-titanium dioxide of the present invention-tri-iron tetroxide compound photochemical catalyst is used for degradating organic dye, and said organic dyestuff is preferably rhodamine B, acid is blue or orange.The photochemical catalyst that in containing the solution of above-mentioned organic dyestuff, adds the present invention's preparation; Under illumination condition, organic dyestuff is degraded, and with common magnet this photochemical catalyst is reclaimed subsequently; Without any need for processing, photochemical catalyst can directly be used for the degraded of next organic dyestuff.
Photochemical catalyst of the present invention is integrated titanium dioxide, Graphene and three kinds of materials of tri-iron tetroxide; Graphene is because himself particular structure; Make its performance with strong absorption, store electrons, so titanium dioxide is when contacting with Graphene, the electronics that titanium dioxide produces under illumination condition can be transferred in the Graphene; Stop electronics and hole-recombination, make the OH in more hole and the water -In conjunction with generating hydroxyl radical free radical; And hydroxyl radical free radical is as the effective degradating organic dye of the strongest material of occurring in nature oxidisability; On this basis, the tri-iron tetroxide of the present invention's preparation is grown on " Graphene-titanium dioxide " structure, and the electronics overwhelming majority in the titanium dioxide is transferred to Graphene; Reduced the electronics that is transferred to tri-iron tetroxide, the Fe in the tri-iron tetroxide 3+Avoid being reduced into Fe 2+So,, the structural stability of Graphene-titanium dioxide-tri-iron tetroxide photochemical catalyst is guaranteed.
In order further to understand the present invention, below in conjunction with embodiment photochemical catalyst provided by the invention is described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
A) get the graphene oxide of 7mL 0.5mg/mL, join in the absolute alcohol of 65mL with the preparation of hummers method;
B) the 180 μ L isopropyl titanates and the 70 μ L concentrated sulfuric acids are dissolved in the 5mL absolute alcohol; Obtain mixture, in the mixture that the slow implantation step of this mixture a) obtains, and it is warmed up to 80 ℃ and keep 12h; Place autoclave to seal product again, react 12h down at 200 ℃;
C) product that step b) is obtained is scattered in the 30mL deionized water, and the stirring of logical nitrogen, adds and contains 3.95mgFeCl 2H 2O and 60mgFeCl 3H 2The 1.56mL deionized water of O, under nitrogen, stir 5h after, with seal of vessel, slowly inject the ammoniacal liquor of 4.6mL1.5mol/L with syringe then after, under sealing state, be warming up to 65 ℃ and keep 2.5h;
D) with product that washed with de-ionized water obtained; Above-mentioned product is dispersed on the plating carbon film copper mesh that testing electronic microscope uses; After treating solvent evaporates; Obtain Graphene-titanium dioxide-tri-iron tetroxide photochemical catalyst, it is the JOEL2100 type high-resolution-ration transmission electric-lens observation down of 200000V that above-mentioned photochemical catalyst is placed accelerating potential.
Fig. 1 is the transmission electron microscope(TEM) photo of the Graphene-titanium dioxide-tri-iron tetroxide photochemical catalyst of embodiment 1 preparation; Illustration is corresponding SEAD style; Can find out that from this figure the titanium dioxide granule size is about 20nm; Ferriferrous oxide particles is about 80nm, and wherein titanium dioxide granule covers on the Graphene thick and fast, and the ferriferrous oxide particles relative density is less.Fig. 2 is the X ray diffracting spectrum of photochemical catalyst, and the ★ curve is Fe among Fig. 2 3O 4Diffraction maximum, ▲ curve is TiO 2Diffraction maximum, from figure can be distinct the diffraction maximum of finding out titanium dioxide and tri-iron tetroxide.
Graphene-titanium dioxide-tri-iron tetroxide photochemical catalyst that following examples are used is by embodiment 1 preparation.
Embodiment 2
A) with photochemical catalyst at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption; Reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
B) mixture with step a) shakes through abundant, and photochemical catalyst is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, places with quartzy bottled 5mL7.7 * 10 -6In the rhodamine B solution of mol/L, the pH value of rhodamine B solution is 7.03;
C) under the Philip-TUV/15W ultra violet lamp, the mixture that step b) is obtained stirs, and behind the degraded 5min, photochemical catalyst is drawn onto a side of quartzy bottle with magnet, gets the 2mL reactant liquor and surveys absorption spectra;
D) repeat present embodiment c), be colourless until reactant liquor, promptly rhodamine B is all degraded, and again photochemical catalyst is used magnet recovery;
E) repeat the step a) ~ step d) four times of present embodiment again, be about to same photochemical catalyst and reuse 5 times, observe the rate variation of its degraded rhodamine B.
