CN102489291B - 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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- CN102489291B CN102489291B CN201110407929.2A CN201110407929A CN102489291B CN 102489291 B CN102489291 B CN 102489291B CN 201110407929 A CN201110407929 A CN 201110407929A CN 102489291 B CN102489291 B CN 102489291B
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- expanded graphite
- bismuth
- photochemical catalyst
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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 bismuth vanadate photocatalyst, particularly a kind of preparation method of expanded graphite load nanometer bismuth vanadate photochemical catalyst.
Background technology
In recent years, with titanium dioxide (TiO
2) for the photocatalysis technology of core representative is in environmental pollution improvement field, particularly the application in waste water difficult for biological degradation processing and air cleaning is more and more extensive, but due to its greater band gap, only can under UV-irradiation, just there is photocatalysis, thereby limit the further expansion of its application.In order to improve TiO
2utilization ratio to sunshine, lot of domestic and international experts and scholars are round visible light-responded TiO
2photochemical catalyst has launched a large amount of research work, mainly for TiO
2photocatalyst surface is structurally-modified, inorganic elements and doped with metal elements modification etc., is intended to expand its spectral response range, improves its visible light catalysis activity.However, the TiO of process modification
2photochemical catalyst still exists the problems such as visible light catalysis activity is undesirable, and light degradation ability is poor at this stage, causes its practicality poor.
Nearest research finds to have the composite oxides pucherite (BiVO of monoclinic system scheelite-type structure
4) under radiation of visible light, just there is photocatalytic activity, can produce oxygen and degradable organic pollutant by decomposition water molecule, be a kind of potential photochemical catalyst.Yet, BiVO
4absorption property very poor, and the photo-generated carrier producing is difficult to migration, easily compound, thereby affected its visible light activity.At present about for BiVO
4research report composite modified and doping less, in addition about being self-assembled to the porous material that absorption property is good, as also few in 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 at present BiVO
4the main research emphasis of high efficiency photocatalyst.
Sewage disposal conventional method mainly contains: physical partition method, biological degradation method, chemical decomposition method etc., but these methods all have some limitations, therefore, researcher start to be devoted to that exploitation is efficient, low energy consumption, applied widely and have a water treatment technology of deep oxidation ability.In recent years, a lot of scholars are by TiO
2organic pollution for photocatalytic degradation water body, although obtained certain effect, due to the restriction of its photoresponse scope, causes treatment effect often not ideal enough.By contrast, BiVO
4in visible region, just having good photocatalytic activity, is a kind of potential desired light catalyst.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of expanded graphite load nanometer bismuth vanadate photochemical catalyst, and the method is with low cost, 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 ray 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 load nanometer bismuth vanadate photochemical catalyst of the present invention, comprising:
(1) bismuth salt, stabilizing agent are joined in phosphate buffer, stir 15～60min, form suspension; Metavanadate is first evenly dissolved in to phosphate buffer, then joins in 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) with alkaline solution, regulate pH value to 4.5～9.0 of above-mentioned clear solution, then at 20～100 ℃, add with bismuth salt mass ratio is the expanded graphite of 5: 1～20: 1, be uniformly mixed, backflow 6-24h, centrifugal, filter, after washing, finally by products therefrom roasting, after cooling grinding, the expanded graphite photochemical catalyst powder of nanometer pucherite that obtained self assembly.
Bismuth salt in described step (1) is bismuth nitrate, basic bismuth carbonate, bismuth chloride or bismuth acetate.
Stabilizing agent in described step (1) is disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt or BTCA.
Metavanadate in described step (1) is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
Phosphate buffer in described 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.
NaOH or potassium hydroxide aqueous solution that alkaline solution in described step (2) is 0.5～1.5mol/L.
Sintering temperature in described step (2) is 180～400 ℃, and roasting time is 2～4h.
The present invention utilizes the features such as the layer chain structure feature, specific area of expanded graphite uniqueness is large, high adsorption capacity, chemical inertness, in conjunction with BiVO
4visible light catalysis activity, successfully by nanometer BiVO
4load on 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 the efficient removal to organic pollutants, particularly conventional treatment is difficult to the persistence micropollutants of effectively removing, and non-secondary pollution, be the technology of environment-friendly type.
In China, expanded graphite resource reserve is very large, but more late due to what find, its development of exploitation level is lower, a little less than adding national nonmetallic ore processing industry basis relative thin, to such an extent as to the application of the great mineral reserve of this economic implications is also only limited to general filler, therefore, the prepared support type visible-light photocatalysis material of the present invention also has advantages of with low cost, has boundless actual application prospect.
beneficial effect
(1) the present invention is with low cost, and preparation method is simple, to equipment require lowly, operability is good;
(2) the expanded graphite powder pucherite self assembly that prepared by the present invention is even, can be under ultraviolet light and visible ray 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, has the features such as the large and high adsorption capacity of specific area, and in wastewater treatment, the while can also reach deodorizing, the beneficial effects such as Adsorption heavy metal ion.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) bismuth nitrate, disodium ethylene diamine tetraacetate are joined in phosphate buffer, magnetic agitation 15min, forms suspension; Sodium metavanadate is first evenly dissolved in to phosphate buffer, then dropwise joins in above-mentioned suspension, 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 comprised of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L dibastic sodium phosphate;
(2) it is 4.5 that the sodium hydrate aqueous solution that employing concentration is 0.5mol/L regulates the pH value of above-mentioned clear solution, then at 60 ℃, add expanded graphite, wherein the mass ratio of bismuth salt and expanded graphite is 1: 5, magnetic agitation is mixed continuously, and backflow 6h, centrifugal, filtration, after washing, can obtain yellow product, finally by products therefrom in 180 ℃ of roasting 2h, after cooling grinding, the expanded graphite photochemical catalyst powder of nanometer pucherite that obtained self assembly.
