CN111468133A - Preparation method of potassium niobate/α -ferric oxide heterogeneous photocatalyst - Google Patents
Preparation method of potassium niobate/α -ferric oxide heterogeneous photocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910003334 KNbO3 Inorganic materials 0.000 claims abstract description 79
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 21
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
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- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 claims 7
- 229910000859 α-Fe Inorganic materials 0.000 claims 7
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 7
- 238000001782 photodegradation Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
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Abstract
The invention discloses a preparation method of a potassium niobate/α -ferric oxide heterogeneous photocatalyst, which comprises the steps of firstly preparing KNbO3(ii) a Then KNbO3Adding the powder to FeCl3·6H2O and Na2SO4Adding glacial acetic acid into the aqueous solution, uniformly stirring, adding the mixture into a reaction kettle, carrying out hydrothermal reaction, cooling, washing and drying the reaction product, and finally calcining to obtain KNbO3/α‑Fe2O3A heterogeneous photocatalyst. The preparation method has the advantages of simple preparation process, low reaction temperature, short reaction time and low material cost, is suitable for industrial production, and the KNbO obtained by the method3/α‑Fe2O3The heterogeneous photocatalyst has many active sites, high separation efficiency of photon-generated carriers and excellent performance of photocatalytic degradation of dyes.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a preparation method of a potassium niobate/α -ferric oxide heterogeneous photocatalyst.
Background
First use of TiO by Japanese scientists since the last 70 s2Since the photocatalytic material is successfully used for realizing the photodecomposition of water, the semiconductor photocatalytic technology attracts more and more attention of domestic and foreign scientists. Through a photocatalysis technology, solar energy can be successfully converted into chemical energy, such as organic fuels like hydrogen prepared by photocatalytic water decomposition and carbon dioxide reduced by photocatalysis. Besides the application in the energy field, the photocatalysis technology can also be applied in the environmental fields of sewage treatment, indoor air purification and the like. Therefore, the photocatalytic technology is considered to be a green technology which has great development prospect and successfully utilizes solar energy. Although having a wide application prospect, the large-scale industrial application of the photocatalytic technology still faces a great challenge, and the low solar energy conversion efficiency is a key factor for restricting the photocatalytic technology from being practical.
The spontaneous polarization field in the ferroelectric material is proved to be capable of effectively driving the separation of photo-generated charges, inhibiting the recombination among the photo-generated charges and improving the photocatalytic efficiency, and is receiving more and more attention of research workers. Ferroelectric KNbO in recent years3Because of their typical ferroelectric properties, crystals have been successfully used as photocatalysts for the degradation of organic dyes, photolysis water and photoreduction of carbon dioxide. However, the forbidden band width is large (3.2 eV), and only visible light can be absorbed, so that visible light in a solar spectrum cannot be fully utilized, and meanwhile, the separation efficiency of internal photo-generated carriers needs to be further improved.
Disclosure of Invention
To overcome ferroelectric KNbO3The invention provides a method for preparing potassium niobate/α -ferric oxide heterogeneous photocatalyst, and the invention constructs KNbO3/α-Fe2O3Heterojunction, using α -Fe while promoting separation of photogenerated carriers2O3Good response to visible light, expanded spectral absorption range of photocatalyst, simple preparation process and prepared KNbO3/α-Fe2O3Heterogeneous photocatalyst with high performance of photodegrading organic dye and photocatalytic effectFar superior to pure phase KNbO3And α -Fe2O3。
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a potassium niobate/α -ferric oxide heterogeneous photocatalyst comprises the following steps:
the method comprises the following steps: preparation of KNbO by hydrothermal reaction3Powder;
step two: KNbO obtained in the step one3Adding the powder to FeCl3·6H2O and Na2SO4Adding glacial acetic acid into the aqueous solution, uniformly stirring, carrying out hydrothermal reaction, cooling, washing and drying the reaction product, and finally calcining to obtain KNbO3/α-Fe2O3A heterogeneous photocatalyst.
