CN115594219B - Eighteen-surface bismuth vanadate as well as preparation method and application thereof - Google Patents
Eighteen-surface bismuth vanadate as well as preparation method and application thereof Download PDFInfo
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- CN115594219B CN115594219B CN202210491262.7A CN202210491262A CN115594219B CN 115594219 B CN115594219 B CN 115594219B CN 202210491262 A CN202210491262 A CN 202210491262A CN 115594219 B CN115594219 B CN 115594219B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 133
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 133
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 66
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 80
- 239000000243 solution Substances 0.000 claims description 32
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 238000006479 redox reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001621 bismuth Chemical class 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 238000011534 incubation Methods 0.000 claims description 4
- 229940107698 malachite green Drugs 0.000 claims description 4
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims 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 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 229960003742 phenol Drugs 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000001782 photodegradation Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- RJOBGTNMWSHFSR-UHFFFAOYSA-N [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] RJOBGTNMWSHFSR-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- AJOAVLIQQBNNNS-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)[Bi] Chemical compound C(CCCCCCCCCCCCCCCCC)[Bi] AJOAVLIQQBNNNS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides an eighteen-surface bismuth vanadate, and a preparation method and application thereof, and belongs to the technical field of catalysts. The eighteen-body bismuth vanadate provided by the invention consists of bismuth vanadate crystals with 2 {010} crystal faces, 8 {110} crystal faces and 18 crystal faces of 8 {121} crystal faces. In the decaoctahedral bismuth vanadate provided by the invention, the exposed high-activity {010} crystal face has a multi-atom center BiV with large density 4 The center can collect photo-generated electrons to promote the separation of carriers, and can rapidly transfer the photo-generated electrons to a capturing agent such as oxygen to accelerate the speed of O 2－ And the generation of active species such as OH and the like is beneficial to the improvement of the photocatalytic activity of the dodecahedral bismuth vanadate; the presence of the high-index {121} crystal face with more surface oxygen vacancies further increases the catalytic activity of bismuth vanadate. Has high catalytic activity on organic pollutants, especially rhodamine B, and has good application prospect as a catalyst.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an octadecanoic bismuth vanadate, and a preparation method and application thereof.
Background
In recent years, the pollution of water resources by refractory organic substances has created a serious challenge to destroy aquatic organisms and even the living environment of human beings. Approximately 30% of the organic dye is discharged randomly through the waste water without treatment, and the organic dye is generally harmful to the human body. Based on this, researchers have developed various methods to alleviate environmental problems caused by organic dyes, and photocatalytic technology is widely used to degrade environmental pollutants as one of the most promising methods. In BiVO 4 The typical Bi-based photocatalyst attracts a great deal of attention from researchers as an excellent photocatalytic material.
The surface structure of the semiconductor material, particularly the exposed active crystal planes, has a crucial influence on the photocatalytic activity. Existing BiVO 4 Most have {010} crystal planesAnd {110} crystal plane, biVO of decahedral structure 4 . However, biVO as described above 4 The catalytic activity towards organic dyes, especially rhodamine B, is not high enough.
Disclosure of Invention
In view of the above, the invention aims to provide a dodecahedral bismuth vanadate, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an eighteen-body bismuth vanadate, which consists of bismuth vanadate crystals with 18 crystal faces, wherein the 18 crystal faces comprise 2 {010} crystal faces, 8 {110} crystal faces and 8 {121} crystal faces.
Preferably, the particle size of the bismuth vanadate crystal is 3-5 μm.
