CN102513091A - Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst - Google Patents
Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst Download PDFInfo
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- CN102513091A CN102513091A CN201110410114XA CN201110410114A CN102513091A CN 102513091 A CN102513091 A CN 102513091A CN 201110410114X A CN201110410114X A CN 201110410114XA CN 201110410114 A CN201110410114 A CN 201110410114A CN 102513091 A CN102513091 A CN 102513091A
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Abstract
The invention relates to a preparation method for a graphene self-assembled nanometer bismuth vanadate photocatalyst. The method comprises the following steps: (1) adding a bismuth salt and a stabilizing agent into a phosphate buffer solution, carrying out stirring to obtain turbid liquid, uniformly dissolving metavanadate in a phosphate buffer solution, adding an obtained mixture into the turbid liquid and carrying out uniform stirring to obtain a transparent solution; and (2) adjusting the pH value of the transparent solution to be in a range of 4.5 to 9.0, adding graphene at a temperature of 20 to 100 DEG C, wherein the mass ratio of graphene to the bismuth salt is 5-20: 1, carrying out stirring and mixing, carrying out reflux for 6 to 24 h, then carrying out centrifugation, filtration and rinsing so as to obtain a product, roasting the obtained product and cooling and grinding the product so as to obtain the photocatalyst. The preparation method provided in the invention has the advantages of low cost, simpleness, practicability and low requirements for equipment; self assembly of prepared graphene bismuth vanadate powder is uniform, and the prepared graphene bismuth vanadate powder can highly efficiently degrade persistant toxic and harmful substances under the conditions of ultraviolet light and visible light, is simple and convenient to recycle and has a wide application prospect.
Description
Technical field
The invention belongs to the preparation field of nanometer pucherite photochemical catalyst, particularly a kind of preparation method of Graphene self-assembled nanometer pucherite photochemical catalyst.
Background technology
In recent years, with titanium dioxide (TiO
2) for the photocatalysis technology of core representative in the environmental pollution improvement field; Particularly the application in microbial degradation wastewater treatment and air cleaning more and more widely; But because its greater band gap; Only can under UV-irradiation, just have photocatalysis, thereby limit the further expansion of its application.In order to improve TiO
2To the utilization ratio of sunshine, lot of domestic and international experts and scholars are round visible light-responded TiO
2Photochemical catalyst has launched number of research projects, is primarily aimed at TiO
2Photocatalyst surface is structurally-modified, inorganic elements and doped with metal elements modification etc., is intended to enlarge its spectral response range, improves its visible light catalysis activity.However, the TiO of process modification
2Photochemical catalyst still exists problems such as visible light catalysis activity is undesirable, and the light degradation ability is relatively poor at this stage, causes its practicality relatively poor.
Nearest discovers to have the composite oxides pucherite (BiVO of monoclinic system scheelite-type structure
4) under radiation of visible light, just have photocatalytic activity, can produce oxygen and degradable organic pollutant by the decomposition water molecule, be a kind of potential photochemical catalyst.Yet, BiVO
4Absorption property very poor, and the photo-generated carrier that produces is difficult to migration, easy compound, thereby influenced its visible light activity.At present about being directed against BiVO
4Composite modified less with the research report that mixes, in addition about it being self-assembled to the good porous material of absorption property, also few like the report of active carbon etc.; Therefore; How strengthening its absorption in visible-range, and improve its visible light catalysis activity, is to research and develop BiVO at present
4The main research emphasis of high efficiency photocatalyst.
The sewage disposal conventional method mainly contains: physical partition method, biological degradation method, chemical decomposition method etc.; But all there is certain limitation in these methods; Therefore, the researcher begins to be devoted to develop efficient, low energy consumption, applied widely and the water treatment technology of deep oxidation ability arranged.In recent years, a lot of scholars are with TiO
2Be used for the organic pollution of photocatalytic degradation water body, though obtained certain effect, because the restriction of its photoresponse scope causes treatment effect often not ideal enough.By contrast, BiVO
4Just having good photocatalytic activity in the visible region, is a kind of potential desired light catalyst.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of Graphene self-assembled nanometer pucherite photochemical catalyst; Operation is simple for this method, with low cost, to equipment require low; The Graphene powder pucherite self assembly of preparation is even; Can be under ultraviolet light and visible light condition efficient degradation persistence poisonous and harmful substance, and reclaiming utilizes easyly, is highly suitable for the advanced treating of waste water.