Further, KNbO in the step one3The preparation method of the powder comprises the following steps: dissolving KOH in deionized water, adding niobium powder, fully stirring on a magnetic stirrer, then transferring to a polytetrafluoroethylene lined reaction kettle, carrying out hydrothermal reaction for 12 hours at 150 ℃, fully washing the obtained product with deionized water until the pH value is neutral, and finally drying for 12 hours at 60 ℃ to obtain KNbO3And (3) powder.
Further, KOH was dissolved in deionized water to obtain a KOH solution with a concentration of 15 mol/L, and the mass of KOH and the mass of niobium powder were 12.624: 0.874.
Further, FeCl in step two3·6H2O and Na2SO4Is 1: 1.
Further, FeCl in step two3·6H2O and KNbO3The molar ratio of (0.4-10): 1.
Further, glacial acetic acid was added in step two to make the concentration in the solution 0.06 mol/L.
Furthermore, the hydrothermal reaction temperature in the second step is 120 ℃, and the hydrothermal reaction time is 8 h.
Furthermore, the calcination temperature in the second step is 500 ℃, and the calcination time is 2 h.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a two-step hydrothermal method to prepare samples, has low temperature and short time of hydrothermal reaction, is suitable for industrialized production, and adopts the method that ferroelectric KNbO is used3α -Fe is introduced to the surface of the powder2O3And construct KNbO3/α-Fe2O3The heterojunction utilizes the built-in electric field of the heterojunction to promote the separation of photon-generated carriers and inhibit the recombination of electrons and holes on the one hand and utilizes the narrow band gap α -Fe on the other hand2O3Good response to visible light, expanded spectral absorption range of photocatalyst and finally obtained KNbO3/α-Fe2O3The heterojunction photocatalyst has high-efficiency performance of photodegrading organic pollutants, and the photodegrading efficiency of the heterojunction photocatalyst is far higher than that of pure-phase KNbO3And α -Fe2O3The heterojunction photocatalyst is expected to be applied to the fields of sewage treatment and the like.
Drawings
FIG. 1 shows different KNbO3With FeCl3·6H2XRD pattern of heterogeneous photocatalyst prepared with molar ratio of O; (a) KNbO3；(b)KNbO3/α-Fe2O3-0.4；(c)KNbO3/α-Fe2O3-2；(d)KNbO3/α-Fe2O3-10；
FIG. 2 shows different KNbO3With FeCl3·6H2An ultraviolet-diffuse reflection absorption spectrogram of the heterogeneous photocatalyst prepared by the molar ratio of O; (a) KNbO3；(b)α-Fe2O3；(c)KNbO3/α-Fe2O3-0.4；(d))KNbO3/α-Fe2O3-2；(e)KNbO3/α-Fe2O3-10；
FIG. 3 shows different KNbO3With FeCl3·6H2Scanning photo picture of heterogeneous photocatalyst prepared by molar ratio of O (a) α -Fe2O3；(b)KNbO3/α-Fe2O3-0.4；(c)KNbO3/α-Fe2O3-2；(d)KNbO3/α-Fe2O3-10；
FIG. 4 shows different KNbO3With FeCl3·6H2A rhodamine B degradation curve of the heterogeneous photocatalyst prepared by the molar ratio of O; (a) KNbO3；(b)α-Fe2O3；(c)KNbO3/α-Fe2O3-0.4；(d)KNbO3/α-Fe2O3-2；(e)KNbO3/α-Fe2O3-10；
FIG. 5 shows different KNbO3With FeCl3·6H2Linear fitting of the photodegradation rate of the heterogeneous photocatalyst prepared by the molar ratio of O; (a) KNbO3；(b)α-Fe2O3；(c)KNbO3/α-Fe2O3-0.4；(d)KNbO3/α-Fe2O3-2；(e)KNbO3/α-Fe2O3-10；
FIG. 6 is KNbO3/α-Fe2O3The photocatalytic mechanism of the heterojunction is schematically shown.