The invention provides a preparation method of the octadecanoic bismuth vanadate in the technical scheme, which comprises the following steps:
placing a nitric acid solution of a bismuth source and an aqueous solution of ammonium metavanadate in a micro-liquid membrane reactor for oxidation-reduction reaction to obtain an amorphous bismuth vanadate suspension;
carrying out hydrothermal reaction on the amorphous bismuth vanadate suspension to obtain decaoctahedral bismuth vanadate;
the hydrothermal reaction comprises sequentially performing a first hydrothermal reaction, a second hydrothermal reaction and a third hydrothermal reaction; the temperature of the first hydrothermal reaction is 90-120 ℃, and the heat preservation time is 0-6 h; the temperature of the second hydrothermal reaction is 120-150 ℃, and the heat preservation time is 0-48 h; the temperature of the third hydrothermal reaction is 150-180 ℃, and the heat preservation time is 0-12 h; the temperature of the first hydrothermal reaction is less than the temperature of the second hydrothermal reaction is less than the temperature of the third hydrothermal reaction; at least 2 of the incubation times of the first, second and third hydrothermal reactions are not 0.
Preferably, the concentration of the bismuth source in the nitric acid solution of the bismuth source is 0.1-0.5 mol/L, and the concentration of the nitric acid solution is 2-8 mol/L; the bismuth source comprises bismuth salt and/or bismuth oxide;
the concentration of the aqueous solution of ammonium metavanadate is 0.1-0.5 mol/;
the molar ratio of the bismuth source to the ammonium metavanadate is 1-1.2: 1 to 1.2.
Preferably, the micro liquid film of the micro liquid film reactor has a width of 100-200 μm.
Preferably, the temperature of the oxidation-reduction reaction is 0-30 ℃ and the time is 1-5 min.
Preferably, the time of the first temperature-controlled hydrothermal reaction is 0-6 h; the time of the second temperature-controlled hydrothermal reaction is 0-48 h; the time of the third temperature-controlled hydrothermal reaction is 0-12 h.
The invention also provides the application of the octadecanoic bismuth vanadate in the technical scheme or the octadecanoic bismuth vanadate obtained by the preparation method in the technical scheme as a catalyst.
Preferably, the octadecanoic bismuth vanadate is applied to photocatalytic water decomposition reaction, photocatalytic reduction of carbon dioxide or photocatalytic degradation of organic pollutants.
Preferably, the mass ratio of the octadecanoic bismuth vanadate to the organic pollutants is 1:0.0002 to 0.001.
Preferably, the organic pollutant comprises one or more of rhodamine B, methylene blue, methyl orange, malachite green and phenol.
The invention provides an eighteen-body bismuth vanadate, which consists of bismuth vanadate crystals with 18 crystal faces, wherein the 18 crystal faces comprise 2 {010} crystal faces, 8 {110} crystal faces and 8 {121} crystal faces. In the decaoctahedral bismuth vanadate provided by the invention, the exposed high-activity {010} crystal face has a multi-atom center BiV with large density 4 The center can collect photo-generated electrons to promote the separation of carriers, and can rapidly transfer the photo-generated electrons to a capturing agent such as oxygen to accelerate the speed of O 2－ And the generation of active species such as OH and the like is beneficial to the improvement of the photocatalytic activity of the dodecahedral bismuth vanadate; the presence of a high-index 121 crystal plane with more surface oxygen vacancies will cause Bi 3+ The surrounding is more intense and the lone pair distortion is caused, so that the Bi 6s and O2 p electron orbitals in the bismuth vanadate valence band are overlapped to a greater degree,further enhances the separation of carriers and is beneficial to the improvement of the photocatalytic activity of the dodecahedral bismuth vanadate. Has high catalytic activity on organic pollutants, especially rhodamine B, and has good application prospect as a catalyst. As shown in the test results of examples, the degradation rate of rhodamine B is over 95% after the decaoctahedral bismuth vanadate provided by the invention is used as a catalyst for degrading rhodamine B for 3 hours.
Furthermore, the bismuth vanadate crystal particle size of the octadecanoic bismuth vanadate provided by the invention is 3-5 mu m, and the octadecanoic bismuth vanadate has good uniformity and monodispersity.