The preparation method of a kind of Graphene self-assembled nanometer pucherite photochemical catalyst of the present invention comprises:
(1) bismuth salt, stabilizing agent are joined in the phosphate buffer, stir 15~60min, form suspension; Metavanadate evenly is dissolved in phosphate buffer; Join then in the described suspension; Stir, form clear solution, wherein the mol ratio of bismuth salt and metavanadate is 1: 1; The amount of substance concentration of bismuth salt and metavanadate is 0.01~0.15mol/L, and the amount of substance concentration of stabilizing agent is 0.01~0.05mol/L;
(2) the pH value scope that adopts alkaline solution to regulate above-mentioned clear solution is 4.5~9.0, is 5~20: 1 Graphene then at 20~100 ℃ of following addings and bismuth salt mass ratio, mixes; Backflow 6-24h; Centrifugal, filter, after the washing, can get yellow product, at last with the gained yellow product in 180~400 ℃ of roasting 2~4h; After cooling is ground, promptly get.
Bismuth salt described in the step (1) is bismuth nitrate, basic bismuth carbonate, bismuth chloride or bismuth acetate.
Stabilizing agent described in the step (1) is disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt or BTCA.
Metavanadate described in the step (1) is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
Phosphate buffer described in the step (1) is that 0.025~0.05mol/L sodium dihydrogen phosphate and 0.05~0.1mol/L sodium hydrogen phosphate are formed by amount of substance concentration all.
Alkaline solution described in the step (2) is NaOH or the potassium hydroxide aqueous solution of concentration 0.5mol/L~1.5mol/L.
The present invention utilize the unique layer chain structure characteristic of Graphene, specific area greatly, characteristics such as high adsorption capacity, chemical inertness, in conjunction with BiVO
4Visible light catalysis activity, the success with nanometer BiVO
4Self-assemble on the Graphene; Be prepared into the high catalytic activity visible-light photocatalysis material that can suspend in water; And be applied to the advanced treating of waste water, can realize efficient removal, particularly conventional treatment is difficult to the effectively persistence micropollutants of removal organic pollution in the water; And non-secondary pollution, be the technology of environment-friendly type.
In China, the Graphene resource reserve is very big, but later owing to what find; Its development of exploitation level is lower; Add a little less than the relative thin of national nonmetallic ore processing industry basis, to such an extent as to the application of the great mineral reserve of this economic implications also is only limited to general filler, therefore; The prepared self assembly type visible-light photocatalysis material of the present invention also has advantage with low cost, has boundless actual application prospect.
Beneficial effect
(1) the present invention is with low cost, and the preparation method is simple, to equipment require lowly, operability is good;
(2) the Graphene powder pucherite self assembly of the present invention preparation is even, can be under ultraviolet light and visible light condition efficient degradation persistence poisonous and harmful substance, reclaiming utilizes easy, is highly suitable for the advanced treating of waste water, has broad application prospects;
(3) Graphene itself is a kind of well behaved conductive compound, can reduce meeting of photohole and electronics, significantly improves BiVO
4Photocatalytic activity, remove beneficial effects such as heavy metal ion.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) bismuth nitrate, disodium ethylene diamine tetraacetate are joined in the phosphate buffer, magnetic agitation 15min forms suspension; Sodium metavanadate evenly is dissolved in phosphate buffer earlier, dropwise joins in the above-mentioned suspension then, magnetic agitation is even, forms clear solution; Wherein the amount of substance concentration of bismuth nitrate, inclined to one side sodium vanadate and disodium ethylene diamine tetraacetate is 0.01mol/L, and phosphate buffer is made up of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L dibastic sodium phosphate;
(2) adopting concentration is that the pH value that the sodium hydrate aqueous solution of 0.5mol/L is regulated above-mentioned clear solution is 4.5, and at 60 ℃ of a certain proportion of Graphenes of adding down, wherein the mass ratio of bismuth salt and Graphene is 1: 5 then; Magnetic agitation is mixed continuously, backflow 6h, centrifugal, filtration; After the washing, can get yellow product, at last with products therefrom in 180 ℃ of roasting 2h; After cooling is ground, the Graphene photochemical catalyst powder of nanometer pucherite that promptly got self assembly.
