CN104437587B - A kind of phosphoric acid bismuthino composite photocatalyst material and preparation method thereof - Google Patents
A kind of phosphoric acid bismuthino composite photocatalyst material and preparation method thereof Download PDFInfo
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- CN104437587B CN104437587B CN201410613403.3A CN201410613403A CN104437587B CN 104437587 B CN104437587 B CN 104437587B CN 201410613403 A CN201410613403 A CN 201410613403A CN 104437587 B CN104437587 B CN 104437587B
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Abstract
The invention discloses a kind of phosphoric acid bismuthino composite photocatalyst material, be made up of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite, wherein the mol ratio of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite is 1:0.1～0.3:0.1～0.3. The invention also discloses its preparation method: be dissolved in salpeter solution by five water bismuth nitrate, be subsequently adding the mixed solution of phosphate, ammonium tungstate, ammonium metavanadate and sodium hydroxide solution, reacting through microwave hydrothermal, centrifugal, dry obtain. Phosphoric acid bismuthino composite photocatalyst material of the present invention, is effectively improved the capture ability of Bismugel (Biothrax)., bismuth tungstate and three kinds of interface place electronics of pucherite by nonmetal fluorine and Nitrogen ion codope, strengthens the transport efficiency of electron hole; Bismugel (Biothrax)., bismuth tungstate and three kinds of semiconductors coupling of pucherite can form heterojunction structure in interface, effectively facilitate the separation of photo-generated carrier, and then improve compound system photocatalytic activity.
Description
Technical field
The invention belongs to inorganic environment-friendly catalysis material technical field, be specifically related to a kind of phosphoric acid bismuthino composite photocatalyst material, the preparation method that the invention still further relates to this composite photocatalyst material.
Background technology
There is high-quantum efficiency, the preparation that can make full use of the Photocatalytic material with high activity of solar energy and application, it has also become the hot subject of materialogy, chemistry, the energy and environmental science extensive concern and research. Two key issues in catalysis material research are the activity improving photocatalyst and the absorbing wavelength expanding photocatalyst, thus the mentality of designing of all of novel photocatalysis system, all carry out for the two problem, from this purpose, novel photocatalysis systems most at present is concentrated mainly on metal composite oxide and based on this sulfur, nitrogen substituted compound. The report relating to phosphate catalysis material is little, and phosphate has many characteristics being beneficial to catalysis activity, such as phosphate structure good stability, in light-catalyzed reaction system higher relative to its Lacking oxygen Formation energy of metal-oxide, it is little that this results in Lacking oxygen defect in phosphate crystal, namely complex centre quantity is few, makes electronics and hole can be easily separated, advantageously forms the carrying out of light-catalyzed reaction. Meanwhile, all can there is cavitation corrosion (ZnO, CdS and MoS in most catalysis materials2) and electrical corrosion (GaP, Cu2O and GaN), and phosphate anion is high-valence state is difficult to be chemically reduced, not easily by photoetch, if the metal ion in phosphate is stable equally, just there is photoetch in this photocatalyst under light illumination hardly. And, phosphate has bigger negative charge, can produce very big inductive effect, thus be conducive to the transmission of light induced electron. Additionally, phosphate surface and water have strong interaction, according to thermodynamic principles, surface phosphoric acid root, when with hydrone effect, can produce strong effect with the proton in water, and then be conducive to the generation hydroxyl that dissociates of hydrone.
Bismugel (Biothrax). as a kind of constitutionally stable phosphate semi-conducting material, optics, the selective catalytic oxidation of alkane, ammonia the field such as catalytic oxidation have many application.Nearly 2 years, relate to the research of bismuth phosphate photocatalyst it has been reported that but the energy gap of such photocatalyst is relatively big, can only by ultraviolet excitation, sunlight utilization rate is relatively low. Therefore, widen the light abstraction width of Bismugel (Biothrax)., the application of Bismugel (Biothrax). catalysis material is had certain scientific meaning.
Summary of the invention
It is an object of the invention to provide a kind of phosphoric acid bismuthino composite photocatalyst material, by oxygen vacancy concentration in nonmetallic ion-doped increase Bismugel (Biothrax)., bismuth tungstate and three kinds of quasiconductors of pucherite, and then improve its photocatalytic activity.
The preparation method that it is a further object to provide a kind of phosphoric acid bismuthino composite photocatalyst material.
The technical solution adopted in the present invention is, a kind of phosphoric acid bismuthino composite photocatalyst material, being made up of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite, wherein the mol ratio of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite is 1:0.1～0.3:0.1～0.3.