The invention provides a preparation method of the octadecanoic bismuth vanadate in the technical scheme. According to the invention, by establishing an acidic micro-environment with higher concentration in the micro-liquid membrane reactor, the hydrolysis of a bismuth source in the amorphous bismuth vanadate formation process is inhibited, and the supersaturation state and nucleation rate of a reaction solution in a micro-scale are effectively controlled; the subsequent dynamic program controlled hydrothermal reaction breaks the hydrolysis balance of the bismuth source, improves the supersaturation degree of a crystallization system, ensures the subsequent ordered growth of bismuth vanadate crystals, thereby forming a high-index {121} crystal face exposing more surface oxygen vacancies, and being beneficial to forming the decaoctahedral bismuth vanadate crystals with uniform crystal particle size and good monodispersity.
In addition, the preparation method provided by the invention can controllably synthesize the bismuth vanadate crystal material with high-index crystal face, uniform crystal size and no agglomeration without adding an organic structure directing agent (such as sodium dodecyl benzene sulfonate) and an inorganic structure directing agent (such as titanium trichloride) in the precipitation nucleation reaction; the preparation method is green, pollution-free, low in production cost, simple in purification process and suitable for industrial production.
Drawings
FIG. 1 is an SEM image of the octadecanoic bismuth vanadate prepared according to example 1;
FIG. 2 is a schematic diagram of the crystal plane of the octadecanoic bismuth vanadate prepared in example 1;
fig. 3 is an SEM image of bismuth vanadate prepared in comparative example 1;
FIG. 4 is an SEM image of bismuth vanadate prepared according to comparative example 2;
FIG. 5 is an SEM image of bismuth vanadate prepared according to comparative example 3;
FIG. 6 is a graph showing the variation of the violet visible spectrum versus time of the octadecyl bismuth vanadate prepared in example 1 as a catalyst for the degradation of rhodamine B aqueous solution;
fig. 7 is a graph showing a change in concentration of rhodamine B solution with respect to time in photodegradation reactions of the octadecanoic bismuth vanadate prepared in example 1 and the decahedral bismuth vanadate prepared in comparative example 1.
Detailed Description
The invention provides an eighteen-body bismuth vanadate, which consists of bismuth vanadate crystals with 18 crystal faces, wherein the 18 crystal faces comprise 2 {010} crystal faces, 8 {110} crystal faces and 8 {121} crystal faces. In the present invention, the particle diameter of the bismuth vanadate crystal is preferably 3 to 5. Mu.m, more preferably 3.5 to 4.5. Mu.m, and still more preferably 4. Mu.m.
The invention provides a preparation method of the octadecanoic bismuth vanadate in the technical scheme, which comprises the following steps:
placing a nitric acid solution of a bismuth source and an aqueous solution of ammonium metavanadate in a micro-liquid membrane reactor for oxidation-reduction reaction to obtain an amorphous bismuth vanadate suspension;
carrying out hydrothermal reaction on the amorphous bismuth vanadate suspension to obtain decaoctahedral bismuth vanadate;
the hydrothermal reaction is carried out under a temperature programming condition, and the temperature programming comprises at least two of a first temperature-controlled hydrothermal reaction, a second temperature-controlled hydrothermal reaction and a third temperature-controlled hydrothermal reaction which are sequentially carried out; the temperature of the first temperature-controlled hydrothermal reaction is 90-120 ℃, the temperature of the second temperature-controlled hydrothermal reaction is 120-150 ℃, and the temperature of the third temperature-controlled hydrothermal reaction is 150-180 ℃.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention puts the nitric acid solution of bismuth source and the aqueous solution of ammonium metavanadate into a micro-liquid membrane reactor for oxidation-reduction reaction to obtain amorphous bismuth vanadate suspension.
In the present invention, the concentration of the bismuth source in the nitric acid solution of the bismuth source is preferably 0.1 to 05mol/L, more preferably 0.2 to 0.4mol/L, still more preferably 0.3mol/L; the concentration of the nitric acid solution is preferably 2 to 8mol/L, more preferably 3 to 7mol/L, and still more preferably 4 to 6mol/L. In the present invention, the bismuth source preferably includes bismuth salt and/or bismuth oxide (Bi 2 O 3 ) The bismuth salt preferably comprises one or more of bismuth nitrate, bismuth sulfate and bismuth chloride; when the bismuth source is a mixture of two or more bismuth salts, the invention is not particularly limited to the ratio of the different bismuth salts, and any ratio may be used. In the present invention, the nitric acid solution of the bismuth source is preferably obtained by dissolving the bismuth source in a nitric acid solution.
