CN110975859A - Preparation method of novel vanadate photocatalytic material - Google Patents
Preparation method of novel vanadate photocatalytic material Download PDFInfo
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 17
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- -1 vanadate compound Chemical class 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 13
- 239000012071 phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a preparation method of a novel vanadate photocatalytic material, belonging to the technical field of preparation of photocatalytic materials. The preparation method comprises the steps of taking ammonium metavanadate and zirconium oxychloride as raw materials, providing a rare earth element lanthanum by lanthanum nitrate, taking citric acid as a cementing agent, and preparing Zr by adopting a sol-gel-calcination method1‑xLaxV2O7‑x/2Powder, wherein x is 0.01-0.1. The preparation method of the invention prepares the novel vanadate compound by rare earth element doping means and using a sol-gel method. The photocatalysis efficiency of the zirconium vanadate doped with the rare earth element lanthanum is improved, and compared with the undoped pure vanadate, the degradation capability of the zirconium vanadate to pollutants is obviously improved.
Description
Technical Field
The invention relates to the technical field of preparation of photocatalytic materials, in particular to a preparation method of a novel vanadate photocatalytic material.
Background
ZrV as a new photocatalytic material2O7Shows specific photocatalytic performance on degradation of different dyes, and shows that ZrV2O7Has important research value in the aspect of photocatalysis. The photocatalysis technology has important significance in solving global energy and environmental crisis. They have been used in many fields like waste water treatment, air purification, water decomposition to produce hydrogen and other environmental problems.
At ZrV2O7In the preparation of (1), a variety of methods have been reported, for example ZrO2And V2O5Solid-phase reaction at high temperature, coprecipitation, and hydrothermal methods. These methods all involve complicated synthetic procedures, which hinder ZrV2O7The applicability of (1). Thus, a simple and environmentally friendly method for preparing ZrV was sought2O7Is crucial in practical application. Therefore, it has become an important research subject.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a novel vanadate photocatalytic material.
The invention provides a preparation method of a novel vanadate photocatalytic material, which is characterized in that ammonium metavanadate and zirconium oxychloride are used as raw materials, lanthanum nitrate is used for providing rare earth element lanthanum, citric acid is used as a cementing agent, and a sol-gel-calcination method is adopted to prepare Zr1- xLaxV2O7-x/2Powder, wherein x is 0.01-0.1.
Preferably, the molar ratio of ammonium metavanadate to zirconium oxychloride is from 1.9:1 to 2: 1.
Preferably, the molar ratio of the citric acid to the lanthanum nitrate is 2:1-3: 1.
Preferably, Zr is prepared by a sol-gel-calcination method1-xLaxV2O7-x/2The method for preparing the powder, wherein x is 0.01-0.1, comprises the following steps:
s1, weighing the raw materials;
s2, adding ammonium metavanadate, zirconium oxychloride and lanthanum nitrate into deionized water, uniformly stirring to prepare a solution, then adding citric acid, magnetically stirring, adding ammonia water to adjust the pH value to 10, and continuing magnetically stirring to preliminarily obtain ZrV2O7And Zr (La) V2O7The mixed sol of (1);
s3, drying and calcining the prepared mixed sol, naturally cooling to room temperature, and finally putting the obtained yellow-green product into a mortar for fully grinding to obtain Zr1-xLaxV2O7-x/2Powder, wherein x is 0.01-0.1.
Preferably, the magnetic stirring after pH adjustment in step S2 is performed at 60 ℃ for 4 h.
Preferably, the drying in step S3 is drying at 80 ℃ for 6 h.
Preferably, the calcination temperature in step S3 is 600 ℃ and the calcination time is 3 h.
The invention also aims to provide the vanadate photocatalytic material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects: ZrOCl is used as a precursor2·8H2O and NH4VO3As a starting material, La (NO)3)3·8H2O provides rare earth element lanthanum, citric acid is used as cementing agent, and a sol-gel-calcination method is adopted to prepare Zr1-xLaxV2O7-x/2And (3) powder. The phase composition and the photocatalytic efficiency of the rare earth vanadate material are researched by means of X-ray diffraction experiments, ultraviolet absorption spectrum and the like. The degradation experiment of methyl orange is carried out under the excitation of ultraviolet light, and the photocatalysis efficiency and the negative thermal expansion performance of the zirconium vanadate doped with the rare earth element lanthanum are improved to a certain extent. The photocatalytic activity of the catalyst is enhanced along with the increase of the doping amount of La ions, and the photocatalytic activity reaches the maximum when the doping amount reaches 10 percent.
