CN104475137A - In-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst and preparation method thereof - Google Patents
In-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst and preparation method thereof Download PDFInfo
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- CN104475137A CN104475137A CN201410614149.9A CN201410614149A CN104475137A CN 104475137 A CN104475137 A CN 104475137A CN 201410614149 A CN201410614149 A CN 201410614149A CN 104475137 A CN104475137 A CN 104475137A
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Abstract
A disclosed in-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst is composed of fluorine-nitrogen co-doped bismuth phosphate and cuprous oxide with the molar ratio of 1:0.2-1. The invention also discloses a preparation method for the photocatalyst. The preparation method comprises: dissolving bismuth nitrate pentahydrate in a nitric acid solution, then adding a phosphate solution and ammonic chloride, then adding a mixed solution of copper sulfate pentahydrate, xylitol and sodium hydroxide, stirring uniformly, and performing microwave hydrothermal reaction, centrifugation and drying to obtain the photocatalyst. Through co-doping of nonmetal fluorine and nitrogen ions, the in-situ doped type bismuth phosphate-cuprous oxide composite photocatalyst effectively improves the electron capture capability of a bismuth phosphate semiconductor at the interface and enhances the electron cavity migration efficiency. Through nonmetal ion co-doping, the oxygen cavity concentration in the bismuth phosphate semiconductor is increased, and further the photocatalytic activity of bismuth phosphate is improved.
Description
Technical field
The invention belongs to inorganic environment-friendly catalysis material technical field, be specifically related to a kind of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, the invention still further relates to the preparation method of this composite photo-catalyst.
Background technology
There is high-quantum efficiency, the preparations and applicatio of the Photocatalytic material with high activity of solar energy can be made full use of, become the hot subject of materialogy, chemistry, the energy and environmental science extensive concern and research.Two key issues in catalysis material research improve the activity of photochemical catalyst and the absorbing wavelength expanding photochemical catalyst, the mentality of designing of thus all novel photocatalysis systems, all carry out for this two problems, from this purpose, novel photocatalysis systems most at present mainly concentrates on composite metal oxide and sulphur, nitrogen substituted compound based on this.The report relating to phosphate catalysis material is little, and phosphate has many characteristics being beneficial to catalytic activity, as phosphate structure good stability, higher relative to its Lacking oxygen Formation energy of metal oxide in light-catalyzed reaction system, this just causes Lacking oxygen defect in phosphate crystal little, namely complex centre quantity is few, and electronics is easily separated with hole, is conducive to the carrying out forming light-catalyzed reaction.Meanwhile, all can there is cavitation corrosion (ZnO, CdS and MoS in most catalysis material
2) and electrical corrosion (GaP, Cu
2o 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 photochemical catalyst under light illumination hardly.And phosphate has larger negative electrical charge, very large inductive effect can be produced, thus be conducive to the transmission of light induced electron.In addition, phosphate surface and water have strong interaction, and 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.
Bismuth phosphate, as the constitutionally stable phosphate semi-conducting material of one, has many application in fields such as the selective catalytic oxidation of optics, alkane, the catalytic oxidations of ammonia.Nearly 2 years, the research relating to bismuth phosphate photocatalyst had been reported, but the energy gap of such photochemical catalyst is comparatively large, can only by ultraviolet excitation, lower to sunshine utilization rate.Therefore, widen the light abstraction width of bismuth phosphate, to the application of bismuth phosphate catalysis material, there is certain scientific meaning.
Summary of the invention
The object of this invention is to provide a kind of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, by oxygen vacancy concentration in nonmetallic ion-doped increase bismuth phosphate semiconductor, and then improve the light-catalysed photocatalytic activity of bismuth phosphate.
Another object of the present invention is to provide the preparation method of a kind of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
The technical solution adopted in the present invention is, in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, is made up of fluorine, nitrogen co-doped bismuth phosphate and cuprous oxide, and wherein the mol ratio of fluorine, nitrogen co-doped bismuth phosphate and cuprous oxide is 1:0.2 ~ 1.
Feature of the present invention is also,
In fluorine, nitrogen co-doped bismuth phosphate, the mol ratio of bismuth ion, fluorine ion and Nitrogen ion is 1:0.5 ~ 1:0.5 ~ 1, and wherein the mol ratio of fluorine ion and Nitrogen ion is 1:1.
Another technical scheme of the present invention is, the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, specifically comprises the following steps:
Step 1: five water bismuth nitrates are dissolved in the salpeter solution that mass concentration is 65%, obtain solution A; Phosphate is water-soluble, obtain solution B; Solution A and solution B are mixed and obtains solution C; Ammonium fluoride is added solution C, obtains solution D; By water-soluble to cupric sulfate pentahydrate, pentitol and NaOH, obtain solution E; Solution E is dropwise added in solution D, mixing and stirring, obtain solution F;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 150 ~ 250 DEG C microwave hydrothermal process 1 ~ 3h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
Feature of the present invention is also,
In step 1, the mass ratio of five water bismuth nitrates and nitric acid is 1:5 ~ 10.
