CN102631939A - Graphene/silver phosphate composite visible light photocatalyst and preparation method thereof - Google Patents
Graphene/silver phosphate composite visible light photocatalyst and preparation method thereof Download PDFInfo
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- CN102631939A CN102631939A CN201210085277XA CN201210085277A CN102631939A CN 102631939 A CN102631939 A CN 102631939A CN 201210085277X A CN201210085277X A CN 201210085277XA CN 201210085277 A CN201210085277 A CN 201210085277A CN 102631939 A CN102631939 A CN 102631939A
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Abstract
The invention discloses a high-efficiency graphene/silver phosphate composite visible light photocatalyst and a preparation method thereof, belonging to the technical field of composite materials and environmental management photocatalysis. The preparation method comprises the following steps: dissolving graphene oxide in water, and carrying out ultrasonic treatment to obtain a graphene oxide dispersed liquid; dissolving silver nitrate in deionized water, gradually and dropwisely adding into the graphene oxide dispersed liquid while stirring to obtain a mixed solution, uniformly stirring, and aging; dropwisely adding a prepared disodium hydrogen phosphate or sodium dihydrogen phosphate solution into the graphene oxide-silver nitrate mixed solution, continuing stirring, transferring into a hydrothermal reaction kettle, carrying out hydrothermal reaction, and cooling to room temperature; and washing the reaction product, and carrying out vacuum drying to obtain the visible light photocatalyst. The invention has the advantages of wide material sources and simple preparation process; and the obtained composite material has the advantages of controllable structure and regular pattern, and has high-efficiency degradation effect on organic dyes rhodamine B and methylene blue with certain concentration under the visible light irradiation.
Description
Technical field
The present invention relates to photochemical catalyst; Refer in particular to a kind of Graphene/silver orthophosphate compounded visible light photocatalyst and preparation method thereof; Be meant a kind of Graphene/silver orthophosphate compounded visible light photocatalyst and hydrothermal preparing process thereof especially, belong to photocatalysis technology field in composite and the environmental improvement.
Background technology
From the seventies in last century; The environmental pollution and the energy shortage that continue; Caused the worry of people,, developed a kind of new technology that environmental improvement can be used for the clean energy resource preparation again that promptly can be used in order to realize the sustainable development of human society to global crisis; Become a urgent and urgent task; Photocatalysis technology prepares the wide application prospects in field such as (conversion of solar energy are a Hydrogen Energy) because of it at environmental protection, clean energy resource, and is paid much attention to, and becomes a kind of technology that has application prospect.
The key of photocatalysis technology research is a photochemical catalyst; For a long time; Based on the photochemical catalyst of conductor oxidates such as titanium dioxide, zinc oxide rely on its under UV-irradiation preferably photocatalysis performance received researcher's attention; But the band gap of its broad has reduced the utilization rate to visible light, has limited their commercial application; Have the utilization rate of photochemical catalyst to visible light now though can improve through technology such as ion doping, modification are compound, increase rate is limited; Therefore, the efficient compound catalyst that development of new is visible light-responded becomes the focus direction that present photocatalysis is studied.
Contain the silver compound of p p-block element p owing to have the band structure of dispersion, can reduce the recombination rate of photo-generated carrier, thereby embody excellent photocatalysis activity; People such as Ye in 2010 (
Nature Mater., 2010,9, the silver orthophosphate of 559-564) at first finding specific morphology has very strong photooxidation under the visible light effect active, and water oxidation quantum yield is near 90%; People such as report Ye etc. in 2011 reported again micron order silver orthophosphate material crystal face regulation and control and photocatalysis performance (
J. Am. Chem. Soc.,2011,133,6490-6492), further disclosed the huge applications prospect of silver orthophosphate in photocatalysis field; Though the silver orthophosphate material size of above-mentioned bibliographical information is regular, pattern is controlled, size is relatively large; Chinese invention patent (CN101648139 B) has been reported a kind of novel visible catalyst-silver phosphate and preparation method thereof; Chinese invention patent (201110020586.4) has been reported a kind of electro-deposition silver orthophosphate photocatalytic semiconductor film and preparation method thereof.