The novel vanadate compound is prepared by a rare earth element doping means and a sol-gel method. Reduction of pollutants compared to undoped pure vanadateThe solution ability is obviously improved, so that the rare earth element is used for doping the ZrV2O7Modification of the photocatalyst is a viable process.
Drawings
FIG. 1 is a flow chart of a process for preparing doped zirconium vanadate powder by a sol-gel method according to the embodiment;
FIG. 2 shows Zr in this example1-xLaxV2O7-x/2(x ═ 0) by the action of methyl orange solution;
FIG. 3 shows Zr in this example1-xLaxV2O7-x/2(x ═ 0.02) ultraviolet-visible absorption spectrum of methyl orange solution;
FIG. 4 shows Zr in this example1-xLaxV2O7-x/2(x ═ 0.05) ultraviolet-visible absorption spectrum of methyl orange solution;
FIG. 5 shows Zr in this example1-xLaxV2O7-x/2(x ═ 0.10) ultraviolet-visible absorption spectrum of methyl orange solution;
FIG. 6 shows Zr contents with different La contents in this example1-x(La)xV2O7-x/2The powder has an XRD pattern (a) x is 0, (b) x is 0.01, (c) x is 0.02, (d) x is 0.03, (e) x is 0.05, (f) x is 0.1;
FIG. 7 shows Zr in this example1-xLaxV2O7-x/2The photodegradation efficiency of the methyl orange solution under the action of the powder changes along with time.
Detailed Description
The following detailed description of the present invention is provided in connection with the accompanying drawings and examples, but it should be understood that the scope of the present invention is not limited to the specific embodiments. All other examples, which can be obtained by a person skilled in the art without inventive step based on the examples of the present invention, are within the scope of the present invention, and the test methods without specifying the specific conditions in the following examples are generally performed according to the conventional conditions or according to the conditions suggested by the respective manufacturers.
Example 1
Firstly, 2.3396g of ammonium metavanadate, 3.1903g of zirconium oxychloride and 0.0433g of lanthanum nitrate are weighed, the medicine is poured into a beaker, deionized water is added, the mixture is fully stirred to prepare a solution, then, citric acid is used as a coagulant, and 11.5284g of citric acid is weighed and added into the solution according to the molar ratio of the citric acid to the metal element of 2: 1. The pH of the solution was adjusted to 10 by dropwise addition of ammonia under a magnetic stirrer. Finally, the temperature of the magnetic stirrer is adjusted to 60 ℃, and the mixture is stirred for 4 hours at the temperature of 60 ℃ to obtain ZrV preliminarily2O7And Zr1-xLaxV2O7-x/2Mixed sol wherein x is 0.01.
Drying the sol in an electrothermal blowing drying oven at 80 deg.C for 6h, loading the dried sample into an alumina crucible, calcining in an electric furnace at 600 deg.C for 3h, and naturally cooling to room temperature by turning off the power supply. Finally, the obtained yellow-green product is put into a mortar for full grinding to obtain Zr1-xLaxV2O7-x/2Powder, x is 0.01.
Example 2
Example 2 the same preparation as in example 1 was carried out, except that the amounts of zirconium oxychloride and lanthanum nitrate used were different, in this example the amount of zirconium oxychloride was 3.1581g and the amount of lanthanum nitrate was 0.0866g, and Zr was prepared1-xLaxV2O7-x/2Powder, x is 0.02.
Example 3
Example 3 Zr was prepared in the same manner as in example 1 except that the amounts of zirconium oxychloride and lanthanum nitrate were different, in this example, the amount of zirconium oxychloride was 3.1258g and the amount of lanthanum nitrate was 0.1299g1-xLaxV2O7-x/2Powder, x is 0.03.
Example 4
Example 4 Zr was prepared in the same manner as in example 1 except that the amounts of zirconium oxychloride and lanthanum nitrate were different, in this example, the amount of zirconium oxychloride was 3.0614g and the amount of lanthanum nitrate was 0.2165g1-xLaxV2O7-x/2Powder, x is 0.05.
Example 5
Example 5 Zr was prepared in the same manner as in example 1 except that the amounts of zirconium oxychloride and lanthanum nitrate were different, in this example, the amount of zirconium oxychloride was 2.9003g and the amount of lanthanum nitrate was 0.4330g1-xLaxV2O7-x/2Powder, x is 0.1.
The raw material amounts in the above examples are specifically shown in table 1;
TABLE 1 amounts of reagents required for the preparation of lanthanum-doped zirconium vanadate of different values of x
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1 except that lanthanum nitrate was not added and the amount of zirconium oxychloride used was 3.2225 g.
