CN103521248A - Method for preparing graphene-based composite visible light catalysis material - Google Patents
Method for preparing graphene-based composite visible light catalysis material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000006555 catalytic reaction Methods 0.000 title claims description 26
- 238000000034 method Methods 0.000 title description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000243 solution Substances 0.000 claims abstract description 58
- 239000011259 mixed solution Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 40
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 31
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- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
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- 238000002360 preparation method Methods 0.000 claims abstract description 17
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims description 50
- 229910021641 deionized water Inorganic materials 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 30
- 239000002055 nanoplate Substances 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 238000005119 centrifugation Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 15
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 15
- 235000019800 disodium phosphate Nutrition 0.000 claims description 15
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 14
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 14
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 14
- 239000001488 sodium phosphate Substances 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- 235000011008 sodium phosphates Nutrition 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000002835 absorbance Methods 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
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- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
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- 239000002086 nanomaterial Substances 0.000 description 15
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical group [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
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Abstract
本发明涉及光催化材料，特指一种石墨烯基复合可见光催化材料的制备方法。步骤如下：将氧化石墨烯溶于水中，超声得到氧化石墨烯分散液；将硝酸银溶液在搅拌的条件下滴加到氧化石墨烯分散液中，搅拌一段时间，得到混合前驱体溶液A；将配置好的二氧化钛溶液缓慢滴加到上述混合前驱体溶液A中，得到混合溶液B；将配制好的磷酸盐溶液缓慢滴加到上述混合溶液B中，继续搅拌一段时间后转入水热反应釜中，一定温度下水热反应，冷却至室温后；产物离心、洗涤、真空干燥后得到所述复合材料。本发明的优点在于制备工艺简单、所需原料充足和产物性能优越，在可见光激发下作用下对有机染料罗丹明B表现出超强的降解活性。
The invention relates to a photocatalytic material, in particular to a preparation method of a graphene-based composite visible light catalytic material. The steps are as follows: dissolving graphene oxide in water and ultrasonically obtaining a graphene oxide dispersion; adding the silver nitrate solution dropwise to the graphene oxide dispersion under stirring conditions, and stirring for a period of time to obtain a mixed precursor solution A; The configured titanium dioxide solution is slowly added dropwise to the above mixed precursor solution A to obtain a mixed solution B; the prepared phosphate solution is slowly added dropwise to the above mixed solution B, continue to stir for a period of time, and then transfer to the hydrothermal reaction kettle During the hydrothermal reaction at a certain temperature, after cooling to room temperature; the product is centrifuged, washed, and vacuum-dried to obtain the composite material. The invention has the advantages of simple preparation process, sufficient required raw materials and superior product performance, and exhibits super-strong degradation activity to the organic dye rhodamine B under excitation of visible light.
Description
Technical field
the present invention relates to catalysis material, refer in particular to a kind of preparation method of graphene-based composite visible light catalysis material, refer to that especially a kind of hydro-thermal legal system of using, for the method for the graphene-based three-system composite visible light of micro-nano structure catalysis material, belongs to composite, photocatalysis technology and water pollution control field.
Background technology
As everyone knows, titanium dioxide has obtained widely and has paid close attention to as conductor photocatalysis material, but titanium dioxide light abstraction width narrower (only limiting to ultraviolet region), quantum efficiency are lower, particularly low its photocatalytic activity under radiation of visible light that causes of its visible light-responded degree is limited; Research shows, has at high proportion and pattern is controlled that { 001} face titanium dioxide nanoplate shows excellent photocatalysis performance under UV-irradiation.
Silver orthophosphate, as a kind of novel catalysis material, under excited by visible light, has the band structure of dispersion, energy gap relative narrower, the recombination rate of photo-generated carrier is reduced greatly, and quantum efficiency is greatly improved, thereby shows excellent visible light photocatalysis active; But, to prepare the compound that silver orthophosphate used argentiferous and make preparation cost higher, the size of the silver orthophosphate material of preparing in addition all bigger than normal and pattern is difficult to control, and the chemical stability of silver orthophosphate material is poor.
Graphene is a kind of allotrope of having of material with carbon element, is a kind of good carrier material, and loaded with nano particle can obtain good dispersiveness in the above; What is more important, Graphene or a kind of electron acceptor material, Graphene and titanium dioxide is compound, and at the interface of bi-material, the optical excitation electrons on titanium dioxide conduction band is transferred to being with of Graphene, thereby greatly reduce the recombination rate of electron-hole pair, be that titanium dioxide has higher catalytic activity, due to the adjustment that can be with, Graphene can also be brought into play the effect of sensitising agent, the light abstraction width that is titanium dioxide expands visible region to, has effectively improved the utilization rate to solar energy.