The feature of the present invention also resides in,
In fluorine, nitrogen co-doped phosphoric acid bismuthino composite photocatalyst material, the mol ratio of bismuth ion, fluorion and Nitrogen ion is 1:0.5～1:0.5～1, and wherein the mol ratio of fluorion and Nitrogen ion is 1:1.
Another technical scheme of the present invention is, the preparation method of a kind of phosphoric acid bismuthino composite photocatalyst material, specifically includes following steps:
Step 1: five water bismuth nitrate are dissolved in the salpeter solution that mass concentration is 65%, obtain solution A; Phosphate, ammonium tungstate and ammonium metavanadate are dissolved in the sodium hydroxide solution that concentration is 1～2mol/L, obtain solution B; Solution A and solution B mix homogeneously are obtained solution C; Ammonium fluoride is added solution C, obtains solution D;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 1～3h to 150～250 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material.
The feature of the present invention also resides in,
In step 1, the mass ratio of five water bismuth nitrate and nitric acid is 1:5～10.
In step 1, the mol ratio of phosphate anion, tungstate ion, vanadic acid radical ion and sodium hydroxide is 1:0.1～0.3:0.1～0.3:1～4.
In step 1, in solution C, the mol ratio of phosphate anion, tungstate ion, vanadic acid radical ion and bismuth ion is 1:0.1～0.3:0.1～0.3:1.3～1.9.
In step 1, the mol ratio of bismuth ion and ammonium fluoride is 1:0.5～1.
In step 1, phosphate is one or more combinations of sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate or potassium dihydrogen phosphate.
The invention has the beneficial effects as follows,
1. phosphoric acid bismuthino composite photocatalyst material of the present invention, have the following characteristics that first, be effectively improved Bismugel (Biothrax). by nonmetal fluorine and Nitrogen ion codope, the capture ability of bismuth tungstate and three kinds of interface place electronics of pucherite, strengthen the transport efficiency of electron hole; The second, oxygen vacancy concentration in Bismugel (Biothrax)., bismuth tungstate and three kinds of quasiconductors of pucherite can be increased by nonmetallic ion-doped, and then improve its light-catalysed photocatalytic activity; 3rd, the existence of low energy gap width quasiconductor bismuth tungstate and pucherite, it is possible to be effectively improved the Bismugel (Biothrax). absorption characteristic at visible ray; 4th, Bismugel (Biothrax)., bismuth tungstate and three kinds of semiconductors coupling of pucherite can form heterojunction structure in interface, effectively facilitate the separation of photo-generated carrier, and then improve compound system photocatalytic activity. Therefore, the present invention proposes fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite composite photocatalyst material are possible not only to widen optical absorption characteristics, it is also possible to improve photocatalytic activity.
2. the preparation method of codope phosphoric acid bismuthino composite photocatalyst material of the present invention, technical process is simple, easy to operate, and compound system component is easily controllable.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
Phosphoric acid bismuthino composite photocatalyst material of the present invention, is made up of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite, and wherein the mol ratio of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite is 1:0.1～0.3:0.1～0.3.
In fluorine, nitrogen co-doped phosphoric acid bismuthino composite photocatalyst material, the mol ratio of bismuth ion, fluorion and Nitrogen ion is 1:0.5～1:0.5～1, and wherein the mol ratio of fluorion and Nitrogen ion is 1:1.
Phosphoric acid bismuthino composite photocatalyst material of the present invention, have the following characteristics that first, be effectively improved Bismugel (Biothrax). by nonmetal fluorine and Nitrogen ion codope, the capture ability of bismuth tungstate and three kinds of interface place electronics of pucherite, strengthen the transport efficiency of electron hole; The second, oxygen vacancy concentration in Bismugel (Biothrax)., bismuth tungstate and three kinds of quasiconductors of pucherite can be increased by nonmetallic ion-doped, and then improve its light-catalysed photocatalytic activity; 3rd, the existence of low energy gap width quasiconductor bismuth tungstate and pucherite, it is possible to be effectively improved the Bismugel (Biothrax). absorption characteristic at visible ray; 4th, Bismugel (Biothrax)., bismuth tungstate and three kinds of semiconductors coupling of pucherite can form heterojunction structure in interface, effectively facilitate the separation of photo-generated carrier, and then improve compound system photocatalytic activity. Therefore, the present invention proposes fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite composite photocatalyst material are possible not only to widen optical absorption characteristics, it is also possible to improve photocatalytic activity.