In the present invention, the concentration of the aqueous solution of ammonium metavanadate is preferably 0.1 to 0.5mol/L, more preferably 0.2 to 0.4mol/L, and still more preferably 0.3mol/L. In the present invention, the aqueous solution of ammonium metavanadate is preferably obtained by dissolving ammonium metavanadate in water; the temperature of the dissolution is preferably 75 to 95 ℃, more preferably 80 to 90 ℃, still more preferably 85 ℃; the invention is not particularly limited to the dissolution temperature, and the ammonium metavanadate can be completely dissolved. In the present invention, the molar ratio of the bismuth source to ammonium metavanadate is preferably 1 to 1.2:1 to 1.2, more preferably 1 to 1.1:1 to 1.1, more preferably 1:1.
In the specific embodiment of the invention, the nitric acid solution of bismuth source and the aqueous solution of ammonium metavanadate are preferably uniformly added into the micro-liquid film reactor for oxidation-reduction reaction. In the present invention, the flow rates of the nitric acid solution of the bismuth source and the aqueous solution of ammonium metavanadate are independently preferably 0.3 to 1.5L/min, more preferably 0.7 to 1L/min. In the present invention, the microfluidic membrane reactor preferably has a microfluidic membrane width of 100 to 200. Mu.m, more preferably 120 to 180. Mu.m, still more preferably 140 to 160. Mu.m. The present invention is not particularly limited to the microfluidic membrane reactor, and the microfluidic membrane reactor known to those skilled in the art may be used. In a specific embodiment of the invention, the microfluidic membrane reactor is preferably a Chi-Ri JMS-50. In the present invention, the temperature of the redox reaction is preferably 0 to 30 ℃, more preferably 15 to 25 ℃, still more preferably 20 ℃; the time for the redox reaction is preferably 1 to 5 minutes, more preferably 2 to 4 minutes, and still more preferably 3 minutes. In the present invention, the reaction occurring during the redox reaction is as follows:
BiONO 3 +VO 3 - →BiVO 4 ↓+NO 3 - 。
after the amorphous bismuth vanadate suspension is obtained, the amorphous bismuth vanadate suspension is subjected to hydrothermal reaction to obtain the decaoctahedral bismuth vanadate.
In the present invention, the hydrothermal reaction includes sequentially performing a first hydrothermal reaction, a second hydrothermal reaction, and a third hydrothermal reaction. In the present invention, the temperature of the first hydrothermal reaction is 90 to 120 ℃, preferably 95 to 115 ℃, more preferably 100 to 110 ℃, still more preferably 105 ℃; the holding time of the first hydrothermal reaction is preferably 0 to 6 hours, more preferably 1 to 5 hours, and still more preferably 2 to 4 hours. In the present invention, the temperature of the second hydrothermal reaction is 120 to 150 ℃, preferably 125 to 145 ℃, more preferably 130 to 140 ℃, still more preferably 135 ℃; the holding time of the second hydrothermal reaction is preferably 0 to 48 hours, more preferably 5 to 40 hours, and still more preferably 10 to 20 hours. In the present invention, the temperature of the third hydrothermal reaction is 150 to 180 ℃, preferably 155 to 175 ℃, more preferably 160 to 170 ℃, still more preferably 165 ℃; the holding time of the third hydrothermal reaction is preferably 0 to 12 hours, more preferably 1 to 10 hours, and even more preferably 3 to 5 hours; the temperature of the first hydrothermal reaction is less than the temperature of the second hydrothermal reaction is less than the temperature of the third hydrothermal reaction; at least 2 of the incubation times of the first, second and third hydrothermal reactions are not 0. In the present invention, the hydrothermal reaction is preferably performed in a hydrothermal reaction kettle; the hydrothermal reaction kettle is preferably provided with a polytetrafluoroethylene liner. The invention carries out hydrothermal reaction under the temperature programming condition, is favorable for avoiding aggregation of particles, changes the crystal from an amorphous state to a crystalline state and can form a high-index {121} crystal face.
