CN115814782A - BiVO 4 Preparation method of base-pressure electro-optic catalytic composite nano material - Google Patents
BiVO 4 Preparation method of base-pressure electro-optic catalytic composite nano material Download PDFInfo
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- 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 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
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- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 14
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 20
- 239000000969 carrier Substances 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 abstract 1
- 229960001482 bismuth subnitrate Drugs 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
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- 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 3
- 238000000034 method Methods 0.000 description 3
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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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Abstract
The invention discloses a BiVO 4 The preparation method of base-pressure electro-optic catalytic composite nano material is characterized by that it uses Bi 2 O 3 P25 and a flux are mixed at a molar ratio of 2 4 Ti 3 O 12 Adding the bismuth nitrate pentahydrate and the sodium dodecyl benzene sulfonate into a nitric acid solution, and uniformly stirring to obtain a precursor solution of bismuth; dissolving ammonium metavanadate in an aqueous solution of sodium hydroxide to obtain a precursor solution of vanadium, dropwise adding the precursor solution of vanadium into a precursor solution of bismuth, uniformly stirring, adjusting the pH value to 3-7, then transferring the solution to a reaction kettle for hydrothermal reaction, and washing, precipitating and drying after the hydrothermal reaction is finished to obtain the vanadium-containing bismuth subnitrate. And pure phase BiVO 4 And the existing BiVO 4 Compared with the base heterojunction photocatalytic material, the invention has the advantages of simple preparation process, low cost, and good photocatalytic effectThe nano material has high transfer efficiency of photo-generated carriers inside, good photocatalytic activity and photocatalytic cycle stability, and strong reduction capability on potassium dichromate pollutants.
Description
Technical Field
The invention belongs to the technical field of photocatalyst preparation and sewage treatment, and particularly relates to BiVO 4 A preparation method of a base-voltage electro-optic catalytic composite nano material.
Background
Photocatalysis as a new high-efficiency and green technology has a huge development prospect in the aspect of water pollution treatment. BiVO 4 As a narrow band gap semiconductor, the material has certain absorption capacity to visible light. Furthermore, biVO 4 Also has excellent oxidizing ability, so that the composite material has great application potential in the aspects of decomposing water and degrading organic pollutants. However, pure phase BiVO 4 The defects of high recombination rate of internal photon-generated carriers lead the photocatalytic performance of the photocatalyst to be relatively low in practical application, and the industrial application of the photocatalyst from a laboratory is inhibited.
By synthesizing BiVO 4 The base heterojunction photocatalytic material can solve the problem and synthesize BiVO 4 The base heterojunction photocatalytic material not only can effectively separate photon-generated carriers, but also can stack the advantages of different element phases to improve BiVO 4 Photocatalytic activity. But the existing BiVO 4 The base heterojunction photocatalytic material still has the problem of poor photocatalytic activity. How to promote BiVO as one of important factors influencing the activity of photocatalyst 4 The migration of the photogenerated carriers in the basic heterostructure becomes the key to improve the photocatalytic activity. If an interface fusion effect is formed between different element phases, a smooth carrier migration channel is constructed, the migration efficiency of photo-generated electrons and holes can be greatly improved, the number of photo-generated carriers participating in a photo-oxidation-reduction reaction is increased, and thus BiVO (BiVO volume) is improved 4 Photocatalytic degradation activity of (1).
Under the action of external force, the piezoelectric material is easy to bend, so that a polarization electric field is generated, and a driving force can be provided for separation of photon-generated carriers。Bi 4 Ti 3 O 12 Has large spontaneous polarization and excellent piezoelectric response effect, and is widely applied to the research of the piezoelectric ceramics. Due to the unique layered perovskite structure, the method also shows wide application in the field of photocatalysis. No introduction of Bi has been found at present 4 Ti 3 O 12 Construction of BiVO 4 Report of base heterojunction photocatalytic materials.