Embodiment 2
(1) bismuth chloride, gluconic acid sodium salt are joined in phosphate buffer, magnetic agitation 35min, forms suspension; Ammonium metavanadate is first evenly dissolved in to phosphate buffer, then dropwise joins in above-mentioned suspension, 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 comprised of 0.03mol/L sodium dihydrogen phosphate and 0.08mol/L dibastic sodium phosphate;
(2) it is 7 that the potassium hydroxide aqueous solution that employing degree is 1mol/L regulates the pH value of above-mentioned clear solution, then at 80 ℃, add expanded graphite, wherein the mass ratio of bismuth salt and expanded graphite is 1: 12, magnetic agitation is mixed continuously, and backflow 15h, centrifugal, filtration, after washing, can obtain yellow product, finally by products therefrom in 300 ℃ of roasting 3h, after cooling grinding, the expanded graphite photochemical catalyst powder of nanometer pucherite that obtained self assembly.
Embodiment 3
(1) bismuth acetate, BTCA are joined in phosphate buffer, magnetic agitation 60min, forms suspension; Potassium metavanadate is first evenly dissolved in to phosphate buffer, then dropwise joins in above-mentioned suspension, 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 comprised of 0.05mol/L sodium dihydrogen phosphate and 0.1mol/L dibastic sodium phosphate;
(2) it is 9 that the sodium hydrate aqueous solution that employing concentration is 1.5mol/L regulates the pH value of above-mentioned clear solution, then at 100 ℃, add expanded graphite, wherein the mass ratio of bismuth salt and expanded graphite is 1: 20, magnetic agitation is mixed continuously, and backflow 24h, centrifugal, filtration, after washing, can obtain yellow product, finally by products therefrom in 400 ℃ of roasting 4h, after cooling grinding, the expanded graphite photochemical catalyst powder of nanometer pucherite that obtained self assembly.
Wastewater treatment experiment: the dyeing waste water of the final discharge of Yi Mou printing and dyeing mill is for processing object, after micro-filtrate membrane filtration pretreatment, add respectively therein same amount to pass through the prepared photochemical catalyst of embodiment 1～embodiment 3, under sunshine, irradiate 6 hours continuously, to the percent of decolourization of dyeing waste water 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 (6)
1. a preparation method for expanded graphite load nanometer bismuth vanadate photochemical catalyst, comprising:
(1) bismuth salt, stabilizing agent are joined in phosphate buffer, stir 15～60min, form suspension; Metavanadate is first evenly dissolved in to phosphate buffer, then joins in 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; Wherein stabilizing agent is disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt or BTCA;
(2) with alkaline solution, regulate pH value to 4.5～9.0 of above-mentioned clear solution, then the expanded graphite that to add with bismuth salt mass ratio at 20～100 ℃ be 5:1～20:1, be uniformly mixed, backflow 6-24h, centrifugal, filter, after washing, finally by products therefrom roasting, after cooling grinding, the expanded graphite photochemical catalyst powder of nanometer pucherite that obtained self assembly.
2. the preparation method of a kind of expanded graphite load nanometer bismuth vanadate photochemical catalyst according to claim 1, is characterized in that: the bismuth salt in described step (1) is bismuth nitrate, basic bismuth carbonate, bismuth chloride or bismuth acetate.
3. the preparation method of a kind of expanded graphite load nanometer bismuth vanadate photochemical catalyst according to claim 1, is characterized in that: the metavanadate in described step (1) is sodium metavanadate, potassium metavanadate or ammonium metavanadate.
4. the preparation method of a kind of expanded graphite load nanometer bismuth vanadate photochemical catalyst according to claim 1, is characterized in that: the phosphate buffer in described 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.
5. the preparation method of a kind of expanded graphite load nanometer bismuth vanadate photochemical catalyst according to claim 1, is characterized in that: NaOH or potassium hydroxide aqueous solution that the alkaline solution in described step (2) is 0.5～1.5mol/L.
6. the preparation method of a kind of expanded graphite load nanometer bismuth vanadate photochemical catalyst according to claim 1, is characterized in that: the sintering temperature in described step (2) is 180～400 ℃, and roasting time is 2～4h.
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| CN105839172B (en) * | 2016-04-25 | 2018-08-17 | 陕西科技大学 | A kind of monoclinic phase BiVO4/ GO/RGO 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 |
| 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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| 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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| 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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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 |