In the embodiments 1 to 5 of the present invention, rare earth element doped zirconium vanadate is prepared, and in order to compare the photocatalytic efficiency of rare earth element doped zirconium vanadate and rare earth element undoped pure zirconium vanadate in each embodiment, the following details are provided:
1) a photochemical reaction instrument of DL-2005 type was used for the photocatalytic experiment.
And under the irradiation of a 300W mercury lamp, detecting the photocatalytic performance of the rare earth element La-doped zirconium vanadate powder by testing the decolorization rate of a methyl orange solution. The test procedure was as follows:
(1) 0.008g of methyl orange is weighed by an electronic balance and placed in a beaker, and 400ml of deionized water is added to prepare 0.04g/L of methyl orange solution.
(2) The prepared methyl orange solution is poured into a glass reactor, and then 0.4g of doped zirconium vanadate powder is added. Then the power supply is turned on to carry out the photocatalytic reaction. The suspension was stirred continuously under the irradiation of a 300W mercury lamp.
(3) Samples were taken at intervals of 5min, 10min, 20min, 30min, 60min, 90min, and 120min from the start time, respectively.
(4) Each of the samples obtained above was centrifuged at 2600r/min in a high speed centrifuge for 4 minutes.
(5) And (3) placing the supernatant of the centrifuged sample in an ultraviolet-visible spectrophotometer, and testing the photocatalytic performance of the product by measuring the decolorization rate of the upper methyl orange solution.
FIGS. 2 to 5 are Zr1-xLaxV2O7-x/2(x is 0, 0.02, x is 0.05, and x is 0.10) and the characteristic spectrogram of the methyl orange solution is very similar and has a wide waveband starting from about 210nm and ending at about 750 nm. And along with the gradual increase of the La doping amount, the photocatalytic efficiency of the zirconium vanadate powder is gradually increased.
2) The phase composition of zirconium vanadate powder with different La doping amounts is analyzed by adopting an X' Pert PRO type X-ray diffractometer in the Pasacaceae of the Netherlands:
the test conditions are CuK α rays, the voltage of an X-ray tube is 40KV, the current is 30mA, the 2 theta scanning range is 0-90 degrees, and the scanning speed is 8 degrees/min.
As shown in FIG. 6, Zr with different La doping amounts is shown1-xLaxV2O7-x/2The XRD pattern of the powder of (a) x is 0, (b) x is 0.01, (c) x is 0.02, (d) x is 0.03, (e) x is 0.05, (f) x is 0.1, we can see by comparing with standard PDF card (# 01-088-: all diffraction peaks of the pure zirconium vanadate powder are matched with those of a standard PDF card, the crystallinity is good, a crystalline phase formed under the sintering at 600 ℃ is a cubic phase, and impurities are hardly introduced. After the zirconium vanadate is doped with the rare earth element La, all diffraction peaks of the prepared powder are matched with those of a standard PDF card (#01-088-0583), the crystallinity is good, and the crystal phase is a cubic phase. Therefore, the sol-gel method successfully realizes the preparation of the rare earth element La-doped zirconium vanadate solid solution. From the figure we know that Zr with different La doping amount1-xLaxV2O7-x/2The XRD diffraction pattern of the powder is almost the same as that of undoped ZrV2O7The diffraction pattern of the powder was the same and no additional impurity peaks were detected, by the same numberComparison of the data in the database reveals that XRD diffraction results confirm that Zr is present in a series1-xLaxV2O7-x/2(x ═ 0.1, 0.05, 0.03, 0.02, 0.01) pure phases of the different components in the powder can be synthesized.
From Lambert Beer's law, the C/C can be derived0＝A/A0Then, the degradation rate of methyl orange can be defined as: degradation (%) ═ C0-Ct/C0＝A0-At/A0In which C istConcentration of methyl orange solution to react for t minutes, C0The concentration of the methyl orange solution At the initial time, namely 0min, At is the ultraviolet and visible light absorption value of the solution At the reaction time of t min, A0Is the UV-Vis absorption value at 0min of the initial solution. And (3) taking the degradation rate as a vertical coordinate and the reaction time as a horizontal coordinate, and making degradation curves of the methyl orange solution under the action of the zirconium vanadate with different La doping amounts. As shown in figure 7 of the drawings,
as can be seen from the degradation curve chart, the degradation rate of methyl orange is gradually increased along with the gradual increase of the La doping amount, and the degradation effect is better and better. The method shows that the photocatalytic activity of the zirconium vanadate can be improved by doping the zirconium vanadate with the rare earth element La, and the photocatalytic activity of the zirconium vanadate is gradually increased along with the gradual increase of the La doping amount. When the doping amount is 10%, the photocatalytic activity of the doped zirconium vanadate reaches a maximum value.