Disclosure of Invention
The invention aims to solve the problem of pure-phase BiVO in the prior art 4 High recombination rate of internal photo-generated carriers and the existing BiVO 4 The problem of poor photocatalytic activity of a base heterojunction photocatalytic material is that BiVO is provided 4 The prepared nano material has high transfer efficiency of photo-generated carriers in the interior, good photocatalytic activity and photocatalytic cycle stability, and strong reduction capability on potassium dichromate pollutants.
Technical scheme
The invention introduces Bi which is also Bi system 4 Ti 3 O 12 By constructing BiVO 4 -Bi 4 V 2 O 10 -Bi 4 Ti 3 O 12 The heterostructure realizes BiVO 4 The photocatalytic pollutant degradation activity is greatly improved, the elementary phase interface fusion of the catalyst and the carrier migration state are regulated, the separation and migration efficiency of photo-generated electrons and holes is improved, and the development of photocatalytic organic pollutant degradation industrialization is facilitated. The specific scheme is as follows:
BiVO 4 The preparation method of the base-pressure electro-optic catalytic composite nano material comprises the following steps:
(1) Adding Bi 2 O 3 P25 and a flux are mixed at a molar ratio of 2 4 Ti 3 O 12 ；
(2) Adding Bi 4 Ti 3 O 12 Adding into nitric acid solution, stirring, adding bismuth nitrate pentahydrate and sodium dodecyl benzene sulfonate, stirring and mixingObtaining precursor solution of bismuth;
(3) Dissolving ammonium metavanadate in an aqueous solution of sodium hydroxide to obtain a precursor solution of vanadium;
(4) Dropwise adding the precursor solution of vanadium into the precursor solution of bismuth, uniformly stirring, and adjusting the pH value to 3-7 to obtain a mixed solution;
(5) Transferring the mixed solution obtained in the step (4) into a reaction kettle for hydrothermal reaction, washing and precipitating with deionized water and absolute ethyl alcohol after the reaction is finished, and finally drying to obtain BiVO 4 A base-pressure electro-optic catalytic composite nano material.
Further, in the step (1), the fluxing agent is composed of KCl and NaCl in a molar ratio of 1:1.
Further, in the step (1), the calcining temperature is 800-900 ℃ and the time is 100-150min.
Further, in the step (1), the drying temperature is 80 ℃.
Further, in the step (2), the Bi 4 Ti 3 O 12 The molar ratio of the bismuth nitrate pentahydrate to the bismuth nitrate pentahydrate is (0.5-8) 100, and the molar ratio is more preferably 3; the molar ratio of the bismuth nitrate pentahydrate to the sodium dodecyl benzene sulfonate is 1: (0.2-0.3).
Further, in the step (2), the concentration of the nitric acid solution is 4mol/L.
Further, in the step (3), the molar ratio of the ammonium metavanadate to the bismuth nitrate pentahydrate is 1:1.
Further, in the step (5), the hydrothermal reaction temperature is 180-200 ℃ and the time is 2-6h.
Further, in the step (5), the drying temperature is 60 ℃ and the drying time is 8-12h.
The invention has the beneficial effects that:
the lamellar BiVO is synthesized by in-situ growth by adopting a simple hydrothermal method 4 -Bi 4 V 2 O 10 -Bi 4 Ti 3 O 12 The pH of the precursor solution is adjusted to regulate the microscopic morphology of the composite nanomaterial, wherein BiVO in the composite nanomaterial 4 、Bi 4 V 2 O 10 And Bi 4 Ti 3 O 12 The energy level matching between the two materials and the interface fusion effect between the two materials inhibit the recombination of photon-generated carriers, and the Bi material 4 Ti 3 O 12 As a piezoelectric material, a generated polarization electric field can effectively separate photon-generated carriers, so that the prepared composite nano material has excellent photocatalytic activity; the composite nano material prepared by the invention shows excellent reduced Cr under the combined action of ultrasound and illumination 6+ The performance is good, and the photocatalytic cycle stability is good; the preparation process of the invention has simple flow and low cost, and is beneficial to industrial popularization and application.