After the hydrothermal reaction is finished, the invention preferably further comprises the steps of cooling the obtained hydrothermal reaction crystal slurry to room temperature, then carrying out solid-liquid separation, and sequentially washing the obtained crystal to neutrality, drying and crushing to obtain the dodecahedral bismuth vanadate. The cooling method is not particularly limited, and a cooling method known to those skilled in the art, such as stationary cooling, may be used. The solid-liquid separation is not particularly limited, and a solid-liquid separation method well known to those skilled in the art, specifically, centrifugal separation may be employed. In the present invention, the water washing is preferably centrifugal water washing. In the present invention, the drying temperature is preferably 50 to 80 ℃, more preferably 60 to 70 ℃; the drying time is not particularly limited, and the drying time is required to be constant. The crushing is not particularly limited, and the crushing may be carried out by crushing to a particle size of 3 to 5. Mu.m, for example, grinding, by a crushing means well known to those skilled in the art.
The invention provides the application of the octadecanoic bismuth vanadate in the technical scheme or the octadecanoic bismuth vanadate obtained by the preparation method in the technical scheme as a catalyst. In the invention, the octadecanoic bismuth vanadate is preferably applied to photocatalytic water splitting reaction, photocatalytic reduction of carbon dioxide or photocatalytic degradation of organic pollutants. In the present invention, the organic contaminant preferably includes one or more of rhodamine B, methylene Blue (MB), methyl Orange (MO), malachite Green (MG), and phenol.
In the invention, the method for photocatalytic degradation of rhodamine B by using the octadecanoic bismuth vanadate preferably comprises the following steps of: mixing the decaoctahedral bismuth vanadate with a rhodamine B-containing water body under a light-shielding condition, and then carrying out photocatalytic reaction under an illumination condition. In the invention, the mass ratio of the octadecanoic bismuth vanadate to the organic pollutant is preferably 1:0.0002 to 0.001, more preferably 1:0.0004 to 0.0008, more preferably 1:0.0004 to 0.0005. In the invention, the concentration of rhodamine B in the rhodamine B-containing water body is preferably 1-5 mg/L, more preferably 2-4 mg/L, and even more preferably 3mg/L. In the present invention, the light-shielding is preferably a dark environment; the temperature of the mixing is preferably room temperature, the time is preferably 15 to 180min, more preferably 30 to 150min, and even more preferably 60 to 120min; according to the invention, the adsorption and desorption balance of the decaoctahedral bismuth vanadate to rhodamine B can be realized by mixing under the light-shielding condition. In a specific embodiment of the invention, the illumination condition is preferably to simulate natural light with a xenon lamp light source with a filter (lambda >420 nm). In the present invention, the temperature of the photocatalytic reaction is preferably room temperature; the time of the photocatalytic reaction is preferably 30 to 300 minutes, more preferably 30 to 180 minutes.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
12.125g of bismuth nitrate pentahydrate (0.025 mol) was dissolved in 100mL of a 4mol/L nitric acid solution to obtain a bismuth nitrate nitric acid solution having a bismuth nitrate concentration of 0.25 mol/L. 2.925g of ammonium metavanadate (0.025 mol) was placed in 100mL of water and heated to 75℃to dissolve the ammonium metavanadate, thereby obtaining an aqueous solution of ammonium metavanadate having an ammonium metavanadate concentration of 0.25 mol/L. Simultaneously pouring a nitric acid solution of bismuth nitrate and an aqueous solution of ammonium metavanadate into a micro-liquid membrane reactor (JMS-50, the width of a liquid membrane is 200 mu m) at a constant speed of 1L/min, reacting for 5min, placing the obtained amorphous bismuth vanadate suspension into a hydrothermal kettle with a polytetrafluoroethylene liner, carrying out hydrothermal reaction for 6h at 90 ℃, carrying out hydrothermal reaction for 48h at 150 ℃, standing and cooling to room temperature, centrifugally separating the obtained hydrothermal reaction crystal slurry, centrifugally washing the obtained crystal with deionized water to be neutral, drying in a 60 ℃ oven to constant weight, and grinding to obtain the decaoctahedral bismuth vanadate.