Detailed Description
Embodiments of the invention are described in further detail below:
KNbO3/α-Fe2O3The preparation method of the heterogeneous photocatalyst comprises the following steps:
the method comprises the following steps: preparation of KNbO3: 12.624g of KOH was dissolved in 15ml of deionized water, then 0.874g of niobium powder was added, and the mixture was stirred sufficiently for 30min on a magnetic stirrer, and then transferred to a 50ml polytetrafluoroethylene-lined reaction vessel and subjected to hydrothermal reaction at 150 ℃ for 12 h. Fully washing the obtained product with deionized water until the pH value is neutral, and finally drying the product for 12 hours at 60 ℃ to obtain KNbO3Powder;
step two: mixing the 0.2g KNbO obtained in the step one3Adding the powder to FeCl3·6H2O and Na2SO4In 25ml of an aqueous solution, FeCl was held3·6H2O and Na2SO4With a molar ratio of 1:1, while adjusting FeCl3·6H2O and KNbO3In a molar ratio of 0.4-10: 1, to obtain a series of different α -Fe2O3Mass fraction heterojunction photocatalyst(ii) a Adding 1.5ml of glacial acetic acid into the solution, and stirring for 30 minutes; stirring uniformly, adding into a 50ml reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling, washing and drying the reaction product, and calcining at 500 ℃ for 2h to obtain KNbO3/α-Fe2O3A heterogeneous photocatalyst.
The present invention is described in further detail below with reference to examples:
comparative example 1
Hydrothermal method for preparing KNbO3The method comprises the following specific steps:
the method comprises the following steps: 12.624g of KOH was weighed and dissolved in 15ml of deionized water;
step two: 0.874g of niobium powder is added into the solution, and the solution is fully stirred for 30min on a magnetic stirrer;
step three: the resulting solution was transferred to a 50ml teflon-lined reaction vessel and subjected to hydrothermal reaction at 150 ℃ for 12 hours.
Step four: after the reaction is finished and cooled, the obtained product is fully washed by deionized water until the pH value is neutral, and finally dried for 12 hours at the temperature of 60 ℃ to obtain KNbO3And (3) powder.
Comparative example 2
Pure α -Fe prepared by hydrothermal method2O3The method comprises the following specific steps:
the method comprises the following steps: weighing 3g FeCl3·6H2Dissolving O in 25ml deionized water;
step two: to the above solution was added 1.578g of Na2SO4To make FeCl3·6H2O and Na2SO4The molar ratio of (1: 1) is fully stirred on a magnetic stirrer;
step three: adding 1.5ml of glacial acetic acid into the solution, and stirring for 30 minutes;
step four: the resulting solution was transferred to a 50ml teflon lined reactor and subjected to hydrothermal reaction at 120 ℃ for 8 h.
Step four: after the reaction is finished and cooled, fully washing the obtained product by using deionized water until the pH value is neutral, and finally drying the product for 12 hours at the temperature of 60 ℃ for later use;
step five, putting the obtained powder into a crucible, and calcining for 2 hours at 500 ℃ to obtain α -Fe2O3。
Example 1
Preparation of KNbO by two-step hydrothermal method3/α-Fe2O3-x, wherein x is 0.4 and x is FeCl3·6H2O and KNbO3The specific steps are as follows:
the method comprises the following steps: preparation of KNbO3: KOH is dissolved in deionized water, then niobium powder is added, the mixture is fully stirred on a magnetic stirrer, and then the mixture is transferred to a lining reaction kettle made of 50ml of polytetrafluoroethylene to carry out hydrothermal reaction for 12 hours at the temperature of 150 ℃. Fully washing the obtained product with deionized water until the pH value is neutral, and finally drying the product for 12 hours at 60 ℃ to obtain KNbO3And (3) powder.
