CN109569573B - Preparation method of chromium-doped tunnel-structure strontium potassium niobate nanorod visible-light-driven photocatalyst - Google Patents
Preparation method of chromium-doped tunnel-structure strontium potassium niobate nanorod visible-light-driven photocatalyst Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 81
- MSJIBCNUPFPONA-UHFFFAOYSA-N [K].[Sr] Chemical compound [K].[Sr] MSJIBCNUPFPONA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title abstract description 16
- 239000011651 chromium Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 7
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000001699 photocatalysis Effects 0.000 claims description 22
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 3
- 230000031700 light absorption Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
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- 238000003421 catalytic decomposition reaction Methods 0.000 description 7
- 230000004298 light response Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention provides a preparation method of a chromium-doped tunnel structure strontium potassium niobate nanorod visible-light-induced photocatalyst, which comprises the steps of respectively weighing raw materials according to molar fraction, putting the raw materials into an agate mortar, fully grinding and uniformly mixing to obtain a raw material mixture; weighing potassium chloride according to the mass ratio of the raw material mixture to the molten salt, fully grinding and uniformly mixing to obtain a mixture, roasting the mixture in a muffle furnace, and naturally cooling to room temperature after the reaction is finished; fully washing the molten salt by using deionized water to obtain a pre-product; and (3) drying the pre-product in an oven to obtain the chromium-doped strontium potassium niobate tunnel type nanorod structure visible light catalyst. According to the invention, the strontium sites are replaced by chromium doping, so that the light absorption range of the catalyst can be widened, and the absorption of visible light is realized; meanwhile, based on the tunnel structure, the transmission of tunnel photon-generated carriers can be realized, the effective separation of photon-generated electrons and holes is promoted, the visible light catalytic performance is improved, the oxygen generation by visible light is realized, and the method can be applied to the fields of efficient utilization of solar energy, new energy development and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, relates to a photocatalyst, and particularly relates to a preparation method of a chromium-doped tunnel structure strontium potassium niobate nanorod visible-light-driven photocatalyst.
Background
With the increasing severity of environmental and energy problems, energy exhaustion and environmental pollution become major problems facing human beings, which brings great challenges and opportunities for the research of photocatalytic technology. Since the last 70 s of the century, metal oxide photocatalysts have been considered as the benchmark, Ultraviolet (UV) light reactions (4% in the solar spectrum). However, the active materials of abundant visible light (percentage ≈ 43% in the solar spectrum) have very limited research and development. The design of the visible light response photocatalyst is imperative, and has certain scientific and practical application significance.
Niobium-based oxides, as a class of emerging nanostructured materials, have excellent physical and chemical properties and are widely used in the fields of capacitors, fluorescent materials, photocatalysts, photolytic water catalysts, magnetic domain materials and the like. Strontium potassium niobate tunnel structure photocatalytic material (Sr)2KNb5O15) Have a distorted metal-oxygen polyhedral structure, induce an electric field between dipole moments, and exhibit excellent electron-hole separation and electrostatic transport properties. The effect on the charge flow is thus modified by changing the fine structure of the cation occupancy. Wangping et al firstly carried out photocatalysis on modified bronze niobate with tunnel structure, but strontium potassium niobate is used as photocatalytic material (Sr) with tunnel structure2KNb5O15) The forbidden band width is larger and is 3.19eV, the light absorption threshold is in an ultraviolet region, the visible part in sunlight cannot be fully utilized, and the research on the photocatalytic performance is limited.
At present, few reports exist on ion doping of strontium potassium niobate composite oxide semiconductor photocatalytic materials and research on visible light catalytic performance of the strontium potassium niobate composite oxide semiconductor photocatalytic materials. The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst is prepared by a simple way, successfully widens the light absorption range, and realizes the performance of oxygen production by visible light catalytic decomposition of water.