Embodiment 2
(1) bismuth chloride, gluconic acid sodium salt are joined in the phosphate buffer, magnetic agitation 35min forms suspension; Ammonium metavanadate evenly is dissolved in phosphate buffer earlier, dropwise joins in the above-mentioned suspension then, magnetic agitation is even, forms clear solution; Wherein bismuth chloride amount of substance concentration is that 0.06mol/L, gluconic acid sodium salt amount of substance concentration are 0.03mol/L, alum acid ammonium amount of substance concentration is 0.06mol/L partially, and phosphate buffer is made up of 0.03mol/L sodium dihydrogen phosphate and 0.08mol/L dibastic sodium phosphate;
(2) the employing degree is that the pH value that the potassium hydroxide aqueous solution of 1mol/L is regulated above-mentioned clear solution is 7, adds a certain proportion of Graphenes down at 80 ℃ then, and wherein the mass ratio of bismuth salt and Graphene is 1: 12; Magnetic agitation is mixed continuously, backflow 15h, centrifugal, filtration; After the washing, can get yellow product, at last with products therefrom in 300 ℃ of roasting 3h; After cooling is ground, the Graphene photochemical catalyst powder of nanometer pucherite that promptly got self assembly.
Embodiment 3
(1) bismuth acetate, BTCA are joined in the phosphate buffer, magnetic agitation 60min forms suspension; Potassium metavanadate evenly is dissolved in phosphate buffer earlier, dropwise joins in the above-mentioned suspension then, magnetic agitation is even, forms clear solution; Wherein bismuth acetate amount of substance concentration is that 0.15mol/L, BTCA amount of substance concentration are 0.05mol/L, the amount concentration of alum acid potassium sodium matter is 0.15mol/L partially, and phosphate buffer is made up of 0.05mol/L sodium dihydrogen phosphate and 0.1mol/L dibastic sodium phosphate;
(2) adopting concentration is that the pH value that the sodium hydrate aqueous solution of 1.5mol/L is regulated above-mentioned clear solution is 9, and at 100 ℃ of a certain proportion of Graphenes of adding down, wherein the mass ratio of bismuth salt and Graphene is 1: 20 then; Magnetic agitation is mixed continuously, backflow 24h, centrifugal, filtration; After the washing, can get yellow product, at last with products therefrom in 400 ℃ of roasting 4h; After cooling is ground, the Graphene photochemical catalyst powder of nanometer pucherite that promptly got self assembly.
The wastewater treatment experiment: the dyeing waste water with the final discharging of certain printing and dyeing mill is a process object; After the micro-filtrate membrane filtration preliminary treatment; Add same amount therein respectively through embodiment 1~example 3 prepared photochemical catalysts, under sunshine, shone 6 hours continuously, decolorization of dyeing rate and COD
CrClearance is as shown in the table respectively:
Percent of decolourization | COD CrClearance | |
Embodiment 1 | 99.2% | 89.6% |
Embodiment 2 | 98.3% | 93.8% |
Embodiment 3 | 99.4% | 95.6% |
Claims (6)
1. the preparation method of a Graphene self-assembled nanometer pucherite photochemical catalyst comprises:
(1) bismuth salt, stabilizing agent are joined in the phosphate buffer, stir 15~60min, form suspension; Metavanadate evenly is dissolved in phosphate buffer; Join then in the described suspension; Stir, form clear solution, wherein the mol ratio of bismuth salt and metavanadate is 1: 1; The amount of substance concentration of bismuth salt and metavanadate is 0.01~0.15mol/L, and the amount of substance concentration of stabilizing agent is 0.01~0.05mol/L;
(2) the pH value scope that adopts alkaline solution to regulate above-mentioned clear solution is 4.5~9.0, is 5~20: 1 Graphene then at 20~100 ℃ of following addings and bismuth salt mass ratio, mixes; Backflow 6-24h; Centrifugal, filter, after the washing, product, at last with products therefrom in 180~400 ℃ of roasting 2~4h; After cooling is ground, promptly get.