The preparation method of above-mentioned phosphoric acid bismuthino composite photocatalyst material, specifically includes following steps:
Step 1: five water bismuth nitrate are dissolved in the salpeter solution that mass concentration is 65%, obtain solution A, wherein the mass ratio of five water bismuth nitrate and nitric acid is 1:5～10; Phosphate, ammonium tungstate and ammonium metavanadate being dissolved in the sodium hydroxide solution that concentration is 1～2mol/L, obtains solution B, wherein the mol ratio of phosphate anion, tungstate ion, vanadic acid radical ion and sodium hydroxide is 1:0.1～0.3:0.1～0.3:1～4; Solution A and solution B mix homogeneously are obtained solution C, and wherein in solution C, the mol ratio of phosphate anion, tungstate ion, vanadic acid radical ion and bismuth ion is 1:0.1～0.3:0.1～0.3:1.3～1.9; Ammonium fluoride being added solution C, obtains solution D, wherein the mol ratio of bismuth ion and ammonium fluoride is 1:0.5～1;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 1～3h to 150～250 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material.
In step 1, phosphate is one or more combinations of the soluble phosphates such as sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate.
The preparation method of codope phosphoric acid bismuthino composite photocatalyst material of the present invention, technical process is simple, easy to operate, and compound system component is easily controllable.
Embodiment 1
Step 1: 6.31g five water bismuth nitrate is dissolved in the salpeter solution that 31.55g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate, 3.04g ammonium tungstate and 0.12g ammonium metavanadate are dissolved in 20ml, concentration is the sodium hydroxide solution of 1mol/L, obtains solution B;Solution A and solution B mix homogeneously are obtained solution C; 0.48g ammonium fluoride is added solution C, obtains solution D;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 1h to 150 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material.
Phosphoric acid bismuthino composite photocatalyst material is prepared by embodiment 1 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added 100mL concentration is the methyl orange solution of 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is more than 90%.
Embodiment 2
Step 1: 9.22g five water bismuth nitrate is dissolved in the salpeter solution that 92.2g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate, 9.12g ammonium tungstate and 0.36g ammonium metavanadate are dissolved in 20ml, concentration is the sodium hydroxide solution of 2mol/L, obtains solution B; Solution A and solution B mix homogeneously are obtained solution C; 0.7g ammonium fluoride is added solution C, obtains solution D;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 3h to 250 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material.
Phosphoric acid bismuthino composite photocatalyst material is prepared by embodiment 2 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added 100mL concentration is the methyl orange solution of 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is more than 90%.
Embodiment 3
Step 1: 6.31g five water bismuth nitrate is dissolved in the salpeter solution that 50.48g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate, 6.08g ammonium tungstate and 0.24g ammonium metavanadate are dissolved in 20ml, concentration is the sodium hydroxide solution of 1.5mol/L, obtains solution B; Solution A and solution B mix homogeneously are obtained solution C; 0.48g ammonium fluoride is added solution C, obtains solution D;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 2.5h to 200 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material.
Phosphoric acid bismuthino composite photocatalyst material is prepared by embodiment 3 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added 100mL concentration is the methyl orange solution of 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is more than 90%.
Embodiment 4
Step 1: 6.31g five water bismuth nitrate is dissolved in the salpeter solution that 37.86g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate, 9.12g ammonium tungstate and 0.36g ammonium metavanadate are dissolved in 20ml, concentration is the sodium hydroxide solution of 1.8mol/L, obtains solution B; Solution A and solution B mix homogeneously are obtained solution C; 0.7g ammonium fluoride is added solution C, obtains solution D;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 2h to 220 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material.
Phosphoric acid bismuthino composite photocatalyst material is prepared by embodiment 4 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added 100mL concentration is the methyl orange solution of 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is more than 90%.
In embodiment 4, phosphate is sodium phosphate, it is also possible to for one or more combinations of the soluble phosphates such as sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate.
Claims (7)
1. a phosphoric acid bismuthino composite photocatalyst material, it is characterised in that be made up of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite, wherein the mol ratio of fluorine, nitrogen co-doped Bismugel (Biothrax)., bismuth tungstate and pucherite is 1:0.1～0.3:0.1～0.3.
2. phosphoric acid bismuthino composite photocatalyst material according to claim 1, it is characterized in that, in fluorine, nitrogen co-doped phosphoric acid bismuthino composite photocatalyst material, the mol ratio of bismuth ion, fluorion and Nitrogen ion is 1:0.5～1:0.5～1, and wherein the mol ratio of fluorion and Nitrogen ion is 1:1.
