CN1311902C - Process for preparing potassium columbate K4Nb6O17 film - Google Patents
Process for preparing potassium columbate K4Nb6O17 film Download PDFInfo
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- CN1311902C CN1311902C CNB2005101239773A CN200510123977A CN1311902C CN 1311902 C CN1311902 C CN 1311902C CN B2005101239773 A CNB2005101239773 A CN B2005101239773A CN 200510123977 A CN200510123977 A CN 200510123977A CN 1311902 C CN1311902 C CN 1311902C
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Abstract
The present invention belongs to the field of functional ceramics. At present, the preparation of niobate films needs niobium alkoxide as raw material and requires accurate control, long time and high cost. The method of the present invention comprises the steps: weighing hydrated niobium oxide and citric acid according to Nb2O5: citric acid=1:10-20, adding the material to ethylene glycol monomethyl ether, adding peroxy water and channeling back for 4 to 8 hours at 70 to 90 DEG C to form a niobium contained solution; dissolving potassium acetate in acetic acid solution to obtain a potassium contained solution; mixing the two solutions according to K: Nb=4.0 to 4.2:6, in a concentration of 0.10 to 0.15m for 30 to 45 minutes and at 70 to 90 DEG C to form precursor liquid; aging for 24 to 48 hours, spin coating to form a film at the spinning speed of 3000 to 4000 round/min for 30 to 45s, drying, pre-treating for 10 to 15 minutes at 350 to 400 DEG C, repeating the film-forming, drying and pretreatment for 3 to 4 times to obtain a film 80 to 100 nm thick, heating to 600 to 700 DEG C at the speed of 10 to 15 DEG C, annealing for 10 to 15 min. The present invention has the advantages of no need of expensive niobium alkoxide, high stability of the precursor liquid, good preferred orientation structure and good potocatalysis water decomposition hydrogen making capability.
Description
Technical field
The present invention relates to a kind of potassium niobate (K with photocatalytic hydrogen production by water decomposition ability
4Nb
6O
17, KN) function ceramics film, its main contents comprise the precursor sol liquid that utilizes the aqua oxidation niobium to prepare potassium niobate thin film, spin-coating method film forming and film heat treatment etc. prepare KN function ceramics film, belong to the specialty films in a kind of new energy materials field.
Background technology
Potassium niobate (K
4N
b6O
17), be a kind of oxide with special layer structure, have good solar energy and semiconductor light-catalyzed reaction hydrogen manufacturing characteristic, aspect the energy and the fuel cell important use is being arranged.For the ease of the regularization of hydrogen producer, the oxide that photocatalysis need be used is fixed on the specific supporter, adopts method for manufacturing thin film to address this problem effectively.At present, the K that is used for photocatalysis hydrogen production
4Nb
6O
17The preparation method of film does not still have patent report.The aqua oxidation niobium that this patent adopts prepares K
4Nb
6O
17The method of film presoma is not used expensive niobium alkoxide, and cost is low, and it is low to have heat treatment temperature, is easy to advantages such as large tracts of land manufacturing.Usually, preparation niobates film is as LiNbO
3, KNbO
3Deng, the alkoxide that adopt niobiums as raw material more: in the method, be the hydrolysis of alkoxide and the separating out of niobium oxide precipitation of avoiding niobium, when preparing film, the hydrolysis rate of necessary strict control niobium alkoxide colloidal sol adds an amount of water at every turn, control suitable acidity, the whole range request of crossing is controlled accurately, and the preparation time is long, and the preparation cost height.
Summary of the invention
The object of the present invention is to provide a kind of preparation potassium niobate (K that does not have niobium alkoxide
4Nb
6O
17) method of film, adopt the aqua oxidation niobium as presoma, need not adopt expensive niobium alkoxide as raw material, only need the chelating-course of dissolution of control aqua oxidation niobium, adds an amount of peroxide water as stabilizing agent, control the stability of aqua oxidation niobium solution.Key is to control the concentration of presoma and the addition of peroxide water.Prepared precursor solution good stability, the resting period is long, as layering hydrolysis phenomenon does not appear in solution after depositing for 3～4 weeks, and precursor solution can be used for the spin-coating film legal system and be equipped with K thus
4Nb
6O
17Film.