Fig. 1 is an SEM image of the octadecanoic bismuth vanadate prepared in example 1, and it can be seen from fig. 1 that bismuth vanadate crystals are in the shape of octadecanoic, exist as about 4 μm of microcrystals, and have good dispersibility. Fig. 2 is a schematic diagram of the crystal planes of the octadecanoic bismuth vanadate prepared in example 1, which includes 2 upper and lower {010} crystal planes, 8 {110} crystal planes with larger side surfaces and 8 high-index {121} crystal planes with smaller side surfaces.
Example 2
9.7g of bismuth nitrate pentahydrate (0.02 mol) was dissolved in 200mL of a nitric acid solution having a concentration of 2mol/L to obtain a nitric acid solution of bismuth nitrate having a concentration of 0.1 mol/L. 2.34g of ammonium metavanadate (0.02 mol) was placed in 200mL of water and heated to 85℃to dissolve the ammonium metavanadate, to obtain an aqueous solution of ammonium metavanadate having an ammonium metavanadate concentration of 0.25 mol/L. Simultaneously pouring a nitric acid solution of bismuth nitrate and an aqueous solution of ammonium metavanadate into a micro-liquid membrane reactor (the width of a liquid membrane is 150 mu m) at a constant speed of 1L/min, reacting for 3min, placing the obtained amorphous bismuth vanadate suspension into a hydrothermal kettle with a polytetrafluoroethylene liner, carrying out hydrothermal reaction for 6h at 90 ℃, carrying out hydrothermal reaction for 12h at 180 ℃, standing and cooling to room temperature, centrifugally separating the obtained hydrothermal reaction crystal slurry, centrifugally washing the obtained crystal with deionized water to be neutral, drying in a 60 ℃ oven to constant weight, and grinding to obtain the decaoctahedral bismuth vanadate.
Example 3
23.65g of bismuth chloride (0.075 mol) was dissolved in 150mL of a nitric acid solution having a concentration of 8mol/L to obtain a nitric acid solution of bismuth chloride having a concentration of 0.5 mol/L. 8.775g of ammonium metavanadate (0.075 mol) was placed in 150mL of water and heated to 95℃to dissolve the ammonium metavanadate, to obtain an aqueous solution of ammonium metavanadate having an ammonium metavanadate concentration of 0.5 mol/L. Simultaneously pouring a nitric acid solution of bismuth nitrate and an aqueous solution of ammonium metavanadate into a micro-liquid membrane reactor (the width of a liquid membrane is 100 mu m) at a constant speed of 1L/min, reacting for 1min, placing the obtained amorphous bismuth vanadate suspension into a hydrothermal kettle with a polytetrafluoroethylene liner, carrying out hydrothermal reaction for 12h at 150 ℃, carrying out hydrothermal reaction for 12h at 180 ℃, standing and cooling to room temperature, centrifugally separating the obtained hydrothermal reaction crystal slurry, centrifugally washing the obtained crystal with deionized water to be neutral, drying in a 60 ℃ oven to constant weight, and grinding to obtain the decaoctahedral bismuth vanadate.
Comparative example 1
Bismuth vanadate was prepared according to the preparation method of example 1, except that the microfluidic membrane reactor was replaced with a beaker under magnetic stirring at 500rpm, as compared to example 1.
Fig. 3 is an SEM image of bismuth vanadate prepared in comparative example 1, from which comparative example 1 can be prepared in fig. 3, which is decahedral bismuth vanadate consisting of 2 {010} crystal planes and 8 {110} crystal planes, in which high-index {121} crystal planes are not present in bismuth vanadate.