3. the preparation method of a phosphoric acid bismuthino composite photocatalyst material, it is characterised in that specifically include following steps:
Step 1: five water bismuth nitrate are dissolved in the salpeter solution that mass concentration is 65%, obtain solution A; Phosphate, ammonium tungstate and ammonium metavanadate are dissolved in the sodium hydroxide solution that concentration is 1～2mol/L, obtain solution B; Solution A and solution B mix homogeneously are obtained solution C; Ammonium fluoride is added solution C, obtains solution D;
Step 2: solution D step 1 obtained is transferred to hydrothermal reaction kettle, it is placed in microwave reactor and utilizes microwave heating to process 1～3h to 150～250 DEG C of microwave hydrothermals, room temperature is naturally cooled to after taking-up, the product centrifugation that will obtain, deionized water wash 3 times, in 80 DEG C of dry 12h, obtain phosphoric acid bismuthino composite photocatalyst material;
In step 1, in solution C, the mol ratio of phosphate anion, tungstate ion, vanadic acid radical ion and bismuth ion is 1:0.1～0.3:0.1～0.3:1.3～1.9.
4. the preparation method of phosphoric acid bismuthino composite photocatalyst material according to claim 3, it is characterised in that in step 1, the mass ratio of five water bismuth nitrate and nitric acid is 1:5～10.
5. the preparation method of phosphoric acid bismuthino composite photocatalyst material according to claim 3, it is characterised in that in step 1, the mol ratio of phosphate anion, tungstate ion, vanadic acid radical ion and sodium hydroxide is 1:0.1～0.3:0.1～0.3:1～4.
6. the preparation method of phosphoric acid bismuthino composite photocatalyst material according to claim 3, it is characterised in that in step 1, the mol ratio of bismuth ion and ammonium fluoride is 1:0.5～1.
7. the preparation method according to the arbitrary described phosphoric acid bismuthino composite photocatalyst material of claim 3～6, it is characterized in that, in step 1, phosphate is one or more combinations of sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate or potassium dihydrogen phosphate.
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| CN104475139B (en) * | 2014-11-04 | 2017-02-01 | 陕西科技大学 | Co-doped bismuth phosphate-base composite photocatalytic material and preparation method thereof |
| CN104971753A (en) * | 2015-06-03 | 2015-10-14 | 河南师范大学 | Bi2O2CO3-BiPO4 composite photocatalyst and preparation method thereof |
| CN104961117B (en) * | 2015-06-29 | 2017-01-11 | 陕西科技大学 | Preparation method for fusiform rod-shaped hexagonal phase BiPO4 powder |
| JP6803065B2 (en) * | 2016-11-09 | 2020-12-23 | 国立大学法人 筑波大学 | Photocatalyst and its manufacturing method |
| CN106824247B (en) * | 2017-02-28 | 2019-01-25 | 陕西科技大学 | A kind of bismuth tungstate/carbonitride/bismuth phosphate composite photo-catalyst and its preparation method and application |
| CN108004526A (en) * | 2017-11-09 | 2018-05-08 | 江苏大学 | A kind of preparation method of phosphorus doping pucherite light anode |
| CN110227519B (en) * | 2019-07-05 | 2022-03-22 | 宿州学院 | Fluoride ion doped bismuth phosphate composite catalyst, preparation method and application thereof |
| CN110614103A (en) * | 2019-09-26 | 2019-12-27 | 黄冈师范学院 | Microwave synthesis method of bismuth vanadate and bismuth phosphate compound visible-light-driven photocatalyst |
| CN111359640B (en) * | 2020-02-19 | 2022-06-21 | 东北师范大学 | Preparation method of multi-heterojunction titanium dioxide-bismuth vanadate-black phosphorus/red phosphorus composite film |
| CN115228501B (en) * | 2022-08-24 | 2023-09-19 | 西安建筑科技大学 | Preparation and application of porous semicoke activated carbon loaded ternary heterojunction photocatalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489324A (en) * | 2011-11-18 | 2012-06-13 | 陕西科技大学 | F and N co-doped visible-light response bismuth vanadate photocatalyst and preparation method thereof |
| CN102513096A (en) * | 2011-11-17 | 2012-06-27 | 陕西科技大学 | Co-doped visible light response bismuth tungstate photochemical catalyst and preparation method thereof |
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| CN102513096A (en) * | 2011-11-17 | 2012-06-27 | 陕西科技大学 | Co-doped visible light response bismuth tungstate photochemical catalyst and preparation method thereof |
| CN102489324A (en) * | 2011-11-18 | 2012-06-13 | 陕西科技大学 | F and N co-doped visible-light response bismuth vanadate photocatalyst and preparation method thereof |
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