The compound prepared composite photo-catalyst of Graphene and titanium dioxide has shown excellent performance, researcher has synthesized Graphene/silver orthophosphate/titanic oxide composite photochemical catalyst material by hydro-thermal method again, profit has obtained the bifunctional visible-light photocatalysis material that specific area is large, heat endurance is high in this way, and this material also has the performance of stronger photocatalytic activity and good degradable organic pollutant; But, this method is in finely dispersed liquor argenti nitratis ophthalmicus, directly to drip sodium hydrogen phosphate, be swift in response and generate silver orthophosphate yellow mercury oxide, and carry out compoundly with graphene oxide and titanium dioxide, because the excessive velocities of reaction can cause the large-area gathering of silver orthophosphate particle, thereby generate the larger spherical silver orthophosphate structure of particle, and, the structure of this material is also uncontrollable, and pattern is also irregular, can affect to a certain extent the ability of photocatalysis performance and the degradable organic pollutant of material; Take titanium dioxide nanoplate, silver nitrate, phosphate and graphene oxide at present as raw material, utilize the cooperative effect of controlling between silver orthophosphate and titanium dioxide nanoplate to improve the photocatalytic activity of composite, by hydro-thermal method, prepare and there is micro-nano structure three-system composite visible light catalysis material, and be applied to photocatalysis degradation organic contaminant and have no report.
Summary of the invention
The object of the present invention is to provide that a kind of flow process is simple, the method for the micro-nano structure composite visible light catalysis material of environmental friendliness, preparation with low cost, the composite photocatalyst material of preparation has visible light-responded characteristic and excellent Photocatalytic Activity for Degradation pollutant performance widely.
Realizing the technical solution adopted in the present invention is: take graphene oxide as precursor material, by hydro-thermal method by titanium dioxide nanoplate and silver orthophosphate uniform particles be compounded on Graphene matrix, its concrete preparation method's step is as follows:
(1) graphene oxide is dissolved in deionized water, ultrasonic being uniformly dispersed obtains the graphene oxide dispersion liquid that concentration is 0.06-0.6 wt%;
(2) silver nitrate is dissolved in deionized water, obtains liquor argenti nitratis ophthalmicus; Under stirring condition, liquor argenti nitratis ophthalmicus is joined in above-mentioned graphene oxide dispersion liquid, stir 6-12h, obtain mixing precursor solution A, in mixed solution, the concentration of silver nitrate is 0.15 mol/L;
(3) titanium dioxide nanoplate is dissolved in to deionized water for ultrasonic and disperses, obtain titanium oxide dispersion; Under stirring condition, be added drop-wise in above-mentioned mixing precursor solution A, obtain mixed solution B, in mixed solution B, the concentration of titanium dioxide is 0.48-1.8 wt%;
(4) phosphate is dissolved in deionized water, obtains the phosphate solution that concentration is 0.15 mol/L;
(5) under stirring condition, phosphate solution prepared by step (4) dropwise adds in the prepared mixed solution B of step (3), reaction system occurs that celadon is muddy, the volume ratio of phosphate solution and mixed solution B is 1: 4, the mixed solution obtaining after dropwising is transferred in polytetrafluoroethylliner liner after continuing to stir 30-60 min, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160-200 ° of C condition, react 20-30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Phosphate described in step 3 is sodium hydrogen phosphate, sodium dihydrogen phosphate or sodium phosphate.
Described titanium dioxide nanoplate preparation process is as follows:
(1) hydrofluoric acid is added in deionized water, obtain hydrofluoric acid solution, in solution, the mass ratio of hydrofluoric acid is 50%;
(2) under magnetic agitation condition, butyl titanate is dropwise slowly added in the prepared hydrofluoric acid solution of step (1), in reaction system, there is white opacity, the volume ratio of butyl titanate and hydrofluoric acid solution is 5:8;
(3) dropwise after rear mixed solution continues to stir and transfer in polytetrafluoroethylliner liner, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
The present invention has the following advantages compared with prior art:
A) titanium dioxide and silver orthophosphate have the band structure matching, and they are compounded to form the separation that heterojunction semiconductor material can promote the electron-hole pair that excitation produces, and can also improve the cyclical stability of material.
B) prepared catalysis material has wider visible light-responded scope and the efficient efficiency of light energy utilization.
C) specific area that Graphene is large and high electric conductivity make composite photocatalyst material have the low plyability of good dispersiveness, adsorptivity and electron-hole pair, make material under visible ray effect, have efficient catalytic oxidation ability.
D) technique prepared is simple, with low cost, the superior performance of energy-conserving and environment-protective and material.