Disclosure of Invention
In order to overcome the problems in the prior art, the preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst provided by the invention comprises the following steps:
the method comprises the following steps: respectively weighing Cr (NO) according to molar ratio3)39H2O、SrCO3、Nb2O5、K2CO3Putting the raw materials into an agate mortar, fully grinding and uniformly mixing to obtain a raw material mixture;
step two: weighing potassium chloride according to the mass ratio of the raw material mixture to the molten salt, fully grinding and uniformly mixing to obtain a mixture,
step three: placing the mixture prepared in the step two in a muffle furnace for roasting, and naturally cooling to room temperature after the reaction is finished;
step four: fully washing the molten salt by using deionized water to obtain a pre-product;
step five: and (3) drying the pre-product in an oven to obtain the chromium-doped strontium potassium niobate tunnel type nanorod structure visible light catalyst.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, the raw materials of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst in the first step are regulated and controlled to be Sr, Cr is 2-0.8, and 0-1.2.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst provided by the invention, Sr, Cr, is 2:0,
in the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst provided by the invention, Sr and Cr are 1.9:0.1
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst provided by the invention, Sr and Cr are 1.8:0.2
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, Sr and Cr are 1.6 to 0.4.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, Sr and Cr are 1.4 to 0.6.
The preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst according to claim 2, wherein the ratio of Sr to Cr is 1.2: 0.8.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, Sr and Cr are 0.8 to 1.2.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, potassium chloride is called according to the relation that the mass ratio of the raw material mixture to the molten salt is 1: 2.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, the mixture prepared in the second step is placed in a muffle furnace to be roasted for 4 hours.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst, the drying time in an oven is 80 ℃ for 6-12 hours.
Compared with the prior art, the invention has the beneficial effects that: the chromium-doped strontium potassium niobate tunnel type nanorod structure visible light catalyst prepared by the invention has high photocatalytic activity under visible light, and particularly has Sr activity in oxygen generation1.6Cr0.4KNb5O15The catalytic activity is optimal. Chromium-doped potassium strontium niobate tunnel-type nanorod structure Sr with proper concentration2KNb5O15The visible light photocatalytic oxygen generation device can successfully widen the light absorption range, reduce the forbidden band width, have visible light response, realize the performance of oxygen generation by visible light catalytic decomposition of water, promote the effective separation of photon-generated carriers and improve the visible light catalytic performance of the photon-generated carriers. In conclusion, the preparation method of the chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst is simple and feasible in process, the chromium doping concentration is regulated and controlled, the amount of substituted strontium site lattice sites is changed, the light absorption range can be widened, the forbidden bandwidth is reduced, the visible light response is realized, the performance of oxygen production by visible light catalytic decomposition of water is realized, and the chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst can be applied to the fields of efficient utilization of solar energy, new energy development and the like.
Drawings
FIG. 1 is an X-ray diffraction diagram of a chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst in an embodiment of the present invention;
fig. 2a is a graph showing an ultraviolet-visible diffuse reflection spectrum of a chromium-doped strontium potassium niobate tunnel-type nanorod structure visible light catalyst material with a molar ratio of Sr to Cr of 2.0-0.8: 0-1.2 in an embodiment of the present invention.
FIG. 2b is a graph showing the performance of catalytic decomposition of water under visible light irradiation (>420nm) for producing oxygen by using the chromium-doped strontium potassium niobate tunnel nanorod structure material with the molar ratio of Sr to Cr being 2.0-0.8: 0-0.8 in the example of the invention-time curve.
Fig. 3a is an ultraviolet-visible diffuse reflection spectrum of the chromium-doped strontium potassium niobate tunnel-type nanorod structure visible light catalyst material with a molar ratio of Sr to Cr of 2.0-0.8: 0-1.2 in the embodiment of the present invention. Fig. 3b is an ultraviolet-visible diffuse reflection spectrum of the chromium-doped strontium potassium niobate tunnel-type nanorod structure visible light catalyst material with a molar ratio of Sr: Cr ═ 2:0 and Sr: Cr ═ 1.6:0.4 in the example of the invention, and a forbidden bandwidth of the sample.
Fig. 4 is an SEM of the chromium-doped potassium strontium niobate-tunneling nanorod structure visible light catalyst material prepared in examples one to seven.