In step 1, the mass ratio of phosphate and water is 1:5 ~ 10.
In step 1, in solution C, the mol ratio of bismuth ion and phosphate anion is 1:1.
In step 1, the mol ratio of bismuth ion and ammonium fluoride is 1:0.5 ~ 1.
In step 1, the mass ratio of cupric sulfate pentahydrate, pentitol, NaOH and water is 1:0.5 ~ 1.5:3 ~ 6:30 ~ 60.
In step 1, the mol ratio of bismuth ion and copper ion is 1:0.2 ~ 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. in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst of the present invention, has following characteristics: the capture ability the first, effectively being improved bismuth phosphate interface place electronics by nonmetal fluorine and Nitrogen ion codope, strengthens the transport efficiency of electron hole; The second, by oxygen vacancy concentration in nonmetallic ion-doped increase bismuth phosphate semiconductor, and then the light-catalysed photocatalytic activity of bismuth phosphate is improved; Three, the existence that low energy gap width semiconductor oxide is cuprous, effectively can improve the absorption characteristic of bismuth phosphate at visible ray; Four, n-type semiconductor bismuth phosphate and p-type semiconductor cuprous oxide can form the heterogeneous joint of p-n in interface, effectively promote the separation of photo-generated carrier, and then improve compound system photocatalytic activity.Therefore, in-situ doping type bismuth phosphate/cuprous oxide composite photo-catalyst that the present invention proposes not only can widen optical absorption characteristics, can also improve photocatalytic activity.
2. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst of the present invention, feature is the synthesis completing material at a lower temperature, and technical process is simple, and compound system composition is easy to control.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
In-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst of the present invention, is made up of fluorine, nitrogen co-doped bismuth phosphate and cuprous oxide, and wherein the mol ratio of fluorine, nitrogen co-doped bismuth phosphate and cuprous oxide is 1:0.2 ~ 1.
In fluorine, nitrogen co-doped bismuth phosphate, the mol ratio of bismuth ion, fluorine ion and Nitrogen ion is 1:0.5 ~ 1:0.5 ~ 1, and wherein the mol ratio of fluorine ion and Nitrogen ion is 1:1.
In-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst of the present invention, has following characteristics: the capture ability the first, effectively being improved bismuth phosphate interface place electronics by nonmetal fluorine and Nitrogen ion codope, strengthens the transport efficiency of electron hole; The second, by oxygen vacancy concentration in nonmetallic ion-doped increase bismuth phosphate semiconductor, and then the light-catalysed photocatalytic activity of bismuth phosphate is improved; Three, the existence that low energy gap width semiconductor oxide is cuprous, effectively can improve the absorption characteristic of bismuth phosphate at visible ray; Four, n-type semiconductor bismuth phosphate and p-type semiconductor cuprous oxide can form the heterogeneous joint of p-n in interface, effectively promote the separation of photo-generated carrier, and then improve compound system photocatalytic activity.Therefore, in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst that the present invention proposes not only can widen optical absorption characteristics, can also improve photocatalytic activity.
The preparation method of above-mentioned in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, specifically comprises the following steps:
Step 1: five water bismuth nitrates are dissolved in the salpeter solution that mass concentration is 65%, obtain solution A, wherein the mass ratio of five water bismuth nitrates and nitric acid is 1:5 ~ 10; Phosphate is water-soluble, and obtain solution B, wherein the mass ratio of phosphate and water is 1:5 ~ 10; Solution A and solution B are mixed and obtain solution C, wherein in solution C, the mol ratio of bismuth ion and phosphate anion is 1:1; Ammonium fluoride is added solution C, obtains solution D, wherein the mol ratio of bismuth ion and ammonium fluoride is 1:0.5 ~ 1; By water-soluble to cupric sulfate pentahydrate, pentitol and NaOH, obtain solution E, wherein the mass ratio of cupric sulfate pentahydrate, pentitol, NaOH and water is 1:0.5 ~ 1.5:3 ~ 6:30 ~ 60; Solution E dropwise added in solution D, mixing and stirring, obtain solution F, wherein the mol ratio of bismuth ion and copper ion is 1:0.2 ~ 1;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 150 ~ 250 DEG C microwave hydrothermal process 1 ~ 3h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
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 in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst of the present invention, feature is the synthesis completing material at a lower temperature, and technical process is simple, and compound system composition is easy to control.
Embodiment 1
Step 1: 4.85g five water bismuth nitrate is dissolved in the salpeter solution that 24.25g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate is dissolved in 8.2g water, obtains solution B; Solution A and solution B are mixed and obtains solution C; 0.185g ammonium fluoride is added solution C, obtains solution D; 0.5g cupric sulfate pentahydrate, 0.25g pentitol and 1.5g NaOH are dissolved in 15g water, obtain solution E; Solution E is dropwise added in solution D, mixing and stirring, obtain solution F;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 150 DEG C microwave hydrothermal process 1h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
Prepared by in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst to embodiment 1 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added the methyl orange solution that 100mL concentration is 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is greater than 90%.