Comparative example 2
Bismuth vanadate was prepared according to the preparation method of example 1, except that the hydrothermal reaction condition was a hydrothermal reaction at 180℃for 24 hours.
Fig. 4 is an SEM image of the bismuth vanadate prepared in comparative example 2, and as can be seen from fig. 4, the bismuth vanadate prepared in comparative example 2 has serious agglomeration, not only reduces the specific surface area of the catalyst, but also causes serious recombination of carriers, and thus has lower photocatalytic activity.
Comparative example 3
Bismuth vanadate was prepared according to the preparation method of example 1, except that 12.125g of bismuth nitrate pentahydrate (0.025 mol) was dissolved in 100mL of a 1mol/L nitric acid solution to give a bismuth nitrate nitric acid solution having a bismuth nitrate concentration of 0.25 mol/L.
Fig. 5 is an SEM image of bismuth vanadate prepared in comparative example 3, and the bismuth vanadate prepared in comparative example 3 may have more serious agglomeration from fig. 5, not only reduces the specific surface area of the catalyst, but also causes serious recombination of carriers, thus having lower photocatalytic activity.
Application example 1
The bismuth vanadate prepared in examples 1 to 3 and comparative examples 1 to 3 was used as a catalyst for photodegradation performance against rhodamine B, an organic pollutant.
0.25g of bismuth vanadate prepared in examples 1-3 and comparative examples 1-3 is added into 50mL of rhodamine B aqueous solution with the concentration of 5mg/L as a catalyst, and the mixture is magnetically stirred for 30min in a dark environment to reach adsorption and desorption equilibrium, and then natural light is simulated by adopting a xenon lamp light source with a filter (lambda >420 nm) to carry out photocatalysis reaction. The degradation effect of rhodamine B is shown in FIGS. 4 to 5 and Table 1.
TABLE 1 degradation effects of bismuth vanadate prepared in examples 1-3 and comparative example 1 on rhodamine B at different photocatalytic reaction times
| Catalyst | 30min | 60min | 90min | 120min | 150min | 180min |
| Example 1 | 43.2 | 68.2 | 83.2 | 93.7 | 95.6 | 96.5 |
| Example 2 | 32.2 | 62.6 | 82.4 | 90.2 | 93.4 | 96.1 |
| Example 3 | 24.3 | 58.5 | 73.7 | 87.6 | 93.0 | 95.5 |
| Comparative example 1 | 16.1 | 36.1 | 50.3 | 66.6 | 79.1 | 87.9 |
| Comparative example 2 | 20.8 | 41.9 | 54.0 | 67.4 | 79.6 | 88.1 |
| Comparative example 3 | 28.0 | 45.1 | 53.6 | 69.5 | 82.3 | 88.7 |
FIG. 6 is a graph showing the change of the ultraviolet visible spectrum of the aqueous rhodamine B solution degraded by using the octadecanoic bismuth vanadate prepared in example 1 as a catalyst, and as shown in FIG. 6 and Table 1, the intensity of the characteristic peak of rhodamine B with the wavelength of 553nm is rapidly reduced as the photocatalytic reaction proceeds.
Fig. 7 is a graph showing a change in concentration of rhodamine B solution with respect to time in photodegradation reactions of the octadecanoic bismuth vanadate prepared in example 1 and the decahedral bismuth vanadate prepared in comparative example 1. As can be seen from fig. 7 and table 1, after photocatalytic degradation for 3 hours, the degradation rate of decahedral bismuth vanadate to rhodamine B was 87.9%, while the degradation rate of octadecanhedral bismuth vanadate to rhodamine B was 96.5%, which indicates that compared with decahedral bismuth vanadate, octadecanhedral bismuth vanadate has better photocatalytic performance, and octadecanhedral bismuth vanadate is an ideal catalyst for photodegradation of rhodamine B.