FIG. 5 shows Sr prepared by the method of the present invention1.6Cr0.4KNb5O15STEM Mapping of the tunneling nanorod structure visible light catalyst material.
FIG. 6 is a graph of performance of catalytic decomposition of water under visible light irradiation (>420nm) of a chromium-doped strontium potassium niobate tunnel-type nanorod structure material with a molar ratio of Sr to Cr of 2.0-1.2: 0-0.8 in an embodiment of the invention, and the performance is plotted versus time.
Detailed Description
The preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst provided by the invention is described in more detail in the following with reference to schematic diagrams, wherein preferred embodiments of the invention are shown, and it should be understood that those skilled in the art can modify the invention described herein, and still achieve the advantageous effects of the invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.
The invention provides a preparation method of a chromium-doped potassium strontium niobate tunnel type nanorod structure visible light catalyst, which comprises the following steps:
step one, respectively weighing Cr (NO) according to molar ratio3)3·9H2O、SrCO3、Nb2O5、K2CO3Putting the raw materials into an agate mortar, regulating and controlling the Sr and Cr to be 2.0-0.8: 0-1.2, fully grinding and uniformly mixing to obtain a raw material mixture;
step two, weighing potassium chloride according to the mass ratio of the raw material mixture to the molten salt of 1:2, fully grinding and uniformly mixing to obtain a mixture;
thirdly, placing the mixture into a corundum crucible, placing the corundum crucible into a muffle furnace at 850 ℃ for roasting for 4 hours, and naturally cooling to room temperature after the reaction is finished;
step four, fully washing the molten salt in the solution by using deionized water to obtain a pre-product;
and fifthly, drying the pre-product in an oven at 80 ℃ for 6-12 hours to obtain the chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst.
In the preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst provided by the invention, the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst also has the following characteristics: wherein in the first step, when Cr: sr is 0-0.666: 1, the chromium-doped strontium potassium niobate tunnel nanorod structure visible light photocatalyst does not undergo phase change, the specific tunnel structure characteristics of the chromium-doped strontium potassium niobate tunnel nanorod structure visible light photocatalyst are retained, and the light absorption range is successfully widened; when the ratio of Cr: sr is 0.666 to 1.5: 1, the chromium-doped strontium potassium niobate tunnel nanorod structure visible light photocatalyst undergoes phase change to generate SrNb6O16The impurity phase exceeds the tolerance of chromium doped crystal lattice, and the original tunnel structure is damaged.
The preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst provided by the invention has the following characteristics: wherein in the first step, Cr: sr is 0.25, which is the optimum doping concentration.
In the preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst provided by the invention, the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst also has the following characteristics: the mass ratio of the raw material mixture to the molten salt is 1: 2.
The invention also provides a chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst prepared by the method for preparing oxygen by visible light catalysis.
< example one >
Step one, respectively weighing 0mol (0g) of Cr (NO)3)39H2O、0.010mol(1.4763g)SrCO3、0.0125mol(3.3226g)Nb2O5、0.0025mol(0.3455g)K2CO3Mixing and grinding the solid powder uniformly to obtain a raw material mixture;
secondly, weighing KCl in a raw material mixture ratio of molten salt to 1:2 in parts by weight, mixing and grinding uniformly again to prepare a mixture;
step three, placing the mixture in a muffle furnace for roasting for 4 hours, and naturally cooling to room temperature after the reaction is finished to obtain a pre-product;
step four, fully washing the pre-product by using deionized water;
and fifthly, drying the pre-product in an oven at 80 ℃ for 6-12 hours to obtain the chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst.