Drawings
FIG. 1 shows BiVO prepared in examples 1 to 3 4 XRD pattern of the base-voltage electro-optic catalytic composite nano material;
FIG. 2 is BiVO prepared in example 1 4 Electron microscope images of the base voltage electro-optic catalytic composite nano-material;
FIG. 3 shows BiVO prepared in examples 1-3 4 DRS diagram of the base voltage electro-optic catalytic composite nano material;
FIG. 4 shows BiVO prepared in examples 1-3 4 Reduction of Cr from base-voltage electro-optic catalytic composite nano material under illumination and ultrasonic conditions 6+ The test result of (1);
FIG. 5 shows BiVO prepared in examples 1-3 4 Reduction of Cr from base-voltage electro-optic catalytic composite nano material under illumination condition 6+ The test result of (2);
FIG. 6 shows BiVO prepared in example 1 4 And testing the chemical stability of the base-voltage electro-optic catalytic composite nano material.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
Example 1
BiVO 4 The preparation method of the base-pressure electro-optic catalytic composite nano material comprises the following steps:
(1) 0.931g of Bi 2 O 3 0.239g P25, 3.727g KCl and 2.922g NaCl, grinding for 30min, calcining at 800 deg.C for 120min, coolingThen respectively centrifugally washing the mixture for 6 times by using deionized water and absolute ethyl alcohol, and drying the mixture for 12 hours at 80 ℃ to obtain Bi 4 Ti 3 O 12 ；
(2) 0.070g of Bi 4 Ti 3 O 12 Adding the bismuth nitrate into 10mL of a 4mol/L nitric acid solution, stirring for 60min, then adding 0.971g of bismuth nitrate pentahydrate and 0.1986g of sodium dodecyl benzene sulfonate, and stirring for 60min to obtain a precursor solution of bismuth;
(3) Dissolving 0.234g of ammonium metavanadate in 10mL of 2mol/L sodium hydroxide aqueous solution to obtain a precursor solution of vanadium;
(4) Dropwise adding the precursor solution of vanadium into the precursor solution of bismuth, stirring for 60min, and adjusting the pH value to 7 by using 2mol/L sodium hydroxide aqueous solution to obtain a mixed solution;
(5) Transferring the mixed solution obtained in the step (4) into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, after the reaction is finished, respectively carrying out centrifugal washing and precipitation for 6 times by using deionized water and absolute ethyl alcohol, and finally drying for 12h at 60 ℃ to obtain BiVO 4 The base-pressure electro-optic catalytic composite nano material is marked as BTO/BVO-3.
Example 2
BiVO 4 The preparation method of the base-pressure electro-optic catalytic composite nano material comprises the following steps:
(1) 0.931g of Bi 2 O 3 0.239g P25, 3.727g KCl and 2.922g NaCl are mixed, ground for 30min, calcined for 120min at 800 ℃, cooled, centrifugally washed for 6 times by deionized water and absolute ethyl alcohol respectively, and dried for 12h at 80 ℃ to obtain Bi 4 Ti 3 O 12 ；
(2) 0.0117g of Bi 4 Ti 3 O 12 Adding the bismuth nitrate into 10mL of a 4mol/L nitric acid solution, stirring for 60min, then adding 0.971g of bismuth nitrate pentahydrate and 0.1986g of sodium dodecyl benzene sulfonate, and stirring for 60min to obtain a precursor solution of bismuth;
(3) Dissolving 0.234g of ammonium metavanadate in 10mL of 2mol/L sodium hydroxide aqueous solution to obtain a precursor solution of vanadium;
(4) Dropwise adding the precursor solution of vanadium into the precursor solution of bismuth, stirring for 60min, and adjusting the pH value to 7 by using 2mol/L sodium hydroxide aqueous solution to obtain a mixed solution;
(5) Transferring the mixed solution obtained in the step (4) into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, after the reaction is finished, respectively carrying out centrifugal washing and precipitation for 6 times by using deionized water and absolute ethyl alcohol, and finally drying for 12h at 60 ℃ to obtain BiVO 4 The base-pressure electro-optic catalytic composite nano material is marked as BTO/BVO-0.5.