When the claims of the present invention refer to numerical ranges, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those of the embodiment, the present invention describes a preferred embodiment and effects thereof in order to prevent redundancy. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a novel vanadate photocatalytic material is characterized in that ammonium metavanadate and zirconium oxychloride are used as raw materials, lanthanum nitrate provides a rare earth element lanthanum, citric acid is used as a cementing agent, and a sol-gel-calcination method is adopted to prepare Zr1- xLaxV2O7-x/2Powder, wherein x is 0.01-0.1.
2. The method of claim 1, wherein the molar ratio of ammonium metavanadate to zirconium oxychloride is from 1.9:1 to 2: 1.
3. The method for preparing a novel vanadate photocatalytic material according to claim 1, wherein the molar ratio of the citric acid to the lanthanum nitrate is 2:1-3: 1.
4. The method for preparing a novel vanadate photocatalytic material according to any one of claims 1 to 3, wherein Zr is prepared by a sol-gel-calcination method1-xLaxV2O7-x/2The method for preparing the powder with x of 0.01-0.1 comprises the following steps:
s1, weighing the raw materials;
s2, adding ammonium metavanadate, zirconium oxychloride and lanthanum nitrate into deionized water, uniformly stirring to prepare a solution, then adding citric acid, magnetically stirring, adding ammonia water to adjust the pH value to 9-10, and continuously magnetically stirring to obtain ZrV preliminarily2O7And Zr (La) V2O7The mixed sol of (1);
s3, drying and calcining the prepared mixed sol, naturally cooling to room temperature, and finally putting the obtained yellow-green product into a mortar for fully grinding to obtain Zr1-xLaxV2O7-x/2The powder body, wherein the value of x is 0.01-0.1.
5. The method of claim 4, wherein the magnetic stirring after the pH adjustment in step S2 is performed at 60 ℃ for 4 h.
6. The method of claim 4, wherein the step S3 is drying at 80 ℃ for 6 h.
7. The method of claim 4, wherein the calcination temperature in step S3 is 600 ℃ and the calcination time is 3 h.
8. Zr prepared by the method for preparing a novel vanadate photocatalytic material according to any one of claims 1 to 71- xLaxV2O7-x/2Powder, wherein x is 0.01-0.1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011138255A2 (en) * | 2010-05-06 | 2011-11-10 | Rhodia Operations | Composition containing oxides of zirconium, cerium and at least one other rare earth and having a specific porosity, method for preparing same and use thereof in catalysis |
| CN103372424A (en) * | 2012-04-12 | 2013-10-30 | 沈阳理工大学 | Synthetic method for high-activity N-F co-doped bismuth vanadate visible light photocatalytic material |
| CN103641170A (en) * | 2013-12-09 | 2014-03-19 | 江苏大学 | Method for directly synthesizing sub-micron zirconium vanadate |
| CN105148899A (en) * | 2015-09-29 | 2015-12-16 | 陕西科技大学 | Rare earth co-doped BiVO4 photocatalyst with upconversion characteristic and preparing method and application thereof |
| JP2016164100A (en) * | 2015-03-06 | 2016-09-08 | 国立大学法人東北大学 | METHOD FOR PRODUCING La2Zr2O7 NANOPARTICLES |
-
2019
- 2019-12-30 CN CN201911399394.1A patent/CN110975859B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011138255A2 (en) * | 2010-05-06 | 2011-11-10 | Rhodia Operations | Composition containing oxides of zirconium, cerium and at least one other rare earth and having a specific porosity, method for preparing same and use thereof in catalysis |
| CN103372424A (en) * | 2012-04-12 | 2013-10-30 | 沈阳理工大学 | Synthetic method for high-activity N-F co-doped bismuth vanadate visible light photocatalytic material |
| CN103641170A (en) * | 2013-12-09 | 2014-03-19 | 江苏大学 | Method for directly synthesizing sub-micron zirconium vanadate |
| JP2016164100A (en) * | 2015-03-06 | 2016-09-08 | 国立大学法人東北大学 | METHOD FOR PRODUCING La2Zr2O7 NANOPARTICLES |
| CN105148899A (en) * | 2015-09-29 | 2015-12-16 | 陕西科技大学 | Rare earth co-doped BiVO4 photocatalyst with upconversion characteristic and preparing method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIU QINQIN ET AL.: "Influence of W doped ZrV2O7 on structure, negative thermal expansion property and photocatalytic performance", 《APPLIED SURFACE SCIENCE》 * |
| 王剑波 等: "La-BiVO4催化剂的制备及其光催化还原CO2", 《石油与天然气化工》 * |
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