The invention provides a kind of potassium niobate K
4Nb
6O
17The preparation method of film is characterized in that, may further comprise the steps:
(1) by mole ratio Nb
2O
5: citric acid=1: (10～20) are weighing aqua oxidation niobium and citric acid respectively, joins in the glycol monoethyl ether solvent, adds Nb again
2O
51～3% peroxide water of mole number, the mixed system of the formation 4～8h that refluxes under 70～90 ℃ temperature all dissolves the aqua oxidation niobium, forms transparent, the stable niobium solution that contains; Simultaneously, potassium acetate (KAc) is dissolved in acetic acid solution, obtains to contain potassium solution;
(2) contain potassium solution and contain niobium solution above-mentioned, by mole ratio K: Nb=(4.0～4.2): 6 ratio is mixed, and the adding glycol monoethyl ether makes K
4Nb
6O
17Concentration reach 0.10～0.15M, be heated to and mixed under 70～90 ℃ 30～45 minutes, form transparent, uniform potassium niobate precursor sol liquid; Before the film forming, this precursor liquid filtered remove behind sediment ageing 24～48h under the condition of sealing;
(3) adopt the spin-coating film thin films, 3000～4000 rev/mins of whirl coating speed, time is 30～45s, dry under 100～120 ℃ temperature then, preliminary treatment is 10～15 minutes under 350 ℃～400 ℃ temperature, through 3～4 above-mentioned film forming-drying-preliminary treatment, after obtaining the film of thickness 80～100nm, rise to 600～700 ℃ temperature again with 10～15 ℃/minute heating rate, annealing in process 10～15min obtains the perfect K of crystallization of the present invention
4Nb
6O
17Film.
Zhi Bei K as stated above
4Nb
6O
17Film has good (040) preferred orientation structure, shows photocatalysis and divides the hydrogen production by water decomposition ability.
Description of drawings
The K that Fig. 1 prepares for the method that provides by the embodiment of the invention 1
4Nb
6O
17Film XRD spectrum.Employed X-ray diffraction equipment is the Advance D8A of Brucker company type X-ray diffractometer, and x-ray source is the Cu target.
Fig. 2 is the AFM shape appearance figure of the film of the method preparation that provides by the embodiment of the invention 1.AFM figure writes down from the Nano scope III type atomic force microscopy instrument that U.S. Veeco company provides.
The K of the method preparation that provides by the embodiment of the invention 1 and embodiment 2 is provided for Fig. 3 and Fig. 4
4Nb
6O
17The photocatalysis hydrogen production curve of film.Used solution medium is that (water: methyl alcohol=2: 1), light source is an xenon lamp, and ordinate is hydrogen output [ml/ (cm for water and methanol mixture
2)], abscissa is light exposure time (min).
The specific embodiment
Further illustrate the substantive distinguishing features and the remarkable advantage of this explanation below by embodiment, the present invention only is confined to the embodiment that stated by no means.
Embodiment 1
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 10, join in the glycol monoethyl ether solvent, add Nb again
2O
52% peroxide water of mole number.The above-mentioned mixed system 4h that refluxes under 80 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.1: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 80 ℃ 30 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.10M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 24h under the condition of sealing.With the precursor liquid spin-coating film, 3000 rev/mins of whirl coating speed, time is 45s, dry under 100 ℃ temperature then, preliminary treatment is 10 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 100nm, rise to 700 ℃ with 15 ℃/minute heating rate again, annealing in process 15min obtains the K of crystallization
4Nb
6O
17Film.Fig. 1, Fig. 2 and Fig. 3 are the K that obtains by described process
4Nb
6O
17XRD figure spectrum, AFM pattern and the photocatalytic hydrogen production by water decomposition curve of film.As seen from the figure, film has good (040) preferred orientation, and film crystal grain is evenly fine and close, and crystallite dimension has the particle of nanoscale about 70-80nm.To obtain the photocatalysis hydrogen production speed of film be 0.0445ml/ (cm in tracing analysis to photocatalysis hydrogen production
2Min), saturated hydrogen manufacturing amount is 14.2ml/cm
2, show good photocatalysis hydrogen production ability.