Chinese invention patent 201210028396.1 discloses a kind of graphene oxide/silver orthophosphate compounded visible light photocatalyst and preparation method thereof; Be to be raw material with graphene oxide, silver acetate; Mix through mechanical agitation earlier, make graphene oxide/silver orthophosphate nano compounded visible light photocatalyst through reaction then with sodium hydrogen phosphate or sodium dihydrogen phosphate; It adopts the solwution method preparation, and composition is graphene oxide-silver orthophosphate, for 1x10
-5Organic dyestuff rhodamine B and the methylene blue solution of mol/L, this nano composite photo-catalyst radiation of visible light after 8 minutes the degradation rate to rhodamine B be 100 %, the degradation rate of methylene blue is also surpassed 90%.
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Summary of the invention
The purpose of this invention is to provide a kind of efficient Graphene/silver orthophosphate compounded visible light photocatalyst with low cost and preparation method thereof; Adopt Hydrothermal Preparation to go out controllable structure, high activity, visible light-responded Graphene/silver orthophosphate composite photo-catalyst first; The in-situ reducing of graphene oxide and effective regulation and control of silver orthophosphate pattern have been realized in the water-heat process; Solve existing photochemical catalyst not high to the visible light utilization rate, to problems such as the high concentrations of organic dye degradation efficiency are low; Graphene/silver orthophosphate composite with the hydro-thermal method in-situ preparing is used for the visible light photocatalysis field first, the preparation method is simple, do not need cost and complex equipment, synthesis condition is gentle, in the composite two phase constituents silver orthophosphate uniform particles effectively compound, that generated be distributed on the Graphene and pattern controlled; And can obtain the composite photocatalyst material of different proportionings through the mass percent of regulating graphene oxide and silver nitrate, can on the basis that does not reduce photocatalytic activity, reduce the cost of material to a certain extent.
The technical scheme that the present invention adopted; Be to be raw material with graphene oxide, silver nitrate; Mix further absorption ageing of back through mechanical agitation earlier; Make graphene oxide/silver orthophosphate through reaction then, under hydrothermal condition, be reduced to Graphene/silver orthophosphate again with sodium hydrogen phosphate or sodium dihydrogen phosphate.
Be specially: a kind of Graphene/silver orthophosphate compounded visible light photocatalyst; It is characterized in that: said compounded visible light photocatalyst is made up of Graphene and silver orthophosphate; The silver orthophosphate particle is wrapped up by the stratiform Graphene; Particle size distribution is between 100-400 nm, and said compounded visible light photocatalyst all has good photocatalytic degradation effect to organic dyestuff rhodamine B and methylene blue under excited by visible light, be 1 for concentration
10
-5The rhodamine B of mol/L and methylene blue solution; This compounded visible light photocatalyst radiation of visible light after 30 seconds the degradation rate to rhodamine B reach 83%,, radiation of visible light after 1 minute the degradation rate to rhodamine B reach 94%, radiation of visible light after 4 minutes the rhodamine B degradation rate be 98%; Radiation of visible light after 30 seconds to the degradation rate of methylene blue just up to 94%, radiation of visible light after 4 minutes methylene blue total degradation rate be 98%; For concentration is 5
10
-5The rhodamine B of mol/L and methylene blue, this composite visible light catalyst radiation of visible light after 2 minutes the degradation rate to rhodamine B have only 25%, radiation of visible light was 94% to the rhodamine B degradation rate after 10 minutes; This compounded visible light photocatalyst radiation of visible light after 2 minutes to the degradation rate of methylene blue just up to 75%, radiation of visible light after 6 minutes methylene blue total degradation rate be 98%.
The preparation method of described a kind of Graphene/silver orthophosphate compounded visible light photocatalyst; Comprise the step 3 that graphene oxide and silver nitrate mechanical agitation mix the step 1 that obtains mixing precursor solution A, the reaction that will mix precursor solution A and sodium hydrogen phosphate or sodium dihydrogen phosphate makes graphene oxide/silver orthophosphate, it is characterized in that: between step 1 and step 3, add mixing the step 2 that precursor solution A carries out ageing; After step 3, carry out the step of hydro-thermal reaction, said is 12 ~ 24h to mixing the time that precursor solution A carries out ageing; The condition of said hydro-thermal reaction is: be sealed in the stainless steel hydrothermal reaction kettle in polytetrafluoroethylliner liner, react 12-24h under the 140-200 ° of C condition.
Ageing is in order to let the silver ion that adds better be adsorbed onto the graphene oxide surface; Because graphene oxide is electronegative; Silver ion is positively charged, and the generation of silver orthophosphate is just on the graphene oxide surface, in the hydrothermal treatment consists process like this; The growth of silver orthophosphate just can be received the restriction of Graphene lamella, can not reunite and grow into very big particle.