Example 3
BiVO 4 The preparation method of the base-pressure electro-optic catalytic composite nano material comprises the following steps:
(1) 0.931g of Bi 2 O 3 0.239g P25, 3.727g KCl and 2.922g NaCl are mixed, ground for 30min, calcined for 120min at 800 ℃, cooled, centrifugally washed for 6 times by deionized water and absolute ethyl alcohol respectively, and dried for 12h at 80 ℃ to obtain Bi 4 Ti 3 O 12 ；
(2) 0.187g of Bi 4 Ti 3 O 12 Adding the bismuth nitrate into 10mL of a 4mol/L nitric acid solution, stirring for 60min, then adding 0.971g of bismuth nitrate pentahydrate and 0.1986g of sodium dodecyl benzene sulfonate, and stirring for 60min to obtain a precursor solution of bismuth;
(3) Dissolving 0.234g of ammonium metavanadate in 10mL of 2mol/L sodium hydroxide aqueous solution to obtain a precursor solution of vanadium;
(4) Dropwise adding the precursor solution of vanadium into the precursor solution of bismuth, stirring for 60min, and adjusting the pH value to 7 by using 2mol/L sodium hydroxide aqueous solution to obtain a mixed solution;
(5) Transferring the mixed solution obtained in the step (4) into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, after the reaction is finished, respectively carrying out centrifugal washing and precipitation for 6 times by using deionized water and absolute ethyl alcohol, and finally drying for 12h at 60 ℃ to obtain BiVO 4 The base-pressure electro-optic catalytic composite nano material is marked as BTO/BVO-8.
Comparative example 1
With Bi 4 Ti 3 O 12 As comparative example 1, bi 4 Ti 3 O 12 The preparation method comprises the following steps: 0.931g of Bi 2 O 3 0.239g P25, 3.727gKCl and 2.922g NaCl, grinding for 30min, and calcining at 800 deg.C for 120min, cooling, respectively centrifugally washing with deionized water and absolute ethyl alcohol for 6 times, and drying at 80 ℃ for 12h to obtain Bi 4 Ti 3 O 12 And is marked as BTO.
Comparative example 2
With BiVO 4 -Bi 4 V 2 O 10 BiVO as comparative example 2 4 -Bi 4 V 2 O 10 The preparation method comprises the following steps: adding 0.971g of bismuth nitrate pentahydrate and 0.1986g of sodium dodecyl benzene sulfonate into 10mL of 4mol/L nitric acid solution, and stirring for 60min to obtain a precursor solution of bismuth; dissolving 0.234g of ammonium metavanadate in 10mL of 2mol/L sodium hydroxide aqueous solution to obtain a precursor solution of vanadium; dropwise adding a vanadium precursor solution into a bismuth precursor solution, stirring for 60min, adjusting the pH value to 7 by using 2mol/L sodium hydroxide aqueous solution, transferring the obtained mixed solution into a 100mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 5h at 200 ℃, respectively carrying out centrifugal washing on precipitates obtained after the reaction for 6 times by using deionized water and penta-ethanol, and finally drying for 12h at 60 ℃ to obtain BiVO 4 -Bi 4 V 2 O 10 And is recorded as BVO.
And (3) performance testing:
1. BiVO prepared in examples 1-3 4 The XRD pattern of the base-voltage electro-optic catalytic composite nano material is shown in figure 1, and different Bi can be seen from figure 1 4 Ti 3 O 12 Content of BiVO 4 -Bi 4 V 2 O 10 -Bi 4 Ti 3 O 12 Characteristic peak of heterojunction and BiVO 4 、Bi 4 V 2 O 10 And Bi 4 Ti 3 O 12 And (5) the consistency is achieved. Thus, the heterojunction photocatalytic material is successfully synthesized.