Embodiment 2
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 20, join in the glycol monoethyl ether solvent, add Nb again
2O
53% peroxide water of mole number.The above-mentioned mixed system 4h that refluxes under 90 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.2: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 70 ℃ 30 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.15M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 36h under the condition of sealing.With the precursor liquid spin-coating film, 3500 rev/mins of whirl coating speed, time is 40s, dry under 100 ℃ temperature then, preliminary treatment is 10 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 100nm, rise to 600 ℃ with 15 ℃/minute heating rate again, annealing in process 10min obtains the K of crystallization
4Nb
6O
17Film.The K of Fig. 4 for obtaining by described process
4Nb
6O
17The photocatalytic hydrogen production by water decomposition curve of film.The photocatalysis hydrogen production speed that this photocatalysis hydrogen production tracing analysis is obtained film is 0.0483ml/ (cm
2Min), saturated hydrogen manufacturing amount is 9.7ml/cm
2, show good photocatalysis hydrogen production ability.
Embodiment 3
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 20, join in the glycol monoethyl ether solvent, add Nb again
2O
51% peroxide water of mole number.The above-mentioned mixed system 8h that refluxes under 70 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.2: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 70 ℃ 30 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.15M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 36h under the condition of sealing.With the precursor liquid spin-coating film, 3500 rev/mins of whirl coating speed, time is 40s, dry under 110 ℃ temperature then, preliminary treatment is 15 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 100nm, rise to 600 ℃ with 15 ℃/minute heating rate again, annealing in process 10min obtains the K of crystallization
4Nb
6O
17Film.
Embodiment 4
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 15, join in the glycol monoethyl ether solvent, add Nb again
2O
52% peroxide water of mole number.The above-mentioned mixed system 4h that refluxes under 90 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.1: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 80 ℃ 45 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.10M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 48h under the condition of sealing.With the precursor liquid spin-coating film, 4000 rev/mins of whirl coating speed, time is 40s, dry under 120 ℃ temperature then, preliminary treatment is 15 minutes under 400 ℃ temperature, after 3 film forming-drying-preliminary treatment, obtain the film of thickness at 80nm, rise to 700 ℃ with 15 ℃/minute heating rate again, annealing in process 20min obtains the K of crystallization
4Nb
6O
17Film.
Embodiment 5
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 15, join in the glycol monoethyl ether solvent, add Nb again
2O
51% peroxide water of mole number.The above-mentioned mixed system 6h that refluxes under 80 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.1: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 80 ℃ 45 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.12M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 36h under the condition of sealing.With the precursor liquid spin-coating film, 3000 rev/mins of whirl coating speed, time is 45s, dry under 100 ℃ temperature then, preliminary treatment is 15 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 100nm, rise to 700 ℃ with 15 ℃/minute heating rate again, annealing in process 15min obtains the K of crystallization
4Nb
6O
17Film.
Embodiment 6
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 15, join in the glycol monoethyl ether solvent, add Nb again
2O
52% peroxide water of mole number.The above-mentioned mixed system 8h that refluxes under 70 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.0: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 70 ℃ 30 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.12M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 48h under the condition of sealing.With the precursor liquid spin-coating film, 3000 rev/mins of whirl coating speed, time is 45s, dry under 110 ℃ temperature then, preliminary treatment is 20 minutes under 350 ℃ temperature, after 3 film forming-drying-preliminary treatment, obtain the film of thickness at 80nm, rise to 600 ℃ with 15 ℃/minute heating rate again, annealing in process 20min obtains the K of crystallization
4Nb
6O
17Film.