Concrete steps are:
(1) graphene oxide is dissolved in deionized water for ultrasonic 3-5 hour, and obtaining concentration is the graphene oxide dispersion liquid of 0.01-2wt%;
(2) silver nitrate is dissolved in the deionized water; Under the magnetic agitation condition, dropwise be added drop-wise in the above-mentioned graphene oxide dispersion liquid; Dropwise back solution and continue to stir after 3-6 hour ageing 12 ~ 24 hours; Obtain mixing precursor solution A, the concentration of mixing silver nitrate among the precursor solution A is 0.2-5wt%;
(3) sodium hydrogen phosphate is dissolved in the deionized water, obtaining concentration is the disodium phosphate soln B of 0.15 mol/L; Or the sodium dihydrogen phosphate solid is dissolved in the deionized water, obtaining concentration is the sodium dihydrogen phosphate C of 0.15 mol/L;
(4) disodium phosphate soln B that under the magnetic agitation condition, step (3) is prepared or sodium dihydrogen phosphate C dropwise add the mixing precursor solution A of step (2) preparation; Pale brown look muddy in reaction system, occurring; Dropwising the back mixed solution at room temperature continues to stir after 20-60 minute and transfers in the polytetrafluoroethylliner liner; The polytetrafluoroethylliner liner that mixed solution is housed is sealed in the stainless steel hydrothermal reaction kettle; React 12-24h under the 140-200 ° of C condition, reaction finishes the afterreaction still and naturally cools to room temperature, and it is dry that resulting product centrifugation back is washed repeatedly final vacuum respectively with deionized water and absolute ethyl alcohol.
The present invention first with Graphene/silver orthophosphate nanocomposite applications in the visible light photocatalysis field, and realize original position redox graphene in the hydrothermal reaction process, thereby realize the effective assembling of silver orthophosphate on the Graphene surface; Graphene is as a kind of novel two-dimensional nano material with carbon element; Have very big specific area, both can be used as a kind of good carrier, better be adsorbed with organic dye and organic pollution; Simultaneously can also form heterojunction structure with silver orthophosphate; Produce built in field, improve the separative efficiency of photo-generated carrier, the compound of silver also has potential antibiotic and sterilizing function simultaneously.
Literature research shows: silver orthophosphate organic dyestuff for high concentration under radiation of visible light embodies photocatalytic degradation effect efficiently; Graphene oxide in the reaction precursor body, owing to have abundant hydrophilic radical, thus have negative electrical charge; After silver ion joined presoma, because the interaction between the electric charge, silver ion fully was adsorbed on the graphene oxide surface; Thereby make diffusion, reaction, nucleation and the growth of reactant mainly occur in the surface of graphene oxide; Under the hydrothermal treatment consists condition, silver orthophosphate reacts nucleation rapidly, but the restriction of lamella graphene-structured is received in its growth and gathering; The pattern of silver orthophosphate particle and crystal face are well limited and are regulated and control, and reunion and dispersiveness are improved.Preparation method of the present invention is simple, and visible light-responded scope is wide, and utilization rate is high, and photocatalytic activity is excellent, helps large-scale popularization.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of Graphene/silver orthophosphate compounded visible light photocatalyst;
Fig. 2 is the X-ray diffractogram of Graphene/silver orthophosphate compounded visible light photocatalyst;
Fig. 3 is that Graphene/silver orthophosphate compounded visible light photocatalyst is 1 to concentration under the different visible light irradiation time
10
-5The photocatalytic degradation curve map of the rhodamine B of mol/L and methylene blue;
1 is rhodamine B; 2 is methylene blue.
Fig. 4 is that Graphene/silver orthophosphate compounded visible light photocatalyst is 5 to concentration under the different visible light irradiation time
10
-5The photocatalytic degradation curve map of the rhodamine B of mol/L and methylene blue;
1 is rhodamine B; 2 is methylene blue.