< example two >
The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst comprises the following specific steps: this example is essentially the same as example 1, except that Cr (NO) is present in step one3)39H2O and SrCO3The molar ratios were 0.0005mol (0.2001g) and 0.0095mol (1.4024g) respectively
< example three >
The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst comprises the following specific steps: this example is essentially the same as example 1, except that Cr (NO) is present in step one3)39H2O and SrCO3The molar ratios were 0.001mol (0.4005g) and 0.0090mol (1.3287g) respectively
< example four >
The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst comprises the following specific steps: this example is essentially the same as example 1, except that Cr (NO) is present in step one3)39H2O and SrCO3The molar ratios were 0.002mol (0.8009g) and 0.0080mol (1.1810g)
< example five >
The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst comprises the following specific steps: this example is essentially the same as example 1, except that Cr (NO) is present in step one3)39H2O and SrCO3The molar ratios were 0.003mol (1.20051g) and 0.007mol (1.0334g)
< example six >
The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst comprises the following specific steps: this example is essentially the same as example 1, except that Cr (NO) is present in step one3)39H2O and SrCO3The molar ratios are respectively 0.004mol (1.6006g) and 0.006mol (0.8858g)
< example seven >
The chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst comprises the following specific steps: this example is essentially the same as example 1, except that Cr (NO) is present in step one3)3·9H2O and SrCO3The molar ratios are respectively 0.006mol (2.4009g) and 0.004mol (0.5905g)
FIG. 1 is an X-ray diffraction diagram of a chromium-doped strontium potassium niobate-tunneling nanorod structure visible light catalyst in an embodiment of the present invention. As shown in fig. 1, in the second embodiment, the third embodiment, the fourth embodiment, the fifth embodiment and the sixth embodiment, the chromium-doped strontium potassium niobate tunnel-type nanorod structure visible light photocatalyst does not undergo phase transition, the doping of Cr ions causes the XRD peak of the sample to slightly shift right, which conforms to the law of bragg equation, and thus, the Cr ions enter the lattice sites of Sr, and the phase transition occurs in the seventh embodiment, which results in the generation of the secondary phase SrNb6O16
FIG. 2(a) shows Sr produced by the method of the present invention2KNb5O15、Sr1.6Cr0.4KNb5O15The Raman spectrum (Raman) of the visible-light-driven photocatalyst material with the tunnel-type nanorod structure is shown in fig. 2(a), and the peaks at the 290370650 positions corresponding to the Raman spectrum characteristic peaks of the sample doped with Cr are all strengthened. FIG. 2(b) shows Sr prepared by the method of the present invention2KNb5O15、Sr1.6Cr0.4KNb5O15X-ray photoelectron spectroscopy (XPS) of the visible-light-induced photocatalyst material with the tunnel-type nanorod structure. FIG. 2(b) XPS test result shows Sr2KNb5O15、Sr1.6Cr0.4KNb5O15Similar XP spectra are shown, clear photoelectron peaks can be seen to have Sr, K, Nb and O as the main constituent elements, and Cr is detected in Cr-doped samples, indicating that Cr ions are successfully doped into the crystal lattice of the samples.
Fig. 3(a) is an ultraviolet-visible diffuse reflection spectrum of a chromium-doped strontium potassium niobate tunnel-type nanorod structure visible light catalyst material with a molar ratio of Sr to Cr of 2.0-0.8: 0-1.2 in an embodiment of the present invention. Fig. 3(b) is an ultraviolet-visible diffuse reflection spectrum of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible-light-induced photocatalyst material with a molar ratio of Sr: Cr ═ 2:0 and Sr: Cr ═ 1.6:0.4 in the example of the invention, and a forbidden bandwidth of the sample.
As shown in fig. 3, it can be seen that the visible light catalyst materials of the chromium-doped strontium potassium niobate tunnel nanorod structure prepared in the second to seventh embodiments of the present invention have a broadened light absorption range with doping, the forbidden bandwidths of the visible light catalyst materials of the chromium-doped strontium potassium niobate tunnel nanorod structure with molar ratios of Sr to Cr 2:0 and Sr to Cr 1.6 to 0.4 in the embodiments are 3.19eV and 2.62eV, respectively, after chromium doping, the sample forbidden bandwidth is reduced, and the visible light catalyst materials have visible light response, improve quantum conversion efficiency, and implement a photocatalytic reaction under visible light conditions.
As shown in fig. 4, an SEM of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst material prepared in embodiments one to seven of the present invention.