2. the preparation method of a kind of Graphene self-assembled nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the bismuth salt described in the step (1) is bismuth nitrate, basic bismuth carbonate, bismuth chloride or bismuth acetate.
3. the preparation method of a kind of Graphene self-assembled nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the stabilizing agent described in the step (1) is disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt or BTCA.
4. the preparation method of a kind of Graphene self-assembled nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the metavanadate described in the step (1) is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
5. the preparation method of a kind of Graphene self-assembled nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the phosphate buffer described in the step (1) is that 0.025~0.05mol/L sodium dihydrogen phosphate and 0.05~0.1mol/L sodium hydrogen phosphate are formed by amount of substance concentration all.
6. the preparation method of a kind of Graphene self-assembled nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the alkaline solution described in the step (2) is NaOH or the potassium hydroxide aqueous solution of concentration 0.5mol/L~1.5mol/L.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103657639A (en) * | 2013-12-31 | 2014-03-26 | 长沙理工大学 | Preparation method of graphene/bismuth tungstate lamellar nanostructure visible light catalytic material and silicon modification method thereof |
CN103801284A (en) * | 2014-01-22 | 2014-05-21 | 浙江大学 | Method for preparing pucherite-graphene composite photocatalyst |
CN106179318A (en) * | 2016-09-27 | 2016-12-07 | 安阳师范学院 | A kind of preparation method of pucherite nano wire graphene photo-catalyst |
CN106268761A (en) * | 2016-08-11 | 2017-01-04 | 广西南宁胜祺安科技开发有限公司 | A kind of Graphene doping bismuth vanadate photocatalyst |
CN110180572A (en) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | A kind of N doping BiVO4The catalysis material of-OVs/GO nano composite structure and its application |
Citations (2)
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CN102125832A (en) * | 2011-01-19 | 2011-07-20 | 南京理工大学 | Visible light responsive pucherite-graphene composite photocatalyst and preparation method thereof |
CN102247831A (en) * | 2011-05-17 | 2011-11-23 | 东华大学 | Method for preparing activated carbon self-assembled bismuth vanadate water treatment agent |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102125832A (en) * | 2011-01-19 | 2011-07-20 | 南京理工大学 | Visible light responsive pucherite-graphene composite photocatalyst and preparation method thereof |
CN102247831A (en) * | 2011-05-17 | 2011-11-23 | 东华大学 | Method for preparing activated carbon self-assembled bismuth vanadate water treatment agent |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103657639A (en) * | 2013-12-31 | 2014-03-26 | 长沙理工大学 | Preparation method of graphene/bismuth tungstate lamellar nanostructure visible light catalytic material and silicon modification method thereof |
CN103657639B (en) * | 2013-12-31 | 2015-05-20 | 长沙理工大学 | Preparation method of graphene/bismuth tungstate lamellar nanostructure visible light catalytic material and silicon modification method thereof |
CN103801284A (en) * | 2014-01-22 | 2014-05-21 | 浙江大学 | Method for preparing pucherite-graphene composite photocatalyst |
CN106268761A (en) * | 2016-08-11 | 2017-01-04 | 广西南宁胜祺安科技开发有限公司 | A kind of Graphene doping bismuth vanadate photocatalyst |
CN106179318A (en) * | 2016-09-27 | 2016-12-07 | 安阳师范学院 | A kind of preparation method of pucherite nano wire graphene photo-catalyst |
CN106179318B (en) * | 2016-09-27 | 2019-03-08 | 安阳师范学院 | A kind of preparation method of vanadic acid bismuth nano-wire-graphene photo-catalyst |
CN110180572A (en) * | 2019-05-08 | 2019-08-30 | 陕西科技大学 | A kind of N doping BiVO4The catalysis material of-OVs/GO nano composite structure and its application |
CN110180572B (en) * | 2019-05-08 | 2022-11-04 | 陕西科技大学 | N-doped BiVO 4 -OVs/GO nano composite structured photocatalytic material and application thereof |
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Application publication date: 20120627 |