2. BiVO prepared in example 1 4 The electron microscope image of the base voltage electro-optic catalytic composite nano material is shown in figure 2, and figures 2 (a) and 2 (b) are respectively a transmission electron microscope image and a scanning electron microscope image of the material, and it can be seen that the BiVO is prepared 4 -Bi 4 V 2 O 10 -Bi 4 Ti 3 O 12 The micro-morphology of the heterojunction is lamellar, more active sites are provided for photocatalytic reaction, good surface-to-surface contact is realized between the active sites, and current carriers are shortenedThe recombination of the photogenerated carriers is suppressed.
3. FIG. 3 shows BiVO prepared in examples 1-3 4 The DRS diagram of the base voltage electro-optic catalytic composite nano material, wherein, the diagram (a) is the ultraviolet visible diffuse reflection spectrum of the material, the diagram (b) is the forbidden bandwidth of the material, and the Bi can be seen 4 Ti 3 O 12 The introduction of (2) reduces the forbidden bandwidth of the photocatalytic material to a certain extent, which shows that the two-dimensional BiVO is constructed 4 -Bi 4 V 2 O 10 -Bi 4 Ti 3 O 12 The heterojunction enables the light absorption intensity of the photocatalyst to be improved to a certain extent, and the absorption band edge of the photocatalyst has a certain red shift, which is beneficial to absorbing more visible light.
4. BiVO prepared in example 1-2 4 The base-pressure electro-optic catalytic composite nano material is used for reducing Cr under different conditions 6+ Tested and compared to BTO of comparative example 1, BVO of comparative example 2:
method I, cr reduction under the conditions of illumination and ultrasound 6+
50mg of photocatalytic material was weighed into 100mL of 4X 10 -5 M K 2 Cr 2 O 7 To the solution, 2mL of methanol solution was added and the mixture was washed with 0.01M H 2 SO 4 Adjusting the pH value to 3, and stirring for 30min under the dark condition to reach adsorption balance. Placing the beaker containing the above solution into an ultrasonic cleaning machine, and subjecting to ultrasonic treatment (200W, 40kHz) and illumination (300W, 205.6mW cm) -2 Xenon lamp) under the combined action of a reducing agent. 4mL of the solution is taken every 10min and centrifuged at 6000R/min for 8min, the centrifuged supernatant is taken, the absorbance is measured in a spectrophotometer, and the degradation efficiency (R) is calculated according to the following formula.
R＝(C 0 -C t )/C 0 X 100% where C 0 Is Cr 6+ Ct is the concentration measured for each sample.
The test results are shown in FIG. 4.
Method II, reducing Cr under illumination condition 6+
50mg of photocatalytic material was weighed into 100mL of 4X 10 -5 M K 2 Cr 2 O 7 To the solution, 2mL of methanol solution was added and the mixture was washed with 0.01M H 2 SO 4 The pH was adjusted to 3. Stirring for 30min under dark condition to reach adsorption equilibrium. The beaker with the above solution was kept in the light condition only (power 300W,205.6mW cm) -2 Xenon lamp) was used. And (3) centrifuging 4mL of solution at a speed of 6000r/min for 8min every 10min, taking the centrifuged supernatant, testing absorbance in a spectrophotometer, and calculating degradation efficiency.
The test results are shown in FIG. 5.
As can be seen from FIGS. 4 and 5, biVO prepared by the example of the present invention 4 The base-pressure electro-optic catalytic composite nano material shows excellent reduced Cr 6+ Performance, reduction of Cr by comparison of photo-catalysis and piezoelectric photo-catalysis 6+ The performance test and the introduction of a built-in electric field can effectively improve the photocatalytic activity. This demonstrates that the built-in electric field favors the separation of photogenerated carriers.
5. BiVO prepared in example 1 4 Chemical stability test of base-voltage electro-optic catalytic composite nano material
50mg of photocatalytic material was weighed into 100mL of 4X 10 -5 M K 2 Cr 2 O 7 To the solution, 2mL of methanol solution was added and the mixture was washed with 0.01M H 2 SO 4 The pH was adjusted to 3. Stirring for 30min under dark condition to reach adsorption equilibrium. The beaker with the above solution was kept in the light condition only (power 300W,205.6mW cm) -2 Xenon lamp) was used. 4mL of the solution was centrifuged at 6000r/min for 8min every 10 min. Taking the centrifuged supernatant, testing the absorbance in a spectrophotometer, and calculating the degradation efficiency. Centrifuging the used catalyst, washing with ethanol for several times, drying, and reducing Cr again under the same conditions 6+ And testing, calculating degradation efficiency, and repeating for 5 times.