Fig. 3 is the degradation rate curve map of the photochemical catalyst of embodiment 1 preparation through degradating organic dye, and illustration is ln (C 0/ C) time dependent curve; The ■ curve is the photochemical catalyst degradation rate curve of degradating organic dye for the first time among the figure; ● curve is the photochemical catalyst degradation rate curve of degradating organic dye for the second time, and ▲ curve is the photochemical catalyst degradation rate curve of degradating organic dye for the third time
Figure BDA00001744445400071
Curve is the degradation rate curve of the 4th degradating organic dye of photochemical catalyst,
Figure BDA00001744445400072
Curve is the degradation rate curve of the 5th degradating organic dye of photochemical catalyst.As can be seen from Figure 3, in 5 degradation processes, the degradation rate of the photochemical catalyst of embodiment 1 preparation remains unchanged basically, explains that the photochemical catalyst of the present invention's preparation has advantages of higher stability, can repeatedly keep stable in the degradation process.Because Graphene absorbs and the performance of store electrons, makes that the light induced electron on the titanium dioxide is transferred to Graphene, has suppressed the compound of electronics and hole on the one hand, has reduced the electronics that is transferred to tri-iron tetroxide on the other hand, has suppressed Fe in the tri-iron tetroxide 3+Be reduced into Fe 2+And diffuse to the process of solution, even therefore through repeatedly degraded, the photochemical catalyst of the present invention's preparation still can keep good catalytic performance.
Embodiment 3
A) with photochemical catalyst at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption, reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
B) mixture with step a) fully vibrates, and photocatalysis is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, is added to quartzy bottled 5mL 7.7 * 10 -6In the mol/L rhodamine B solution, regulate rhodamine B pH value of solution value to 5.02;
C) under the Philip-TUV/15W ultra violet lamp, the mixture that step b) is obtained stirs, and behind the degraded 5min, photochemical catalyst is drawn onto a side of quartzy bottle with magnet, gets the 2mL reactant liquor and surveys absorption spectra;
D) step a) ~ step c) of repetition present embodiment wherein in step b), transfers to 9.6 with rhodamine B pH value of solution value, and all the other operations are constant fully.
E) step a) ~ step c) of repetition present embodiment wherein in step b), transfers to 11.51 with rhodamine B pH value of solution value, and all the other are constant fully.
Rhodamine B pH value of solution value is 5.02,9.6 and 11.51 o'clock; Combining rhodamine B pH value of solution value among the embodiment 2 in addition is 7.03 degradation process; Can obtain under each pH value the organic dyestuff photochemical catalyst to the degraded change procedure of rhodamine B; As shown in Figure 4; Fig. 4 is the degradation rate curve map of the different pH rhodamine B of the photocatalyst for degrading solution of embodiment 1 preparation; The ■ curve is the degradation rate curve of 11.5 rhodamine B solution for photocatalyst for degrading pH among the figure; ● curve is the degradation rate curve of 9.6 rhodamine B solution for photocatalyst for degrading pH, and ▲ curve is the degradation rate curve of 7.03 rhodamine B solution for photocatalyst for degrading pH, and curve is the degradation rate curve of 5.02 rhodamine B solution for photocatalyst for degrading pH.Visible from Fig. 4; In neutral and weakly acidic solution environmental, degradation rate is constant basically, and degradation rate increases in the alkaline solution; Because hydroxide ion is more in alkaline solution, make titanium dioxide granule surface on the photochemical catalyst by polyhydroxyl ion modification more.On the one hand, hydroxide ion benefits the hole being modified with of titanium dioxide surface and combines with hydroxide ion to generate hydroxyl radical free radical, has promoted the oxidation of organic dyestuff, has promptly promoted the degraded of dyestuff; On the other hand, hydroxide ion is modified into elecrtonegativity with titanium dioxide surface, helps rhodamine B solution and is adsorbed on its surface, has therefore also promoted the degraded of dyestuff.
