CN102489291A - Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst - Google Patents
Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst Download PDFInfo
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- CN102489291A CN102489291A CN2011104079292A CN201110407929A CN102489291A CN 102489291 A CN102489291 A CN 102489291A CN 2011104079292 A CN2011104079292 A CN 2011104079292A CN 201110407929 A CN201110407929 A CN 201110407929A CN 102489291 A CN102489291 A CN 102489291A
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Abstract
The invention relates to a method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst, which comprises the following steps: 1 adding bismuthate and stabilizing agent into phosphate buffer, stirring for 15 to 60 minutes to form turbid liquid, dissolving metavanadate into the phosphate buffer uniformly, adding the phosphate buffer into the turbid liquid, and stirring the solution to be uniform to form transparent solution; and 2 regulating potential of hydrogen (pH) value through alkaline solution, adding expanded graphite at the temperature of 20 DEG C to 100 DEG C, stirring, mixing, refluxing for 6 hours to 24 hours, centrifuging, filtering, washing, finally roasting the obtained products, cooling and grinding to obtain the final product. The method is low in cost, easy to apply and good in maneuverability and has low requirements for devices. The obtained expanded graphite powder bismuth vanadate is even in self-assembly, can efficiently degrade durable toxic and harmful substances under conditions of ultraviolet light and visible light, can be recovered and recycled easily and conveniently and is very suitable for deep processing of waste water.
Description
Technical field
The invention belongs to the preparation field of pucherite photochemical catalyst, particularly a kind of preparation method of expanded graphite supporting 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 waste water difficult for biological degradation processing 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 expanded graphite supporting nanometer pucherite photochemical catalyst, and this method is with low cost, and is simple, to equipment require lowly, operability is good; The expanded graphite powder pucherite self assembly of 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.
The preparation method of a kind of expanded graphite supporting 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 earlier, joins then in the above-mentioned suspension, stir, form clear solution; Wherein, the mol ratio of bismuth salt and metavanadate is 1: 1, and bismuth salt and the metavanadate concentration in solution is 0.01～0.15mol/L, and the concentration of stabilizing agent in solution is 0.01～0.05mol/L;
(2) regulate pH value to 4.5～9.0 of above-mentioned clear solution with alkaline solution; Be 5: 1～20: 1 expanded graphite then at 20～100 ℃ of following addings and bismuth salt mass ratio, mix backflow 6-24h; Centrifugal, filter, after the washing; At last with the products therefrom roasting, after cooling is ground, the expanded graphite photochemical catalyst powder of nanometer pucherite that promptly got self assembly.
Bismuth salt in the said step (1) is bismuth nitrate, basic bismuth carbonate, bismuth chloride or bismuth acetate.
Stabilizing agent in the said step (1) is disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt or BTCA.
Metavanadate in the said step (1) is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
Phosphate buffer in the said step (1) is 0.025～0.05mol/L sodium dihydrogen phosphate and the solution composition of 0.05～0.1mol/L dibastic sodium phosphate by concentration.
Alkaline solution in the said step (2) is NaOH or the potassium hydroxide aqueous solution of 0.5～1.5mol/L.
Sintering temperature in the said step (2) is 180～400 ℃, and roasting time is 2～4h.
The present invention utilize the unique layer chain structure characteristic of expanded graphite, specific area greatly, characteristics such as high adsorption capacity, chemical inertness, in conjunction with BiVO
4Visible light catalysis activity, the success with nanometer BiVO
4Load on the expanded graphite; 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 expanded graphite 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 support 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 expanded graphite 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;
(3) expanded graphite itself is a kind of well behaved adsorbent, have specific area big with characteristics such as high adsorption capacity, in wastewater treatment, can also reach deodorizing simultaneously, beneficial effects such as absorption removal 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 adding expanded graphites down, wherein the mass ratio of bismuth salt and expanded graphite is 1: 5 then; Magnetic agitation is mixed continuously, and backflow 6h, centrifugal, filtration are after the washing; Can get yellow product; At last with products therefrom in 180 ℃ of roasting 2h, after cooling is ground, the expanded graphite 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 expanded graphites down at 80 ℃ then, and wherein the mass ratio of bismuth salt and expanded graphite is 1: 12; Magnetic agitation is mixed continuously, and backflow 15h, centrifugal, filtration are after the washing; Can get yellow product; At last with products therefrom in 300 ℃ of roasting 3h, after cooling is ground, the expanded graphite 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 adding expanded graphites down, wherein the mass ratio of bismuth salt and expanded graphite is 1: 20 then; Magnetic agitation is mixed continuously, and backflow 24h, centrifugal, filtration are after the washing; Can get yellow product; At last with products therefrom in 400 ℃ of roasting 4h, after cooling is ground, the expanded graphite 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～embodiment 3 prepared photochemical catalysts; Under sunshine, shone 6 hours continuously, to decolorization of dyeing rate and COD
CrClearance is as shown in the table respectively:
| Percent of decolourization | COD CrClearance | |
| Embodiment 1 | 99.3％ | 89.8％ |
| Embodiment 2 | 98.1％ | 93.9％ |
| Embodiment 3 | 99.5％ | 95.7％ |
Claims (7)
1. the preparation method of an expanded graphite supporting 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 earlier, joins then in the above-mentioned suspension, stir, form clear solution; Wherein, the mol ratio of bismuth salt and metavanadate is 1: 1, and bismuth salt and the metavanadate concentration in solution is 0.01～0.15mol/L, and the concentration of stabilizing agent in solution is 0.01～0.05mol/L;
(2) regulate pH value to 4.5～9.0 of above-mentioned clear solution with alkaline solution; Be 5: 1～20: 1 expanded graphite then at 20～100 ℃ of following addings and bismuth salt mass ratio, mix backflow 6-24h; Centrifugal, filter, after the washing; At last with the products therefrom roasting, after cooling is ground, the expanded graphite photochemical catalyst powder of nanometer pucherite that promptly got self assembly.
