CN109985657B - BiVO4/2D g-C3N4Preparation method of Z-type heterojunction photocatalyst - Google Patents
BiVO4/2D g-C3N4Preparation method of Z-type heterojunction photocatalyst Download PDFInfo
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- 229910002915 BiVO4 Inorganic materials 0.000 title claims abstract description 57
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000002360 preparation method Methods 0.000 claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003517 fume Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 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 abstract description 4
- 229940043267 rhodamine b Drugs 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
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- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
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- 229920000877 Melamine resin Polymers 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
- 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 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
Abstract
The invention discloses a BiVO4/2D g‑C3N4The preparation method of the Z-type heterojunction photocatalyst comprises the following specific steps: firstly preparing BiVO by a hydrothermal reaction method4Preparation of graphite-phase carbon nitride (g-C) by thermal polymerization of melamine3N4) 2D g-C obtained by thermal oxidation stripping3N4Then, using methanol as a solvent to prepare BiVO by an ultrasonic-assisted chemical adsorption method4/2D g‑C3N4A Z-type heterojunction photocatalyst. BiVO prepared by the invention4/2D g‑C3N42D g-C in Z-type heterojunction photocatalyst3N4Distributed in BiVO4The surface of the material forms a Z-shaped heterojunction structure, so that photoproduction electrons and holes can be quickly separated, the service life of photoelectrons is prolonged, the recombination rate of the photoproduction electrons and the holes is reduced, the material has good response to visible light, and after the catalytic reaction is carried out for 40min, the degradation rate of the rhodamine B solution can reach 93.0%. The material can be used for photodegradation of organic pollutants and has important significance for environmental management.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and relates to BiVO4/2D g-C3N4A preparation method of a Z-type heterojunction photocatalyst.
Background
The photocatalysis technology using semiconductor oxide as a main body has the advantages of no pollution, simple finished process, capability of directly utilizing solar energy as a reaction light source andcan produce clean energy and the like, and becomes an effective technology for treating environmental pollutants at present. BiVO4As a novel semiconductor material, the photocatalyst has a narrow band gap (about 2.40 eV), excellent visible light response and proper conduction band and valence band positions (compared with a standard hydrogen electrode), and is an effective semiconductor photocatalyst with the capabilities of photolyzing water to generate oxygen, reducing and degrading pollutants. However, BiVO4The photocatalyst has the characteristics of poor charge transport capacity, fast combination, poor adsorptivity and the like, and the photocatalytic activity of the photocatalyst is limited. BiVO4The construction of a proper composite photocatalytic material with other semiconductors is one of effective ways for improving the photoproduction charge separation and prolonging the service life of the photoproduction electron-hole pair.
g-C3N4Is an organic polymer semiconductor, is formed by stacking single-layer carbon nitride sheets layer by layer, has a sheet structure similar to that of graphene, and is called graphite-like phase carbon nitride. The basic constituent structural units on the layer may consist of triazine rings (C)3N3) And heptazine ring (C)6N7) And (4) forming. In both structural units, the C, N atom is sp-bonded2Hybridization by PzThe lone pair electrons on the orbit form a large pi bond similar to a benzene ring structure to form a highly delocalized conjugated system. g-C3N4The conduction band of (A) is composed of C atoms PzAn orbital composition with a conduction band position of about-1.30 eV; and the valence band is P of N atomzOrbital composition, valence band position about 1.40eV, g-C3N4The band gap width of (2.70 eV). As we know, BiVO4And g-C3N4The photocatalyst is compounded into a heterojunction, so that the photocatalytic activity can be improved.
The preparation method in the prior art has the defects of large transmission distance of photon-generated carriers from bulk phase to surface and high recombination rate of photon-generated electron-hole pairs, so that BiVO (BiVO)4And g-C3N4The synergistic effect is difficult to effectively exert, and the further improvement of the photocatalytic activity is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a methodBiVO4/2D g-C3N4The Z-type heterojunction photocatalyst prepared by the preparation method can promote efficient charge separation and has high photocatalytic activity, and 2D g-C in the composite photocatalyst3N4Distributed in BiVO4The surface of the substrate is compounded to form a Z-shaped heterojunction structure, the high oxidation and reduction capacities of the two are fully utilized, and simultaneously, the g-C after thermal oxidation stripping3N4The edge of the Conduction Band (CB) moves to a more negative position, so that the transmission distance of a photon-generated carrier from a bulk phase to the surface is reduced, the separation efficiency of photon-generated electrons and holes is improved, and the photocatalytic performance is effectively improved. Has wide application prospect in the fields of environmental pollution control, energy sources and the like.