FIG. 6 shows the results of the chemical stability test, and it can be seen that BiVO 4 -Bi 4 V 2 O 10 -Bi 4 Ti 3 O 12 The heterojunction is subjected to 5-cycle test, and then Cr is reduced 6+ Only a slight decrease in performance occurred. This illustrates the formation of components between the heterostructures built by in situ hydrothermal methodStronger chemical bond is formed, and the chemical stability of the catalyst is improved.
Claims (9)
1. BiVO 4 The preparation method of the base-pressure electro-optic catalytic composite nano material is characterized by comprising the following steps of:
(1) Adding Bi 2 O 3 P25 and a flux are mixed at a molar ratio of 2 4 Ti 3 O 12 ；
(2) Adding Bi 4 Ti 3 O 12 Adding the bismuth nitrate pentahydrate and the sodium dodecyl benzene sulfonate into a nitric acid solution, stirring uniformly, and then adding the bismuth nitrate pentahydrate and the sodium dodecyl benzene sulfonate, stirring and mixing uniformly to obtain a precursor solution of bismuth;
the Bi 4 Ti 3 O 12 The molar ratio of the bismuth nitrate pentahydrate to the bismuth nitrate pentahydrate is (0.5-8) and 100, and the molar ratio of the bismuth nitrate pentahydrate to the sodium dodecyl benzene sulfonate is 1: (0.2-0.3);
(3) Dissolving ammonium metavanadate in an aqueous solution of sodium hydroxide to obtain a precursor solution of vanadium;
(4) Dropwise adding the precursor solution of vanadium into the precursor solution of bismuth, uniformly stirring, and adjusting the pH value to 3-7 to obtain a mixed solution;
(5) Transferring the mixed solution obtained in the step (4) into a reaction kettle for hydrothermal reaction, washing and precipitating with deionized water and absolute ethyl alcohol after the reaction is finished, and finally drying to obtain BiVO 4 The base-pressure electro-optic catalytic composite nano material.
2. BiVO according to claim 1 4 The preparation method of the base-voltage electro-optic catalytic composite nano material is characterized in that in the step (1), the fluxing agent consists of KCl and NaCl with the molar ratio of 1:1.
3. BiVO according to claim 1 4 The preparation method of the base-pressure electro-optic catalytic composite nano material is characterized in that in the step (1), the calcination temperature is 800-900 ℃ and the calcination time is 100-150min.
4. BiVO according to claim 1 4 The preparation method of the base-voltage electro-optic catalytic composite nano material is characterized in that in the step (1), the drying temperature is 80 ℃.
5. BiVO according to claim 1 4 The preparation method of the base-pressure electro-optic catalytic composite nano material is characterized in that in the step (2), the Bi is 4 Ti 3 O 12 The molar ratio of the bismuth nitrate pentahydrate to the bismuth nitrate pentahydrate is 3.
6. BiVO of claim 1 4 The preparation method of the base-pressure electro-optic catalytic composite nano material is characterized in that in the step (2), the concentration of the nitric acid solution is 4mol/L.
7. BiVO according to claim 1 4 The preparation method of the base-pressure electro-optic catalytic composite nano material is characterized in that in the step (3), the molar ratio of the ammonium metavanadate to the bismuth nitrate pentahydrate is 1:1.
8. BiVO according to claim 1 4 The preparation method of the base-pressure electro-optic catalytic composite nano material is characterized in that in the step (5), the hydrothermal reaction temperature is 180-200 ℃ and the time is 2-6h.
9. BiVO according to any one of claims 1 to 8 4 The preparation method of the base-voltage electro-optic catalytic composite nano material is characterized in that in the step (5), the drying temperature is 60 ℃ and the time is 8-12h.
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