Embodiment 7
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 20, join in the glycol monoethyl ether solvent, add Nb again
2O
53% peroxide water of mole number.The above-mentioned mixed system 4h that refluxes under 90 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.2: 6 ratio, join and close in the niobium solution, be heated to and mixed under 70 ℃ 40 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.10M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 36h under the condition of sealing.With the precursor liquid spin-coating film, 4000 rev/mins of whirl coating speed, time is 30s, dry under 120 ℃ temperature then, preliminary treatment is 10 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 90nm, rise to 650 ℃ with 10 ℃/minute heating rate again, annealing in process 20min obtains the K of crystallization
4Nb
6O
17Film.
Embodiment 8
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 10, join in the glycol monoethyl ether solvent, add Nb again
2O
52% peroxide water of mole number.The above-mentioned mixed system 4h that refluxes under 90 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.1: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 70 ℃ 45 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.15M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 36h under the condition of sealing.With the precursor liquid spin-coating film, 4000 rev/mins of whirl coating speed, time is 30s, dry under 120 ℃ temperature then, preliminary treatment is 10 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 100nm, rise to 650 ℃ with 10 ℃/minute heating rate again, annealing in process 15min obtains the K of crystallization
4Nb
6O
17Film.
Embodiment 9
By mole ratio Nb
2O
5: citric acid=respectively measure aqua oxidation niobium and citric acid at 1: 10, join in the glycol monoethyl ether solvent, add Nb again
2O
52% peroxide water of mole number.The above-mentioned mixed system 4h that refluxes under 80 ℃ temperature range forms the transparent niobium solution that contains.With the acetum of potassium acetate (KAc), in mole ratio K: Nb=4.2: 6 ratio, join and contain in the niobium solution, be heated to and mixed under 80 ℃ 30 minutes, form transparent, uniform potassium niobate precursor sol liquid, the concentration of precursor liquid is 0.10M.Before the film forming, precursor liquid filter is removed behind the sediment ageing 24h under the condition of sealing.With the precursor liquid spin-coating film, 3000 rev/mins of whirl coating speed, time is 45s, dry under 100 ℃ temperature then, preliminary treatment is 10 minutes under 400 ℃ temperature, after 4 film forming-drying-preliminary treatment, obtain the film of thickness at 100nm, rise to 650 ℃ with 15 ℃/minute heating rate again, annealing in process 15min obtains the K of crystallization
4Nb
6O
17Film.
The K of the method preparation that provides by various embodiments of the present invention has been provided table 1
4Nb
6O
17The photocatalytic hydrogen production by water decomposition performance parameter of film.