The specific embodiment
To combine specific embodiment further to illustrate content of the present invention below, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
Getting 20 mg graphene oxides disperseed 3 hours in 20 mL deionized water for ultrasonic; Under the magnetic agitation condition, 1.53 g silver nitrates are dissolved in the 20mL deionized water, obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 12h after 3 hours, obtain mixing precursor solution A; 0.43 g sodium hydrogen phosphate is dissolved in the 20mL deionized water, obtains the disodium phosphate soln that concentration is 0.15mol/L; Under the magnetic agitation condition, disodium phosphate soln is dropwise added mixing precursor solution A, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 20 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 140 ° of C reacted 24 hours, were cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Getting 50 mg graphene oxides disperseed 3 hours in 30 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 16h after 4 hours; 0.43 g sodium hydrogen phosphate is dissolved in the 20mL deionized water, obtains the disodium phosphate soln that concentration is 0.15 mol/L; Under the magnetic agitation condition, disodium phosphate soln is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 30 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 160 ° of C reacted 20 hours, were cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Embodiment 3
Getting 100 mg graphene oxides disperseed 4 hours in 30 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 20h after 5 hours; 0.43 g sodium hydrogen phosphate is dissolved in the 20mL deionized water, obtains the disodium phosphate soln that concentration is 0.15 mol/L; Under the magnetic agitation condition, disodium phosphate soln is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 40 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 180 ° of C reacted 16 hours, were cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
The scanning electron microscope diagram of graphene oxide/silver orthophosphate compounded visible light photocatalyst that Fig. 1 goes out for this embodiment is prepared; We can know and find out that resulting silver orthophosphate is wrapped up by very thin lamellar graphite alkene from figure, and particle size distribution is between 100-400 nm; The X-ray diffracting spectrum of Graphene/silver orthophosphate composite visible light catalyst that Fig. 2 goes out for this embodiment is prepared; Diffraction maximums all among the figure all match with the silver orthophosphate thing; The resulting Graphene of in-situ reducing is because content is less relatively; And with respect to the very strong silver orthophosphate of the good diffraction maximum of crystallization, its X-ray diffraction peak can't be observed in the drawings.
Embodiment 4
Getting 200 mg graphene oxides disperseed 5 hours in 40 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 24h after 6 hours; 0.43 g sodium hydrogen phosphate is dissolved in the 20mL deionized water, obtains the disodium phosphate soln that concentration is 0.15 mol/L; Under the magnetic agitation condition, disodium phosphate soln is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 50 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 200 ° of C reaction 12h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Embodiment 5
Getting the 500mg graphene oxide disperseed 5 hours in 50 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 24h after 6 hours; 0.43 g sodium hydrogen phosphate is dissolved in the 20mL deionized water, obtains the disodium phosphate soln that concentration is 0.15 mol/L; Under the magnetic agitation condition, disodium phosphate soln is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 60 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 200 ° of C reaction 12h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Getting 20 mg graphene oxides disperseed 3 hours in 20 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 12h after 3 hours; 0.36 g sodium dihydrogen phosphate is dissolved in the 20mL deionized water, obtains the sodium dihydrogen phosphate that concentration is 0.15 mol/L; Under the magnetic agitation condition, sodium dihydrogen phosphate is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 20 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 140 ° of C reaction 24h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Embodiment 7
Getting 50 mg graphene oxides disperseed 3 hours in 30 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 16h after 4 hours; 0.36 g sodium dihydrogen phosphate is dissolved in the 20mL deionized water, obtains the sodium dihydrogen phosphate that concentration is 0.15 mol/L; Under the magnetic agitation condition, sodium dihydrogen phosphate is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 30 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 160 ° of C reaction 20h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Getting 100 mg graphene oxides disperseed 4 hours in 30 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 20h after 5 hours; 0.36 g sodium dihydrogen phosphate is dissolved in the 20mL deionized water, obtains the sodium dihydrogen phosphate that concentration is 0.15 mol/L; Under the magnetic agitation condition, sodium dihydrogen phosphate is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 40 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 180 ° of C reaction 16h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Embodiment 9
Getting 200 mg graphene oxides disperseed 4 hours in 40 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 24h after 6 hours; 0.36 g sodium dihydrogen phosphate is dissolved in the 20mL deionized water, obtains the sodium dihydrogen phosphate that concentration is 0.15 mol/L; Under the magnetic agitation condition, sodium dihydrogen phosphate is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 50 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 200 ° of C reaction 12h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Getting 500 mg graphene oxides disperseed 5 hours in 50 mL deionized water for ultrasonic; Under the magnetic agitation condition; 1.53 g silver nitrates are dissolved in the 20mL deionized water; Obtain the liquor argenti nitratis ophthalmicus that concentration is 0.45mol/L, dropwise add in the above-mentioned graphene oxide dispersion liquid, continue to stir ageing 24h after 6 hours; 0.36 g sodium dihydrogen phosphate is dissolved in the 20mL deionized water, obtains the sodium dihydrogen phosphate that concentration is 0.15 mol/L; Under the magnetic agitation condition, sodium dihydrogen phosphate is dropwise added graphene oxide/liquor argenti nitratis ophthalmicus, pale brown look muddy in reaction system, occurring; At room temperature continue after dropwising to stir 60 minutes, mixed liquor is gone in the hydrothermal reaction kettle, 200 ° of C reaction 12h are cooled to room temperature; Suction filtration cleans repeatedly vacuum drying with sediment with deionized water and absolute ethyl alcohol.
