CN110975859B - Preparation method of vanadate photocatalytic material - Google Patents
Preparation method of vanadate photocatalytic material Download PDFInfo
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- CN110975859B CN110975859B CN201911399394.1A CN201911399394A CN110975859B CN 110975859 B CN110975859 B CN 110975859B CN 201911399394 A CN201911399394 A CN 201911399394A CN 110975859 B CN110975859 B CN 110975859B
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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 35
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 16
- 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 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 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
- 229910052761 rare earth metal Inorganic materials 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 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 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
- 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 claims description 5
- 229940012189 methyl orange Drugs 0.000 claims description 5
- 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
- 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
- 238000001816 cooling Methods 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
- 230000000593 degrading effect Effects 0.000 claims 1
- 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 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 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 3
- 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 6
- 239000000243 solution Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002474 experimental method Methods 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000003054 catalyst Substances 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
- 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
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004887 air purification Methods 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
- 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
- 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
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 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
- 238000001228 spectrum Methods 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 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 method 1‑x La x V 2 O 7‑x/2 Powder, 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 vanadate photocatalytic material.
Background
ZrV as a new photocatalytic material 2 O 7 Shows specific photocatalytic performance on degradation of different dyes, and shows that ZrV 2 O 7 Has 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 ZrV 2 O 7 In the preparation of (1), aVarious methods of preparation have been reported, for example ZrO 2 And V 2 O 5 Solid-phase reaction at high temperature, coprecipitation, and hydrothermal methods. These methods all involve complicated synthetic procedures, which hinder ZrV 2 O 7 The applicability of (1). Thus, a simple and environmentally friendly method for preparing ZrV was sought 2 O 7 Is crucial in practical application. Therefore, it is an important research subject.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a vanadate photocatalytic material.
The invention provides a preparation method of vanadate photocatalytic material, which takes ammonium metavanadate and zirconium oxychloride as raw materials, lanthanum nitrate provides rare earth element lanthanum, citric acid is taken as cementing agent, and a sol-gel-calcination method is adopted to prepare Zr 1- x La x V 2 O 7-x/2 Powder, wherein x is 0.01-0.1.
Preferably, the molar ratio of ammonium metavanadate to zirconium oxychloride is 1.9.
Preferably, the molar ratio of citric acid to lanthanum nitrate is 2.
Preferably, the sol-gel-calcining method is adopted to prepare Zr 1-x La x V 2 O 7-x/2 The method for preparing the powder, wherein x is 0.01-0.1, comprises the following steps:
s1, weighing 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, continuing to magnetically stirring to preliminarily obtain ZrV 2 O 7 And Zr (La) V 2 O 7 The mixed sol of (1);
s3, drying and calcining the prepared mixed sol, naturally cooling to room temperature, and finally fully grinding the obtained yellow-green product in a mortar to obtain Zr 1-x La x V 2 O 7-x/2 Powder, wherein x is 0.01-0.1.
Preferably, the magnetic stirring after pH adjustment in step S2 is performed at 60 ℃ for 4h.
Preferably, the drying in step S3 is drying at 80 ℃ for 6h.
Preferably, the calcination temperature in step S3 is 600 ℃ and the calcination time is 3h.
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 precursor 2 ·8H 2 O and NH 4 VO 3 As a starting material, la (NO) 3 ) 3 ·8H 2 O provides rare earth element lanthanum, citric acid is used as cementing agent, and a sol-gel-calcination method is adopted to prepare Zr 1-x La x V 2 O 7-x/2 And (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 of the catalyst 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. Compared with undoped pure vanadate, the degradation capability of the vanadate to pollutants is obviously improved, so that ZrV is doped by using rare earth elements 2 O 7 Modification 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 example 1-x La x V 2 O 7-x/2 (x = 0) uv-vis absorption spectrum of methyl orange solution;
FIG. 3 shows Zr in this example 1-x La x V 2 O 7-x/2 (x = 0.02) uv-vis absorption spectrum of methyl orange solution;
figure 4 is the bookExample Zr 1-x La x V 2 O 7-x/2 (x = 0.05) uv-vis absorption spectrum of methyl orange solution;
FIG. 5 shows Zr in this example 1-x La x V 2 O 7-x/2 (x = 0.10) uv-vis absorption spectrum of methyl orange solution;
FIG. 6 shows Zr contents with different La contents in this example 1-x (La) x V 2 O 7-x/2 The XRD pattern of the powder (a) x =0, (b) x =0.01, (c) x =0.02, (d) x =0.03, (e) x =0.05, (f) x =0.1;
FIG. 7 shows Zr in this example 1-x La x V 2 O 7-x/2 The 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, and then, by taking citric acid as a coagulant, 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 2. 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 preliminarily 2 O 7 And Zr 1-x La x V 2 O 7-x/2 Mixed sols where x =0.01.
Drying the sol in an electrothermal blowing drying oven at 80 deg.CAnd 6h, then putting the dried sample into an alumina crucible, putting the alumina crucible into an electric furnace, calcining the alumina crucible at 600 ℃ for 3h, and then turning off a power supply to naturally cool the alumina crucible to room temperature. Finally, the obtained yellow-green product is put into a mortar for full grinding to obtain Zr 1-x La x V 2 O 7-x/2 Powder, x =0.01.
Example 2
Example 2 the same preparation method as example 1 was used, except that the amounts of zirconium oxychloride and lanthanum nitrate were different, in this example, 3.1581g of zirconium oxychloride and 0.0866g of lanthanum nitrate were used, and Zr was prepared 1-x La x V 2 O 7-x/2 Powder, x =0.02.