Table 1 is by the K of various embodiments of the present invention provider method preparation
4Nb
6O
17The photocatalysis hydrogen production performance of film
| Embodiment | Saturated hydrogen manufacturing amount (ml/cm 2) | Hydrogen manufacturing speed (ml/cm 2·min) |
| 1 | 14.2 | 0.0445 |
| 2 | 9.7 | 0.0483 |
| 3 | 9.9 | 0.0478 |
| 4 | 13.7 | 0.0445 |
| 5 | 13.6 | 0.0452 |
| 6 | 10.7 | 0.0479 |
| 7 | 10.4 | 0.0478 |
| 8 | 11.8 | 0.0467 |
| 9 | 12.9 | 0.0462 |
Claims (1)
1, a kind of potassium niobate K
4Nb
6O
17The preparation method of film is characterized in that, may further comprise the steps:
1) by mole ratio Nb
2O
5: citric acid=1: 10～20 are weighing aqua oxidation niobium and citric acid respectively, joins in the glycol monoethyl ether solvent, adds Nb again
2O
51～3% peroxide water of mole number, the mixed system of the formation 4～8h that refluxes under 70～90 ℃ temperature all dissolves the aqua oxidation niobium, forms transparent, the stable niobium solution that contains; Simultaneously, potassium acetate is dissolved in acetic acid solution, obtains to contain potassium solution;
2) contain potassium solution and contain niobium solution above-mentioned, mix by the ratio of mole ratio K: Nb=4.0～4.2: 6, the adding glycol monoethyl ether makes K
4Nb
6O
17Concentration reach 0.10～0.15M, be heated to and mixed under 70～90 ℃ 30～45 minutes, form transparent, uniform potassium niobate precursor sol liquid; Before the film forming, this precursor liquid filtered remove behind sediment ageing 24～48h under the condition of sealing;
3) adopt the spin-coating film thin films, 3000～4000 rev/mins of whirl coating speed, time is 30～45s, dry under 100～120 ℃ temperature then, preliminary treatment is 10～15 minutes under 350 ℃～400 ℃ temperature, through 3～4 above-mentioned film forming-drying-preliminary treatment, after obtaining the film of thickness 80～100nm, rise to 600～700 ℃ temperature again with 10～15 ℃/minute heating rate, annealing in process 10～15min obtains the perfect K of crystallization of the present invention
4Nb
6O
17Film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101239773A CN1311902C (en) | 2005-11-25 | 2005-11-25 | Process for preparing potassium columbate K4Nb6O17 film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101239773A CN1311902C (en) | 2005-11-25 | 2005-11-25 | Process for preparing potassium columbate K4Nb6O17 film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN1311902C true CN1311902C (en) | 2007-04-25 |
Family
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|---|---|---|---|
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008096456A1 (en) | 2007-02-08 | 2008-08-14 | Central Japan Railway Company | Photocatalyst thin-film, process for forming photocatalyst thin-film, and product coated with photo thin-film |
| CN102000559B (en) * | 2010-11-18 | 2012-06-27 | 中国海洋石油总公司 | Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst |
| CN102502833B (en) * | 2011-10-27 | 2014-06-18 | 浙江大学 | Method for preparing K3Nb7019 hexagonal sheet in micro-nano structure |
| CN112536024B (en) * | 2019-09-20 | 2023-04-11 | 中国石油化工股份有限公司 | Homogeneous niobium catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003126695A (en) * | 2001-10-22 | 2003-05-07 | National Institute Of Advanced Industrial & Technology | Potassium niobate photocatalyst and manufacturing method therefor |
| CN1559675A (en) * | 2004-02-16 | 2005-01-05 | 武汉理工大学 | Niobium potassium compound oxide photocatalyst and its preparation method |
| CN1597097A (en) * | 2004-08-30 | 2005-03-23 | 南京大学 | Preparation method of high specific surface tantalate and niobate photo catalyst |
-
2005
- 2005-11-25 CN CNB2005101239773A patent/CN1311902C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003126695A (en) * | 2001-10-22 | 2003-05-07 | National Institute Of Advanced Industrial & Technology | Potassium niobate photocatalyst and manufacturing method therefor |
| CN1559675A (en) * | 2004-02-16 | 2005-01-05 | 武汉理工大学 | Niobium potassium compound oxide photocatalyst and its preparation method |
| CN1597097A (en) * | 2004-08-30 | 2005-03-23 | 南京大学 | Preparation method of high specific surface tantalate and niobate photo catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 层状新型纳米复合功能材料研究进展 张莉莉，赵朴素等，化学世界，第10期 2005 * |
| 层状结构金属化合物薄膜的制备及表征 袁坚，陶武刚等，机械工程材料，第28卷第6期 2004 * |
| 层状结构金属化合物薄膜的制备及表征 袁坚，陶武刚等，机械工程材料，第28卷第6期 2004;层状新型纳米复合功能材料研究进展 张莉莉，赵朴素等，化学世界，第10期 2005 * |
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