E) titanium dioxide nanoplate has better visible absorption effect than titanium dioxide granule, for composite, can improve the response of composite to visible ray, thereby the visible light photocatalysis effect of composite is improved.
Accompanying drawing explanation
Fig. 1 is the surface sweeping Electronic Speculum figure of prepared titanium dioxide nanoplate material, visible a large amount of thin plate-like titanium dioxide materials in figure; The size of resulting titanium dioxide nanoplate is between 50-70 nm;
In Fig. 2, the high-resolution-ration transmission electric-lens figure of titanium dioxide nanoplate material shows, the thickness of resulting titanium dioxide nanoplate is between 4-5 nm;
Fig. 3 is the scanning electron microscope diagram of micro-nano structure composite visible light catalysis material;
Fig. 4 is the X ray diffracting spectrum of micro-nano structure composite visible light catalysis material;
Fig. 5 is the UV-vis DRS spectrogram of micro-nano structure composite visible light catalysis material;
Fig. 6 is the Photocatalytic Activity for Degradation curve map of micro-nano structure composite visible light catalysis material to rhodamine B.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate content of the present invention, but these embodiment do not limit the scope of the invention.
Embodiment 1
20 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 300 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30 min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
50 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 240 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 3
100 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 600 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 4
200 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 900 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.426 g sodium hydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain disodium phosphate soln, under magnetic stirrer, the disodium phosphate soln preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 5
20 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 300 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 6
50 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 240 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 7
100 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 600 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 8
200 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 900 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.36 g sodium dihydrogen phosphate solid is dissolved in 20 ml deionized waters, obtain sodium dihydrogen phosphate, under magnetic stirrer, the sodium dihydrogen phosphate preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
Embodiment 9
20 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 300 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 30 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
50 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 240 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 40 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
Embodiment 11
100 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 600 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 50 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 200 ° of C conditions, react 20 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
Embodiment 12
200 mg graphene oxides are scattered in to 30 ml deionized water for ultrasonic and within 5 hours, obtain graphene oxide dispersion liquid, taking 0.1529 g silver nitrate is dissolved in 20 ml deionized waters, obtain liquor argenti nitratis ophthalmicus, under magnetic stirrer, above-mentioned liquor argenti nitratis ophthalmicus is dropwise joined in graphene oxide dispersion liquid, stir 12 hours, form and mix precursor solution A, 900 mg titanium dioxide nanoplates are dissolved in to 30 ml deionized water for ultrasonic and disperse 30min, obtain titanium oxide dispersion, under the condition of magnetic stirrer, be added drop-wise to above-mentioned closing in precursor solution A, obtain mixed solution B, taking 0.49 g sodium phosphate solid is dissolved in 20 ml deionized waters, obtain sodium radio-phosphate,P-32 solution, under magnetic stirrer, the sodium radio-phosphate,P-32 solution preparing is dropwise added in mixed solution B, reaction system occurs that celadon is muddy, dropwising rear mixed solution continuation stirring transferred in polytetrafluoroethylliner liner after 60 minutes, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160 ° of C conditions, react 30 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
Fig. 3 is the scanning electron microscope (SEM) photograph of prepared micro-nano structure composite visible light catalysis material, and from figure, we can see tiny silver orthophosphate spheric granules and titanium dioxide lamellar structure; Fig. 4 is the X-ray diffractogram of prepared micro-nano structure three compound catalyze materials, diffraction maximums all in diffraction pattern are all well corresponding to the silver orthophosphate and the titanium dioxide that respond, owing to adding in reactant, graphene oxide amount is less, so the Graphene content obtaining after reduction is also lower, the silver orthophosphate of the relative crystallization of diffraction peak intensity of Graphene and titanium dioxide diffraction maximum are very weak in addition, so fail to observe the diffraction maximum that derives from Graphene in X ray diffracting spectrum; Fig. 5 is the UV-vis DRS spectrogram of prepared micro-nano structure composite visible light catalysis material, and from figure, we can find out, this composite has good absorption in the ultraviolet-visible district of 200-800 nm, and absorbance is all greater than 0.4.