Example 3
Example 3 Zr was prepared in the same manner as in example 1 except that zirconium oxychloride and lanthanum nitrate were used in different amounts, in this example 3.1258g of zirconium oxychloride and 0.1299g of lanthanum nitrate were used 1-x La x V 2 O 7-x/2 Powder, x =0.03.
Example 4
Example 4 Zr was prepared in the same manner as in example 1 except that zirconium oxychloride and lanthanum nitrate were used in different amounts, in this example 3.0614g of zirconium oxychloride and 0.2165g of lanthanum nitrate were used 1-x La x V 2 O 7-x/2 Powder, x =0.05.
Example 5
Example 5 was prepared in the same manner as in example 1 except that zirconium oxychloride and lanthanum nitrate were used in different amounts, 2.9003g in this example and 0.4330g in lanthanum nitrate, to obtain Zr 1-x La x V 2 O 7-x/2 Powder, x =0.1.
The raw material amounts in the above examples are specifically shown in table 1;
TABLE 1 amounts of reagents required to prepare lanthanum-doped zirconium vanadate of different x values
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1 except that lanthanum nitrate was not added and zirconium oxychloride was used in an amount of 3.2225g.
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 a 0.04g/L 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) Sampling is respectively carried out at intervals of 5min, 10min, 20min, 30min, 60min, 90min and 120min from the start time.
(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 Zr 1-x La x V 2 O 7-x/2 (x =0,0.02,x =0.05,x = 0.10) and the characteristic spectrum of the methyl orange solution is very similar, starting from about 210nm and ending at about 750nm. And along with the gradual increase of the La doping amount, the zirconium vanadate powderThe photocatalytic efficiency of (a) gradually increases.
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 were: cuKalpha ray, X-ray tube voltage 40KV, current 30mA,2 theta scanning range 0-90 DEG, and scanning speed 8 DEG/min.
As shown in FIG. 6, zr with different La doping amounts is shown 1-x La x V 2 O 7-x/2 The XRD pattern of the powder of (a) x =0, (b) x =0.01, (c) x =0.02, (d) x =0.03, (e) x =0.05, and (f) x =0.1, we can see that, by comparing it with a standard PDF card (# 01-088-0583): 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 standard PDF cards (# 01-088-0583), the crystallinity is good, and the crystal phase is cubic. 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 amount 1-x La x V 2 O 7-x/2 The XRD diffraction pattern of the powder is almost the same as that of undoped ZrV 2 O 7 The diffraction pattern of the powder is the same, no additional impurity peak is detected, and the XRD diffraction result proves that the Zr exists in a series of Zr by comparing with the data in the database 1-x La x V 2 O 7-x/2 (x =0.1,0.05,0.03,0.02, 0.01) pure phases of the different components in the powder are synthesizable.
From Lambert Beer's law, the C/C can be derived 0 ＝A/A 0 Then, the degradation rate of methyl orange can be defined as: degradation (%) = C 0 -C t /C 0 ＝A 0 -A t /A 0 In which C is t Concentration of methyl orange solution to react for t minutes, C 0 The concentration of the methyl orange solution At the initial time, namely 0min, and At is the ultraviolet visible light when the solution reacts for t minutesLight absorption value, A 0 Is 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 doping amount of the La. 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 (7)
1. A preparation method of vanadate photocatalytic material is characterized in that ammonium metavanadate and zirconium oxychloride are used as raw materials, lanthanum nitrate provides rare earth element lanthanum, citric acid is used as a cementing agent, and a sol-gel-calcination method is adopted to prepare Zr 1- x La x V 2 O 7-x/2 Powder, wherein x is 0.01-0.1;
the preparation method specifically comprises the following steps:
s1, weighing raw materials;
s2, adding ammonium metavanadate, zirconium oxychloride and lanthanum nitrate into deionized water, uniformly stirring to prepare a solution, adding citric acid, magnetically stirring, adding ammonia water to adjust the pH value to 9-10, and continuously magnetically stirring to obtain ZrV preliminarily 2 O 7 And Zr (La) V 2 O 7 The mixed sol of (1);
s3, drying and calcining the prepared mixed sol, naturally cooling to room temperature, and finally fully grinding the obtained yellow-green product in a mortar to obtain Zr 1-x La x V 2 O 7-x/2 Powder, wherein x is 0.01-0.1;
zr obtained 1-x La x V 2 O 7-x/2 The powder is used for degrading methyl orange.
2. The method for preparing a vanadate photocatalytic material according to claim 1, wherein the molar ratio of ammonium metavanadate to zirconium oxychloride is 1.9.
3. The method for preparing a vanadate photocatalytic material according to claim 1, wherein the molar ratio of citric acid to lanthanum nitrate is 2.
4. The method of claim 1, wherein the magnetic stirring after the pH adjustment in step S2 is performed at 60 ℃ for 4h.
5. The method of claim 1, wherein the drying in step S3 is performed at 80 ℃ for 6h.
6. The method for preparing vanadate photocatalytic material according to claim 1, wherein the calcination temperature in step S3 is 600 ℃ and the calcination time is 3 hours.
7. Method for preparing vanadate photocatalytic material according to any of claims 1-6Zr prepared by the preparation method 1- x La x V 2 O 7-x/2 Powder, wherein x is 0.01-0.1.
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| CN201911399394.1A CN110975859B (en) | 2019-12-30 | 2019-12-30 | Preparation method of vanadate photocatalytic material |
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