Embodiment 4
A) with photochemical catalyst at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption.Reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
B) mixture with step a) fully vibrates, and photocatalysis is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, is added to in the quartzy bottled 4.9mL dye solution, and above-mentioned dye solution is by 5 * 10 of 20 μ L -35 * 10 of acid indigo plant, 20 μ L -35 * 10 of the orange and 3 μ L of mol/L -3The mol/L rhodamine B is dissolved in the 4.857mL deionized water and joins;
C) under the Philip-TUV/15W ultra violet lamp, the mixture that step b) is obtained stirs, and behind the degraded 5min, photochemical catalyst is drawn onto a side of quartzy bottle with magnet, gets the 2mL reactant liquor and surveys absorption spectra;
D) repeat present embodiment c), be colourless until reactant liquor, promptly rhodamine B is all degraded, and photochemical catalyst is used magnet recovery;
Fig. 5 is the change procedure figure that acid mixed solution blue, orange and rhodamine B is degraded under the photochemical catalyst effect; Curve a is the absorption spectra of organic dyestuff when not degrading among the figure; Absorption spectra when curve b is photocatalyst for degrading organic dyestuff 10min, the absorption spectra when curve c is photocatalyst for degrading organic dyestuff 20min, the absorption spectra when curve d is photocatalyst for degrading organic dyestuff 30min; Absorption spectra when curve e is photocatalyst for degrading organic dyestuff 40min; Absorption spectra when curve f is photocatalyst for degrading organic dyestuff 50min, the absorption spectra when curve g is photocatalyst for degrading organic dyestuff 60min, the absorption spectra when curve h is photocatalyst for degrading organic dyestuff 70min; Absorption spectra when curve i is photocatalyst for degrading organic dyestuff 80min, the absorption spectra when curve j is photocatalyst for degrading organic dyestuff 90min.Can know that by Fig. 5 under the situation that three kinds of dyestuffs mix, the photochemical catalyst of the present invention's preparation still can because the hydroxyl radical free radical that photochemical catalyst produces has extremely strong oxidisability, therefore be enough to the organic dyestuff that oxidation mixes effectively with its degraded.
Embodiment 5
A) with photochemical catalyst at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption.Reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
B) mixture with step a) shakes through abundant, and photochemical catalyst is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, places with quartzy bottled 5mL7.7 * 10 -6In the rhodamine B solution of mol/L, the pH value of rhodamine B solution is 7.03;
C) under solar simulator (Oriel Sol3A Class AAA Solar Simulators) irradiation; The mixture that step b) is obtained stirs; After degraded a period of time, photochemical catalyst is drawn onto a side of quartzy bottle with magnet, gets the 2mL reactant liquor and survey absorption spectra;
D) repeat present embodiment c), be colourless until reactant liquor, promptly rhodamine B is all degraded, and photochemical catalyst is used magnet recovery.
Fig. 6 is the conditional curve figure of organic dyestuff photocatalyst for degrading rhodamine B solution under solar light irradiation; Curve a is the absorption spectra of organic dyestuff when not degrading in the picture in picture; Absorption spectra when curve b is photocatalyst for degrading organic dyestuff 30min; Absorption spectra when curve c is photocatalyst for degrading organic dyestuff 60min; Absorption spectra when curve d is photocatalyst for degrading organic dyestuff 90min, the absorption spectra when curve e is photocatalyst for degrading organic dyestuff 120min, the absorption spectra when curve f is photocatalyst for degrading organic dyestuff 150min; Absorption spectra when curve g is photocatalyst for degrading organic dyestuff 210min, the absorption spectra when curve h is photocatalyst for degrading organic dyestuff 270min.As can beappreciated from fig. 6, under the irradiation of sunlight, photochemical catalyst also can be degraded organic dyestuff; Reason is the composition that contains ultraviolet light in the sunshine; And Graphene contacts with titanium dioxide, and the part carbon is doped in the titanium dioxide, and then the band gap width of titanium dioxide diminishes; Make the absorption bands of this photochemical catalyst widen, then photochemical catalyst also degradable organic dyestuff under solar light irradiation to visible part.
Comparative example 1
A) get the 7mL deionized water, join in the absolute alcohol of 65mL;
B) the 180 μ L isopropyl titanates and the 70 μ L concentrated sulfuric acids are dissolved in the 5mL absolute alcohol, obtain mixture, in the mixture that the slow implantation step of this mixture a) obtains, and it is warmed up to 80 ℃ and keep 12h;
C) with product that washed with de-ionized water obtained; Above-mentioned product is dispersed on the plating carbon film copper mesh that testing electronic microscope uses; After treating solvent evaporates, obtain titanium dioxide optical catalyst, it is the JOEL2100 type high-resolution-ration transmission electric-lens observation down of 200000V that titanium dioxide is placed accelerating potential;
D) with titanium dioxide at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption, reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
E) mixture with step d) shakes through abundant, and photochemical catalyst is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, places with quartzy bottled 5mL7.7 * 10 -6In the rhodamine B solution of mol/L, the pH value of rhodamine B solution is 7.03;
F) mixture that step e) is obtained stirs under ultra violet lamp, behind the degraded 5min, with solution centrifugal, gets the 2mL supernatant and surveys absorption spectra;
G) repeat present embodiment f), be colourless until reactant liquor, promptly rhodamine B is all degraded, and photochemical catalyst titanium dioxide is used magnet recovery.