Prepared Graphene/silver orthophosphate the compounded visible light photocatalyst that goes out of the present invention is used to the photocatalytic degradation experiment of organic dyestuff rhodamine B and methylene blue, and detailed process and step are following:
Graphene/silver orthophosphate composite photo-catalyst of 100 mg is scattered in 100 milliliter 1 respectively
10
-5Mol/L, 100 milliliter 5
10
-5(concentration is 1 mg/mL) back is ultrasonic 10 minutes in the rhodamine B and methylene blue solution of mol/L; The dispersion liquid that mixes is transferred in the quartzy bottle in the xenon lamp catalytic reactor; Dark condition is opened xenon source after stirring down and making it reach adsorption equilibrium in 30 minutes; Every separated half a minute is extracted the postradiation mixed dispersion liquid of 4 mL with syringe and transfers in the centrifuge tube of mark; Close xenon source behind the radiation of visible light certain hour; Sample in all centrifuge tubes is centrifugalized; The resulting supernatant liquor in centrifugal back is further transferred in the quartz colorimetric utensil in the absorbance of measuring on the ultraviolet-visible spectrophotometer under the different photocatalysis time, thus obtain Graphene under each time period/silver orthophosphate composite photo-catalyst under radiation of visible light to the rhodamine B of variable concentrations and the photocatalytic degradation curve map of methylene blue.
Graphene/silver orthophosphate composite photo-catalyst that Fig. 3 goes out for embodiment 3 is prepared is 1 to concentration under the visible light condition
10
-5The photocatalytic degradation curve map of the rhodamine B of mol/L and methylene blue; As can be seen from Figure 3; This composite photo-catalyst radiation of visible light after 30 seconds the degradation rate to rhodamine B reach 83%; Radiation of visible light after 1 minute the degradation rate to rhodamine B reach 94%, continue the radiation of visible light degradation rate increase few, radiation of visible light after 4 minutes the rhodamine B degradation rate be 98%.Graphene/silver orthophosphate composite photo-catalyst radiation of visible light after 30 seconds to the degradation rate of methylene blue just up to 94%, continue radiation of visible light methylene blue degradation rate increase few, radiation of visible light after 4 minutes methylene blue total degradation rate be 98%.The bright Graphene of the photocatalytic degradation curve table of Fig. 3/silver orthophosphate composite photo-catalyst is 1 to concentration under radiation of visible light
10
-5The organic dyestuff rhodamine B of mol/L and methylene blue all have photocatalytic degradation effect efficiently; When radiation of visible light just begins; The efficient of photocatalytic degradation methylene blue is better than the efficient of photocatalytic degradation rhodamine B, and both photocatalytic degradation effects of radiation of visible light 1 minute are more or less the same.
Graphene/silver orthophosphate composite photo-catalyst that Fig. 4 goes out for embodiment 3 is prepared is 5 to concentration under the visible light condition
10
-5The photocatalytic degradation curve map of the rhodamine B of mol/L and methylene blue; As can be seen from Figure 4; This composite photo-catalyst radiation of visible light after 2 minutes the degradation rate to rhodamine B have only 25%; Continue increasing radiation of visible light time degradation rate increases obviously, and radiation of visible light was 94% to the rhodamine B degradation rate after 10 minutes.And Graphene/silver orthophosphate composite photo-catalyst radiation of visible light after 2 minutes to the degradation rate of methylene blue just up to 75%; Continuing radiation of visible light methylene blue degradation rate is improved to some extent; Radiation of visible light after 6 minutes methylene blue total degradation rate be 98%, after this degradation rate does not have obvious increase.We can find out as a result from the photocatalytic degradation curve of Fig. 4, and Graphene/silver orthophosphate composite photo-catalyst is 5 to concentration under radiation of visible light
10
-5The photocatalytic degradation effect of the methylene blue of mol/L obviously is better than the degradation effect with the rhodamine B of concentration.