Step two: mixing the 0.2g KNbO obtained in the step one3Adding the powder to FeCl3·6H2O and Na2SO4In 25ml of deionized water, FeCl was held3·6H2O and Na2SO4With a molar ratio of 1:1, while adjusting FeCl3·6H2O and KNbO3In a molar ratio of 0.4: 1; adding 1.5ml of glacial acetic acid into the solution, and stirring for 30 minutes; stirring uniformly, adding into a 50ml reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling, washing and drying the reaction product, and calcining at 500 ℃ for 2h to obtain KNbO3/α-Fe2O3-0.4 heterogeneous photocatalyst.
Example 2
Preparation of KNbO by two-step hydrothermal method3/α-Fe2O3-x, wherein x is 2 and x is FeCl3·6H2O and KNbO3The specific steps are as follows:
the method comprises the following steps: preparation of KNbO3: KOH is dissolved in deionized water, then niobium powder is added, the mixture is fully stirred on a magnetic stirrer, and then the mixture is transferred to a lining reaction kettle made of 50ml of polytetrafluoroethylene to carry out hydrothermal reaction for 12 hours at the temperature of 150 ℃. The resulting product was de-ionizedFully washing with water until the pH value is neutral, and finally drying at 60 ℃ for 12 hours to obtain KNbO3And (3) powder.
Step two: mixing the 0.2g KNbO obtained in the step one3Adding the powder to FeCl3·6H2O and Na2SO4In 25ml of deionized water, FeCl was held3·6H2O and Na2SO4With a molar ratio of 1:1, while adjusting FeCl3·6H2O and KNbO3In a molar ratio of 2: 1; adding 1.5ml of glacial acetic acid into the solution, and stirring for 30 minutes; stirring uniformly, adding into a 50ml reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling, washing and drying the reaction product, and calcining at 500 ℃ for 2h to obtain KNbO3/α-Fe2O3-2 heterogeneous photocatalyst.
Example 3
Preparation of KNbO by two-step hydrothermal method3/α-Fe2O3-x, wherein x is 10 and x is FeCl3·6H2O and KNbO3The specific steps are as follows:
the method comprises the following steps: preparation of KNbO3: KOH is dissolved in deionized water, then niobium powder is added, the mixture is fully stirred on a magnetic stirrer, and then the mixture is transferred to a lining reaction kettle made of 50ml of polytetrafluoroethylene to carry out hydrothermal reaction for 12 hours at the temperature of 150 ℃. Fully washing the obtained product with deionized water until the pH value is neutral, and finally drying the product for 12 hours at 60 ℃ to obtain KNbO3And (3) powder.
Step two: mixing the 0.2g KNbO obtained in the step one3Adding the powder to FeCl3·6H2O and Na2SO4In 25ml of deionized water, FeCl was held3·6H2O and Na2SO4With a molar ratio of 1:1, while adjusting FeCl3·6H2O and KNbO3In a molar ratio of 10: 1; adding 1.5ml of glacial acetic acid into the solution, and stirring for 30 minutes; stirring uniformly, adding into a 50ml reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling, washing and drying the reaction product, and calcining at 500 ℃ for 2h to obtain KNbO3/α-Fe2O3-10 heterogeneous photocatalysts.