Comparative example 2
A) get the graphene oxide of 7mL 0.5mg/L, join in the absolute alcohol of 65mL, obtain the graphene oxide predecessor with the preparation of hummers method;
B) the 180 μ L isopropyl titanates and the 70 μ L concentrated sulfuric acids are dissolved in the 5mL absolute alcohol, obtain mixture, in the mixture that the slow implantation step of this mixture a) obtains, and it is warmed up to 80 ℃ and keep 12h;
C) with product that washed with de-ionized water obtained; Above-mentioned product is dispersed on the plating carbon film copper mesh that testing electronic microscope uses; After treating solvent evaporates, obtain Graphene-titanium dioxide compound, being placed on accelerating potential is the JOEL2100 type high-resolution-ration transmission electric-lens observation down of 200000V;
D) with photochemical catalyst Graphene-titanium dioxide at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption, reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
E) mixture with step d) shakes through abundant, and photochemical catalyst is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, places with quartzy bottled 5mL7.7 * 10 -6In the rhodamine B solution of mol/L, the pH value of rhodamine B solution is 7.03;
F) under ultraviolet irradiation, after the mixture that step e) is obtained stirs 5min,, get the 2mL supernatant and survey its absorption spectra solution centrifugal;
G) repeat present embodiment f), be colourless until reactant liquor, promptly rhodamine B is all degraded, and photochemical catalyst is used magnet recovery.
Comparative example 3
A) get the graphene oxide of 7mL 0.5mg/L, join in the absolute alcohol of 65mL, obtain the graphene oxide predecessor with the preparation of hummers method;
B) the 180 μ L isopropyl titanates and the 70 μ L concentrated sulfuric acids are dissolved in the 5mL absolute alcohol, obtain mixture, in the mixture that the slow implantation step of this mixture a) obtains, and it is warmed up to 80 ℃ and keep 12h;
C) remove change FeCl 36H 2O, FeCl 24H 2The amount of O and ammoniacal liquor, all the other the operation with embodiment 1 in step c) consistent, FeCl 36H 2O, FeCl 24H 2The concrete change amount of O and ammoniacal liquor is as shown in table 1;
D) with product that washed with de-ionized water obtained; Above-mentioned product is dispersed on the plating carbon film copper mesh that testing electronic microscope uses, treat solvent evaporates after, obtain six kinds of Graphene-titanium dioxide-tri-iron tetroxides; In above-mentioned six kinds of Graphene-titanium dioxide-tri-iron tetroxide compound; The amount of tri-iron tetroxide has nothing in common with each other, and is numbered a ~ f respectively, and being placed on accelerating potential is the JOEL2100 type high-resolution-ration transmission electric-lens observation down of 200000V;
E) with photochemical catalyst a ~ f at rhodamine B solution soaking 12h, make rhodamine B saturated in its surface adsorption, reclaim this photochemical catalyst, it is dispersed in the 71mL deionized water;
F) mixture with step e) shakes through abundant, and photochemical catalyst is uniformly dispersed in deionized water, gets the photochemical catalyst mixture of 100 μ L, places with quartzy bottled 5mL7.7 * 10 -6In the rhodamine B solution of mol/L, the pH value of rhodamine B solution is 7.03;
G) under the Philip-TUV/15W ultra violet lamp, the mixture that step f) is obtained stirs, and behind the degraded 5min, photochemical catalyst is drawn onto a side of quartzy bottle with magnet, gets the 2mL reactant liquor and surveys absorption spectra;
H) repeat present embodiment g), be colourless until reactant liquor, promptly rhodamine B is all degraded, and photochemical catalyst is used magnet recovery.
Table 1 FeCl 36H 2O, FeCl 24H 2The concrete change amount of O and ammoniacal liquor
Figure BDA00001744445400121
Can obtain the different organic dyestuff photochemical catalyst a ~ f of tri-iron tetroxide content by this comparative example; Its transmission electron microscope photo is as shown in Figure 7; Fig. 7 is the transmission electron microscope photo of the different photochemical catalyst of tri-iron tetroxide content; A) ~ F) corresponding to the sample a ~ f in this comparative example step 3, wherein illustration is the electron diffraction pattern of choosing separately.Corresponding with it electron spectrum is as shown in Figure 8, and the Fe signal strengthens gradually among visible sample a ~ f.Table 2 is the mol ratio of tri-iron tetroxide and the titanium dioxide of photochemical catalyst a ~ f.