In addition, the prepared micro-nano structure three-system composite visible light catalysis material of the present invention is used to the photocatalytic degradation experiment of organic dyestuff rhodamine B, and detailed process and step are as follows:
Micro-nano structure silver orthophosphate based composites prepared by 100 mg is ultrasonic be scattered in the rhodamine B solution of 100 milliliter of 10 mg/L after ultrasonic 10 minutes, the dispersion liquid mixing is transferred in the quartzy bottle in xenon lamp catalytic reactor, under dark condition, stir after within 30 minutes, making it reach adsorption equilibrium and open xenon source, every 5 minutes, with syringe, extracting the postradiation mixed dispersion liquid of 4 mL transfers in the centrifuge tube of mark, the radiation of visible light of 400-800 nm is after half an hour, by the sample centrifugation in all centrifuge tubes, centrifugal rear resulting supernatant liquor is further transferred to and in quartz colorimetric utensil, on ultraviolet-visible spectrophotometer, is measured the absorbance under the different photocatalysis time, thereby obtain micro-nano structure phosphoric acid money base composite visible light catalysis material photocatalytic degradation curve map to rhodamine B under the radiation of visible light of 400-800 nm under each time period.
Fig. 6 is prepared micro-nano structure phosphoric acid money base composite visible light catalysis material photocatalytic degradation curve map to rhodamine B under visible ray condition, as can be seen from Figure 4, this composite under dark condition to the adsorption rate of rhodamine B 22%, reach after adsorption-desorption balance, turn on light radiation of visible light rhodamine B degraded in 30 minutes completely; Photocatalytic degradation curve map shows that micro-nano structure silver orthophosphate based composites has certain adsorption effect to rhodamine B, has good photocatalytic degradation effect to rhodamine B under radiation of visible light.
Claims (6)
1. a preparation method for graphene-based composite visible light catalysis material, is characterized in that preparation process is as follows:
(1) graphene oxide is dissolved in deionized water, ultrasonic being uniformly dispersed obtains the graphene oxide dispersion liquid that concentration is 0.06-0.6 wt%;
(2) silver nitrate is dissolved in deionized water, obtains liquor argenti nitratis ophthalmicus; Under stirring condition, liquor argenti nitratis ophthalmicus is joined in above-mentioned graphene oxide dispersion liquid, stir 6-12h, obtain mixing precursor solution A, in mixed solution, the concentration of silver nitrate is 0.15 mol/L;
(3) titanium dioxide nanoplate is dissolved in to deionized water for ultrasonic and disperses, obtain titanium oxide dispersion; Under stirring condition, be added drop-wise in above-mentioned mixing precursor solution A, obtain mixed solution B, in mixed solution B, the concentration of titanium dioxide is 0.48-1.8 wt%;
(4) phosphate is dissolved in deionized water, obtains the phosphate solution that concentration is 0.15 mol/L;
(5) under stirring condition, phosphate solution prepared by step (4) dropwise adds in the prepared mixed solution B of step (3), reaction system occurs that celadon is muddy, the volume ratio of phosphate solution and mixed solution B is 1: 4, the mixed solution obtaining after dropwising is transferred in polytetrafluoroethylliner liner after continuing to stir 30-60 min, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 160-200 ° of C condition, react 20-30 h, reaction finishes rear reactor and naturally cools to room temperature, after resulting product centrifugation, with deionized water and absolute ethyl alcohol, wash respectively final vacuum dry.
2. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, is characterized in that: the phosphate described in step 3 is sodium hydrogen phosphate, sodium dihydrogen phosphate or sodium phosphate.
3. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, is characterized in that described titanium dioxide nanoplate preparation process is as follows:
(1) hydrofluoric acid is added in deionized water, obtain hydrofluoric acid solution, in solution, the mass ratio of hydrofluoric acid is 50%;
(2) under magnetic agitation condition, butyl titanate is dropwise slowly added in the prepared hydrofluoric acid solution of step (1), in reaction system, there is white opacity, the volume ratio of butyl titanate and hydrofluoric acid solution is 5:8;
(3) dropwise after rear mixed solution continues to stir and transfer in polytetrafluoroethylliner liner, and inner bag is sealed in stainless steel hydrothermal reaction kettle, under 180 ° of C conditions, react 24 h, reaction finishes rear reactor and naturally cools to room temperature, washs respectively final vacuum dry after resulting product centrifugation with deionized water and absolute ethyl alcohol.
4. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 3, is characterized in that: the size of described titanium dioxide nanoplate is between 50-70 nm, and thickness is between 4-5 nm.
5. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, it is characterized in that: described graphene-based composite visible light catalysis material has good absorption in the ultraviolet-visible district of 200-800 nm, and absorbance is all greater than 0.4.
6. the preparation method of a kind of graphene-based composite visible light catalysis material as claimed in claim 1, it is characterized in that: described graphene-based composite visible light catalysis material under dark condition to the adsorption rate of the rhodamine B in the rhodamine B solution of 10 mg/L 22%, reach after adsorption-desorption balance, under the radiation of visible light of 400-800 nm, rhodamine B degraded in 30 minutes completely.
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