Claims (3)
1. Graphene/silver orthophosphate compounded visible light photocatalyst; It is characterized in that: said compounded visible light photocatalyst is made up of Graphene and silver orthophosphate; The silver orthophosphate particle is wrapped up by the stratiform Graphene; Particle size distribution is between 100-400 nm, and said compounded visible light photocatalyst all has good photocatalytic degradation effect to organic dyestuff rhodamine B and methylene blue under excited by visible light, be 1 for concentration
10
-5The rhodamine B of mol/L and methylene blue solution; This compounded visible light photocatalyst radiation of visible light after 30 seconds the degradation rate to rhodamine B reach 83%,, radiation of visible light after 1 minute the degradation rate to rhodamine B reach 94%, radiation of visible light after 4 minutes the rhodamine B degradation rate be 98%; Radiation of visible light after 30 seconds to the degradation rate of methylene blue just up to 94%, radiation of visible light after 4 minutes methylene blue total degradation rate be 98%; For concentration is 5 ' 10
-5The rhodamine B of mol/L and methylene blue, this composite visible light catalyst radiation of visible light after 2 minutes the degradation rate to rhodamine B have only 25%, radiation of visible light was 94% to the rhodamine B degradation rate after 10 minutes; This compounded visible light photocatalyst radiation of visible light after 2 minutes to the degradation rate of methylene blue just up to 75%, radiation of visible light after 6 minutes methylene blue total degradation rate be 98%.
2. the preparation method of a kind of Graphene as claimed in claim 1/silver orthophosphate compounded visible light photocatalyst; Comprise the step 3 that graphene oxide and silver nitrate mechanical agitation mix the step 1 that obtains mixing precursor solution A, the reaction that will mix precursor solution A and sodium hydrogen phosphate or sodium dihydrogen phosphate makes graphene oxide/silver orthophosphate, it is characterized in that: between step 1 and step 3, add mixing the step 2 that precursor solution A carries out ageing; After step 3, carry out the step of hydro-thermal reaction, said is 12 ~ 24h to mixing the time that precursor solution A carries out ageing; The condition of said hydro-thermal reaction is: be sealed in the stainless steel hydrothermal reaction kettle in polytetrafluoroethylliner liner, react 12-24h under the 140-200 ° of C condition.
3. the preparation method of a kind of Graphene as claimed in claim 2/silver orthophosphate compounded visible light photocatalyst is characterized in that comprising following concrete steps:
(1) graphene oxide is dissolved in deionized water for ultrasonic 3-5 hour, and obtaining concentration is the graphene oxide dispersion liquid of 0.01-2wt%;
(2) silver nitrate is dissolved in the deionized water; Under the magnetic agitation condition, dropwise be added drop-wise in the above-mentioned graphene oxide dispersion liquid; Dropwise back solution and continue to stir after 3-6 hour ageing 12 ~ 24 hours; Obtain mixing precursor solution A, the concentration of mixing silver nitrate among the precursor solution A is 0.2-5wt%;
(3) sodium hydrogen phosphate is dissolved in the deionized water, obtaining concentration is the disodium phosphate soln B of 0.15 mol/L; Or the sodium dihydrogen phosphate solid is dissolved in the deionized water, obtaining concentration is the sodium dihydrogen phosphate C of 0.15 mol/L;
(4) disodium phosphate soln B that under the magnetic agitation condition, step (3) is prepared or sodium dihydrogen phosphate C dropwise add the mixing precursor solution A of step (2) preparation; Pale brown look muddy in reaction system, occurring; Dropwising the back mixed solution at room temperature continues to stir after 20-60 minute and transfers in the polytetrafluoroethylliner liner; The polytetrafluoroethylliner liner that mixed solution is housed is sealed in the stainless steel hydrothermal reaction kettle; React 12-24h under the 140-200 ° of C condition, reaction finishes the afterreaction still and naturally cools to room temperature, and it is dry that resulting product centrifugation back is washed repeatedly final vacuum respectively with deionized water and absolute ethyl alcohol.
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