After chromium doping, the specific rod-shaped structure of the nanorod is not changed, the growth of the nanorod is well regulated, and the nanorod after chromium doping is more uniform in size, which indicates that the growth of the nanorod can be regulated by chromium doping.
FIG. 5 shows Sr prepared by the method of the present invention1.6Cr0.4KNb5O15STEM Mapping of the tunneling nanorod structure visible light catalyst material. As can be seen from FIG. (a), Sr1.6Cr0.4KNb5O15The sample is a rod-like structure, and it can be seen from the graphs (b), (c), (d), (e) and (f) that the corresponding O, K, Cr, Sr and Nb elements are present in the nanorods.
FIG. 6 is a graph of performance of catalytic decomposition of water under visible light irradiation (>420nm) of a chromium-doped strontium potassium niobate tunnel-type nanorod structure material with a molar ratio of Sr to Cr of 2.0-1.2: 0-0.8 in an embodiment of the invention, and the performance is plotted versus time.
As shown in fig. 6, the chromium-doped strontium potassium niobate tunnel nanorod structure materials prepared in the first to sixth examples were subjected to a visible light irradiation (>420nm) catalytic decomposition aqueous performance test, and 30mg of the chromium-doped strontium potassium niobate tunnel nanorod structure visible light catalyst materials prepared in the first to sixth examples were added to 30mL of deionized water under a 500W medium pressure mercury lamp (with a filter to cut off ultraviolet light of <420 nm). As can be seen from the figure, the sample without doping chromium does not have visible light photocatalytic oxygen production, the prepared chromium-doped strontium potassium niobate tunnel type nanorod structure visible light photocatalyst realizes catalytic oxygen production performance under visible light conditions, and the oxygen production performance has a tendency of increasing first and then decreasing with the increase of chromium doping concentration, wherein when Sr: Cr is 1.6:0.4, that is, the chromium-doped strontium potassium niobate tunnel type nanorod structure material prepared in the fourth embodiment has the best visible light photocatalytic oxygen production effect, has visible light response capability, and realizes photocatalytic water decomposition oxygen production under visible light conditions.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a chromium-doped strontium potassium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen is characterized by comprising the following steps:
the method comprises the following steps: respectively weighing Cr (NO) according to molar ratio3)3•9H2O、SrCO3、Nb2O5、K2CO3Putting the raw materials into an agate mortar, fully grinding and uniformly mixing to obtain the productA mixture of raw materials;
step two: weighing potassium chloride according to the mass ratio of the raw material mixture to the molten salt, fully grinding and uniformly mixing to obtain a mixture,
step three: placing the mixture prepared in the step two in a muffle furnace for roasting, and naturally cooling to room temperature after the reaction is finished;
step four: fully washing the molten salt by using deionized water to obtain a pre-product;
step five: drying the pre-product in an oven to obtain the chromium-doped strontium potassium niobate tunnel type nanorod structure visible light catalyst; wherein chromium replaces the lattice site of strontium;
the raw materials in the first step are regulated, wherein Cr is = 2-0.8: 0-1.2; the chromium content is different from 0;
and weighing potassium chloride according to the mass ratio of the raw material mixture to the molten salt of 1: 2.
2. The preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein Sr: Cr =1.9: 0.1.
3. The preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein Sr: Cr =1.8: 0.2.
4. The preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein Sr: Cr =1.6: 0.4.
5. The preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein Sr: Cr =1.4: 0.6.
6. The preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein Sr: Cr =1.2: 0.8.
7. The preparation method of the chromium-doped potassium strontium niobate tunnel-type nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein Sr: Cr =0.8: 1.2.
8. The preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst for photocatalytic decomposition of water to produce oxygen according to claim 1, wherein the mixture prepared in the second step is placed in a muffle furnace to be calcined for 4 hours.
9. The preparation method of the chromium-doped potassium strontium niobate tunnel nanorod structure visible light catalyst for photocatalytic water decomposition and oxygen production according to claim 1, wherein the drying in an oven is 80 ℃ for 6-12 hours.
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