Embodiment 2
Step 1: 4.85g five water bismuth nitrate is dissolved in the salpeter solution that 48.5g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate is dissolved in 16.4g water, obtains solution B; Solution A and solution B are mixed and obtains solution C; 0.37g ammonium fluoride is added solution C, obtains solution D; 2.5g cupric sulfate pentahydrate, 3.75g pentitol and 15g NaOH are dissolved in 150g water, obtain solution E; Solution E is dropwise added in solution D, mixing and stirring, obtain solution F;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 250 DEG C microwave hydrothermal process 3h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
Prepared by in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst to embodiment 2 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added the methyl orange solution that 100mL concentration is 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is greater than 90%.
Embodiment 3
Step 1: 4.85g five water bismuth nitrate is dissolved in the salpeter solution that 38.8g mass concentration is 65%, obtains solution A; 1.64g sodium phosphate is dissolved in 12.3g water, obtains solution B; Solution A and solution B are mixed and obtains solution C; 0.259g ammonium fluoride is added solution C, obtains solution D; 1.25g cupric sulfate pentahydrate, 1.25g pentitol and 5g NaOH are dissolved in 50g water, obtain solution E; Solution E is dropwise added in solution D, mixing and stirring, obtain solution F;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 200 DEG C microwave hydrothermal process 2h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
Prepared by in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst to embodiment 3 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added the methyl orange solution that 100mL concentration is 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is greater than 90%.
Embodiment 4
Step 1: 4.85g five water bismuth nitrate is dissolved in the salpeter solution that 29.1g mass concentration is 65%, obtains solution A; 1.64g phosphate is dissolved in 14.76g water, obtains solution B; Solution A and solution B are mixed and obtains solution C; 0.296g ammonium fluoride is added solution C, obtains solution D; 2g cupric sulfate pentahydrate, 2.4g pentitol and 10g NaOH are dissolved in 100g water, obtain solution E; Solution E is dropwise added in solution D, mixing and stirring, obtain solution F;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 180 DEG C microwave hydrothermal process 2.5h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
Prepared by in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst to embodiment 4 and carries out light degradation experiment, selection methyl orange is target contaminant, above-mentioned for 0.02g composite photocatalyst material is added the methyl orange solution that 100mL concentration is 10mg/L, after 100min radiation of visible light (300W xenon lamp), methyl orange degradation efficiency is greater than 90%.
In embodiment 4, phosphate is sodium phosphate, also can be 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 (10)
1. in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, is characterized in that, is made up of fluorine, nitrogen co-doped bismuth phosphate and cuprous oxide, and wherein the mol ratio of fluorine, nitrogen co-doped bismuth phosphate and cuprous oxide is 1:0.2 ~ 1.
2. in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 1, it is characterized in that, in fluorine, nitrogen co-doped bismuth phosphate, the mol ratio of bismuth ion, fluorine ion and Nitrogen ion is 1:0.5 ~ 1:0.5 ~ 1, and wherein the mol ratio of fluorine ion and Nitrogen ion is 1:1.
3. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst, is characterized in that, specifically comprise the following steps:
Step 1: five water bismuth nitrates are dissolved in the salpeter solution that mass concentration is 65%, obtain solution A; Phosphate is water-soluble, obtain solution B; Solution A and solution B are mixed and obtains solution C; Ammonium fluoride is added solution C, obtains solution D; By water-soluble to cupric sulfate pentahydrate, pentitol and NaOH, obtain solution E; Solution E is dropwise added in solution D, mixing and stirring, obtain solution F;
Step 2: solution F is transferred to hydrothermal reaction kettle, and be placed in microwave reactor and utilize heating using microwave to 150 ~ 250 DEG C microwave hydrothermal process 1 ~ 3h, room temperature is naturally cooled to after taking-up, by the product centrifugation obtained, deionized water washs 3 times, in 80 DEG C of dry 12h, obtain in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst.
4. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 3, is characterized in that, in step 1, the mass ratio of five water bismuth nitrates and nitric acid is 1:5 ~ 10.
5. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 3, is characterized in that, in step 1, the mass ratio of phosphate and water is 1:5 ~ 10.
6. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 3, is characterized in that, in step 1, in solution C, the mol ratio of bismuth ion and phosphate anion is 1:1.
7. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 3, is characterized in that, in step 1, the mol ratio of bismuth ion and ammonium fluoride is 1:0.5 ~ 1.
8. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 3, is characterized in that, in step 1, the mass ratio of cupric sulfate pentahydrate, pentitol, NaOH and water is 1:0.5 ~ 1.5:3 ~ 6:30 ~ 60.
9. the preparation method of in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst according to claim 3, is characterized in that, in step 1, the mol ratio of bismuth ion and copper ion is 1:0.2 ~ 1.
10. according to the preparation method of the arbitrary described in-situ doping type bismuth phosphate-cuprous oxide composite photo-catalyst of claim 3 ~ 9, 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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