As can be seen from Table 1, after photocatalytic degradation for 3 hours, the degradation rates of the decaoctahedral bismuth vanadate prepared in example 2 and example 3 on rhodamine B were 96.1% and 95.5%, respectively.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An eighteen-body bismuth vanadate, consisting of bismuth vanadate crystals having 18 crystal planes, the 18 crystal planes comprising 2 {010} crystal planes, 8 {110} crystal planes and 8 {121} crystal planes;
the preparation method of the octadecanoic bismuth vanadate comprises the following steps:
placing a nitric acid solution of a bismuth source and an aqueous solution of ammonium metavanadate in a micro-liquid membrane reactor for oxidation-reduction reaction to obtain an amorphous bismuth vanadate suspension;
carrying out hydrothermal reaction on the amorphous bismuth vanadate suspension to obtain decaoctahedral bismuth vanadate;
the hydrothermal reaction comprises sequentially performing a first hydrothermal reaction, a second hydrothermal reaction and a third hydrothermal reaction; the temperature of the first hydrothermal reaction is 90-120 ℃, and the heat preservation time is 0-6 h; the temperature of the second hydrothermal reaction is 120-150 ℃, and the heat preservation time is 0-48 h; the temperature of the third hydrothermal reaction is 150-180 ℃, and the heat preservation time is 0-12 h; the temperature of the first hydrothermal reaction is less than the temperature of the second hydrothermal reaction is less than the temperature of the third hydrothermal reaction; at least 2 of the incubation times of the first, second and third hydrothermal reactions are not 0.
2. The decaoctahedral bismuth vanadate according to claim 1, wherein the bismuth vanadate crystals have a particle size of 3 to 5 μm.
3. The method for preparing the octadecanoic bismuth vanadate according to claim 1 or 2, comprising the following steps:
placing a nitric acid solution of a bismuth source and an aqueous solution of ammonium metavanadate in a micro-liquid membrane reactor for oxidation-reduction reaction to obtain an amorphous bismuth vanadate suspension;
carrying out hydrothermal reaction on the amorphous bismuth vanadate suspension to obtain decaoctahedral bismuth vanadate;
the hydrothermal reaction comprises sequentially performing a first hydrothermal reaction, a second hydrothermal reaction and a third hydrothermal reaction; the temperature of the first hydrothermal reaction is 90-120 ℃, and the heat preservation time is 0-6 h; the temperature of the second hydrothermal reaction is 120-150 ℃, and the heat preservation time is 0-48 h; the temperature of the third hydrothermal reaction is 150-180 ℃, and the heat preservation time is 0-12 h; the temperature of the first hydrothermal reaction is less than the temperature of the second hydrothermal reaction is less than the temperature of the third hydrothermal reaction; at least 2 of the incubation times of the first, second and third hydrothermal reactions are not 0.
4. The method according to claim 3, wherein the concentration of the bismuth source in the nitric acid solution of the bismuth source is 0.1 to 0.5mol/L, and the concentration of the nitric acid solution is 2 to 8mol/L; the bismuth source comprises bismuth salt and/or bismuth oxide;
the concentration of the ammonium metavanadate aqueous solution is 0.1-0.5 mol/;
the molar ratio of the bismuth source to the ammonium metavanadate is 1-1.2: 1 to 1.2.
5. The method according to claim 3, wherein the micro liquid film of the micro liquid film reactor has a width of 100 to 200 μm.
6. The method according to claim 3 or 5, wherein the temperature of the oxidation-reduction reaction is 0 to 30 ℃ for 1 to 5 minutes.
7. Use of the dodecahedral bismuth vanadate as claimed in any one of claims 1 to 2 or the octadecathedral bismuth vanadate as obtainable by the process as claimed in any one of claims 3 to 6 as a catalyst.
8. The use according to claim 7, characterized in that the use of the octadecanoic bismuth vanadate for photocatalytic water splitting reactions, photocatalytic reduction of carbon dioxide or photocatalytic degradation of organic pollutants.
9. The use according to claim 7, characterized in that the mass ratio of the octadecanoic bismuth vanadate to the organic contaminants is 1:0.0002 to 0.001.
10. The use according to claim 8 or 9, wherein the organic contaminant comprises one or more of rhodamine B, methylene blue, methyl orange, malachite green and phenol.
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