The tri-iron tetroxide of every kind of photochemical catalyst of table 2 photochemical catalyst a ~ f and the mol ratio of titanium dioxide
Figure BDA00001744445400122
In conjunction with comparative example 1, comparative example 2 and comparative example 3; Can obtain changing in titanium dioxide, Graphene-titanium dioxide and Graphene-titanium dioxide-tri-iron tetroxide the amount of tri-iron tetroxide degraded correlation curve Fig. 9 as photochemical catalyst; The ■ curve is the degradation rate curve of titanium dioxide optical catalyst degradating organic dye among the figure; ● curve is the speed degradation curve of Graphene-titanium dioxide optical catalyst degradating organic dye; ▲ curve is the rate curve of photochemical catalyst a degradating organic dye; curve is the rate curve of photochemical catalyst b degradating organic dye; curve is the rate curve of photochemical catalyst c degradating organic dye;
Figure BDA00001744445400133
curve is the rate curve of photochemical catalyst d degradating organic dye; ◆ curve is the rate curve of photochemical catalyst e degradating organic dye, and
Figure BDA00001744445400134
curve is the rate curve of photochemical catalyst f degradating organic dye.Visible by Fig. 9, the degradation rate of titanium dioxide is slower, along with the combining of Graphene; Its degradation rate increases rapidly; Slightly reduce after the tri-iron tetroxide in the growth, but reach tri-iron tetroxide at 2.78 o'clock with mol ratio titanium dioxide, its degradation rate is still greater than simple titanium dioxide.Therefore, the design that Graphene, titanium dioxide and tri-iron tetroxide are integrated that the present invention proposes is significant, and promptly degradation rate is still higher, and the while can repeatedly repeat degraded again and not reduce degradation rate.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (10)

  1. One kind be easy to reclaim, the preparation method of reused organic dyestuff photocatalyst composite, may further comprise the steps:
    A) graphene oxide solution, isopropyl titanate, sulfuric acid and alcohol are mixed, obtain mixed liquor;
    B), obtain Graphene-titanium dioxide compound with the heating of said mixed liquor and react;
    C) with said Graphene-titanium dioxide compound, contain Fe 2+And Fe 3+Solution with contain OH -Solution mix, heat and react, obtain photocatalyst composite.
  2. 2. preparation method according to claim 1 is characterized in that, said step a) is specially:
    With proportioning is graphene oxide solution, isopropyl titanate, sulfuric acid and the alcohol mixing of 4 ~ 10mL:40 ~ 100 μ L:110 ~ 250 μ L:20 ~ 200mL, obtains mixed liquor, and the concentration of said graphene oxide solution is 0.5mg/mL.
  3. 3. preparation method according to claim 1 is characterized in that, heating described in the step b) is divided into heating for the first time and heating for the second time.
  4. 4. preparation method according to claim 3 is characterized in that, the temperature of the said heating first time is 60 ℃ ~ 100 ℃, and the time of the said heating first time is 4h ~ 30h.
  5. 5. preparation method according to claim 3 is characterized in that, the temperature of the said heating second time is 150 ℃ ~ 240 ℃, and the time of the said heating second time is 4h ~ 30h.
  6. 6. preparation method according to claim 1 is characterized in that, said Fe 2+And Fe 3+Mol ratio be (1.4 ~ 2.6): (2.4 ~ 3.6).
  7. 7. preparation method according to claim 1 is characterized in that, the said Fe that contains 2+And Fe 3+Solution be FeCl 2H 2O and FeCl 3H 2The aqueous solution of O.
  8. 8. preparation method according to claim 1 is characterized in that, the temperature that heats described in the step c) is 50 ℃ ~ 100 ℃.
  9. 9. preparation method according to claim 1 is characterized in that, the time of heating described in the step c) is 2h ~ 10h.
  10. 10. one kind is easy to recovery, reused organic dyestuff photocatalyst composite, it is characterized in that, comprising: graphene layer, titanium dioxide granule layer and magnetite layer; Said titanium dioxide granule layer is positioned on the said graphene layer, and said magnetite layer is positioned on the said titanium dioxide granule layer.
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CN103007944A (en) * 2012-12-13 2013-04-03 同济大学 Preparation method of graphene-based magnetic composite visible light catalysis material Fe3O4-G-TiO2
CN104229924A (en) * 2014-08-15 2014-12-24 扬州大学 Method for photocatalyzing dye wastewater with double-rare-earth oxide graphene composite
CN109399781A (en) * 2019-01-02 2019-03-01 广东石油化工学院 The catalysis of support type graphene produces potentiometric titrations oxidation processes waste water from dyestuff method
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