As can be seen from FIG. 1, FeCl is added with the preparation process3·6H2O and KNbO3Of α -Fe2O3At KNbO3/α-Fe2O3The mass fraction in the heterojunction increases with it, at KNbO3/α-Fe2O310 Simultaneous observation of membership to KNbO3And α -Fe2O3FIG. 2 demonstrates a diffraction peak with α -Fe2O3Increase in mass fraction, KNbO3/α-Fe2O3The visible light absorption capability of the heterojunction photocatalyst is significantly improved, while the scanning photograph of fig. 3 also demonstrates α -Fe2O3Second phase growth in KNbO3Cubic surfaces and heterostructures, and α -Fe was observed2O3At KNbO3The surfaces of the cubic blocks are not obviously agglomerated and are in a rough form of hairy antler, so that the photocatalyst can provide more reaction active sites and improve the photocatalytic efficiency, and the effect is attributed to the fact that the weak acid glacial acetic acid is added in the preparation process and can control Fe3+Slow hydrolysis occurs. As shown in FIG. 4, KNbO can be found by a test of degrading the organic dye rhodamine B under simulated sunlight3/α-Fe2O3-2 and KNbO3/α-Fe2O3-10 heterojunction photocatalysts show advantages over pure KNbO3And α -Fe2O3The photodegradation efficiency of, wherein KNbO3/α-Fe2O3The photodegradability of-10 is optimal. Calculation of photodegradation rates by kinetic modeling, as shown in FIG. 5 and Table 1, it was found that KNbO3/α-Fe2O3The degradation rate of-10 is KNbO3273.5 times of that of pure α -Fe2O33.3 times of that of the dye, the percentage of degradation of the dye is close to 100% under 15 minutes of light.
TABLE 1 photodegradation rate tables of different photocatalysts
This is well documented in KNbO3Surface loading of α -Fe2O3The two forms a heterojunction structure which is an effective strategy for developing a high-efficiency photocatalyst, and one aspect utilizes α -Fe2O3The strong absorption of visible light widens the spectrum absorption range of the photocatalyst, and on the other hand, the built-in electric field of the heterostructure is utilized to promote the migration of photon-generated carriers, and electrons are removed from KNbO3Transfer of conduction band to α -Fe2O3Conduction band of (5), hole from α -Fe2O3Valence band transfer to KNbO3Thereby realizing effective separation of electrons and holes, inhibiting electron-hole recombination and improving the photocatalytic efficiency.
KNbO prepared by the invention3/α-Fe2O3The heterogeneous photocatalyst has simple preparation process, low temperature of hydrothermal reaction and short time, is suitable for industrial production, and the prepared KNbO3/α-Fe2O3The heterogeneous photocatalyst has many active sites, high separation efficiency of photon-generated carriers, high performance of photodegradation of organic dyes and is expected to be applied to the fields of sewage treatment and the like.
Claims (8)
1. A preparation method of a potassium niobate/α -ferric oxide heterogeneous photocatalyst is characterized by comprising the following steps:
the method comprises the following steps: preparation of KNbO by hydrothermal reaction3Powder;
step two: KNbO obtained in the step one3Adding the powder to FeCl3·6H2O and Na2SO4Adding glacial acetic acid into the aqueous solution, uniformly stirring, carrying out hydrothermal reaction, cooling, washing and drying the reaction product, and finally calcining to obtain KNbO3/α-Fe2O3A heterogeneous photocatalyst.
2. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 1, wherein KNbO in the first step3The preparation method of the powder comprises the following steps: dissolving KOH in deionized water, adding niobium powder, fully stirring on a magnetic stirrer, then transferring to a polytetrafluoroethylene lined reaction kettle, carrying out hydrothermal reaction for 12 hours at 150 ℃, fully washing the obtained product with deionized water until the pH value is neutral, and finally drying for 12 hours at 60 ℃ to obtain KNbO3And (3) powder.
3. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 2, wherein KOH is dissolved in deionized water to obtain a KOH solution with a concentration of 15 mol/L, and the mass of KOH and the mass of niobium powder are 12.624: 0.874.
4. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 1, wherein FeCl is added in the second step3·6H2O and Na2SO4Is 1: 1.
5. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 1, wherein FeCl in step two3·6H2O and KNbO3The molar ratio of (0.4-10): 1.
6. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 1, wherein glacial acetic acid is added in the second step to make its concentration in the solution 0.06 mol/L.
7. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 1, wherein the hydrothermal reaction temperature in step two is 120 ℃ and the hydrothermal reaction time is 8 h.
8. The method for preparing potassium niobate/α -iron oxide heterogeneous photocatalyst according to claim 1, wherein the calcination temperature in step two is 500 ℃ and the calcination time is 2 h.
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