2. the preparation method of a kind of expanded graphite supporting nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the bismuth salt in the said step (1) is bismuth nitrate, basic bismuth carbonate, bismuth chloride or bismuth acetate.
3. the preparation method of a kind of expanded graphite supporting nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the stabilizing agent in the said step (1) is disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt or BTCA.
4. the preparation method of a kind of expanded graphite supporting nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the metavanadate in the said step (1) is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
5. the preparation method of a kind of expanded graphite supporting nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the phosphate buffer in the said step (1) is 0.025～0.05mol/L sodium dihydrogen phosphate and the solution composition of 0.05～0.1mol/L dibastic sodium phosphate by concentration.
6. the preparation method of a kind of expanded graphite supporting nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the alkaline solution in the said step (2) is NaOH or the potassium hydroxide aqueous solution of 0.5～1.5mol/L.
7. the preparation method of a kind of expanded graphite supporting nanometer pucherite photochemical catalyst according to claim 1 is characterized in that: the sintering temperature in the said step (2) is 180～400 ℃, and roasting time is 2～4h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105839172A (en) * | 2016-04-25 | 2016-08-10 | 陕西科技大学 | Monoclinic-phase BiVO4/GO (graphene oxide)/RGO (reduced graphene oxide) crystal and preparation method thereof |
| CN109796059A (en) * | 2019-01-29 | 2019-05-24 | 山西能源学院 | A method of utilizing photocatalysis technology purification of organic waste water |
| CN110252382A (en) * | 2019-06-28 | 2019-09-20 | 华南理工大学 | A kind of composite photo-catalyst of basic salt of bismuth-containing and preparation method thereof |
| CN113351222A (en) * | 2021-06-23 | 2021-09-07 | 湖北民族大学 | Bismuth vanadate and manganese dioxide magnetic composite photocatalysis-oxidizing agent and preparation method thereof |
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| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
| 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 |
| CN102157315A (en) * | 2011-03-21 | 2011-08-17 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
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Patent Citations (3)
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| CN101857222A (en) * | 2010-05-28 | 2010-10-13 | 常州大学 | Preparation method of large-area and continuous graphen/zinc oxide composite structure |
| 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 |
| CN102157315A (en) * | 2011-03-21 | 2011-08-17 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105839172A (en) * | 2016-04-25 | 2016-08-10 | 陕西科技大学 | Monoclinic-phase BiVO4/GO (graphene oxide)/RGO (reduced graphene oxide) crystal and preparation method thereof |
| CN109796059A (en) * | 2019-01-29 | 2019-05-24 | 山西能源学院 | A method of utilizing photocatalysis technology purification of organic waste water |
| CN110252382A (en) * | 2019-06-28 | 2019-09-20 | 华南理工大学 | A kind of composite photo-catalyst of basic salt of bismuth-containing and preparation method thereof |
| CN110252382B (en) * | 2019-06-28 | 2020-08-18 | 华南理工大学 | Bismuth-containing basic salt composite photocatalyst and preparation method thereof |
| CN113351222A (en) * | 2021-06-23 | 2021-09-07 | 湖北民族大学 | Bismuth vanadate and manganese dioxide magnetic composite photocatalysis-oxidizing agent and preparation method thereof |
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Inventor after: Gu Yongxing Inventor after: Li Hao Inventor after: Liu Baojiang Inventor after: Gao Pin Inventor before: Li Hao Inventor before: Liu Baojiang Inventor before: Gao Pin |
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Granted publication date: 20140813 Termination date: 20181209 |