The invention is realized by the following steps:
BiVO4/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst specifically comprises the following steps:
s1 preparation of BiVO by hydrothermal reaction method4：
With Bi (NO)3)3·5H2Dissolving O as raw material in HNO with the concentration of 2mol/L3Fully stirring the solution to form solution A; by NH4VO3Dissolving the raw materials in 2mol/L NaOH solution, and fully stirring to form solution B; slowly pouring the solution B into the solution A, continuously stirring to form a yellow mixture suspension, adjusting the pH value to 7-9 by using a NaOH solution with the concentration of 2mol/L, fully stirring, and then, adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle for hydrothermal reaction, respectively washing the sample with water and ethanol after the reaction kettle is cooled to room temperature, and drying to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Will be provided with C3N3(NH2)3The crucible is put into a muffle furnace, calcined to 550 ℃ at the heating rate of 4 ℃/min, calcined for 4 hours, cooled to room temperature, ground, and the obtained sample is bulk phase g-C3N4；
S3, thermal peeling to obtain 2D g-C3N4：
Taking the bulk phase g-C obtained in the step S23N4Performing thermal stripping in an air atmosphere, and calcining at 550 ℃ for 2-4 h at a heating rate of 4-5 ℃/min to obtain 2D g-C3N4；
S4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
2D g-C3N4Dispersing in methanol solution, ultrasonic reacting at room temperature, adding BiVO4Continuing to perform ultrasonic treatment for 1h, stirring in a fume hood for 24h, volatilizing methanol, collecting the obtained product, and drying at 60 ℃ for 12h to obtain BiVO4/2Dg-C3N4A Z-type heterojunction photocatalyst.
Preferably, Bi (NO) is added in step S13)3·5H2O and NH4VO3The molar ratio is 1: 1.
Preferably, the hydrothermal reaction in step S1 is carried out at 180 ℃ for 12h, the drying temperature is 80 ℃, and the drying time is 6-12 h.
Preferably, the thermal peeling is controlled to obtain 2D g-C in step S33N4Mass is thermal peeling precursor phase g-C3N44 to 6 percent of the mass.
Preferably, the ultrasonic reaction time in the step S4 is 1-2 h, and the ultrasonic power is 100-150W.
Preferably, 2D g-C in step S43N4The relation between the addition amount and the methanol addition amount is 10 mg-90 mg/100 mL.
Preferably, BiVO in step S44The addition amount is 2D g-C3N4The mass ratio of the addition amount is (0.1-10): 1.
Compared with the prior art, the invention has the following beneficial effects:
BiVO of the invention4/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is simple, easy to operate, low in cost and environment-friendly. The prepared Z-type heterojunction photocatalyst can promote the efficient separation of charges and has high performancePhotocatalytic activity, 2D g-C in the photocatalyst3N4Distributed in BiVO4The surface of the substrate is compounded to form a Z-shaped heterojunction structure, the high oxidation and reduction capacities of the two are fully utilized, and simultaneously, the g-C after thermal oxidation stripping3N4The edge of the Conduction Band (CB) moves to a more negative position, so that the transmission distance of a photon-generated carrier from a bulk phase to the surface is reduced, the separation efficiency of photon-generated electrons and holes is improved, the photon-generated electron-hole separation device has a quick photon-generated electron-hole separation effect and electron transfer capability, the service life of photoelectrons is prolonged, and the composite photocatalyst has more efficient photocatalytic activity. Has wide application prospect in the fields of environmental pollution control, energy sources and the like.
Drawings
FIG. 1 is BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4XRD pattern of Z type heterojunction photocatalyst;
FIG. 2 is BiVO prepared in example 14/2D g-C3N4SEM image of Z-type heterojunction photocatalyst;
FIG. 3 is BiVO prepared in example 14/2D g-C3N4A high resolution of the Z-type heterojunction photocatalyst;
FIG. 4 is BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4The effect diagram of the Z-type heterojunction photocatalyst for degrading rhodamine B under the irradiation of visible light;
FIG. 5a is BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4An electron spin resonance map of the Z-type heterojunction photocatalyst;
FIG. 5b is BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4Electron spin resonance image of Z-type heterojunction photocatalyst.
Detailed Description
Exemplary embodiments, features and performance aspects of the present invention will be described in detail below with reference to the accompanying drawings.
The invention provides a BiVO4/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst comprises the step of preparing BiVO through a hydrothermal reaction method4Preparation of graphite-phase carbon nitride (g-C) by thermal polymerization of melamine3N4) 2D g-C obtained by thermal oxidation stripping3N4Then, using methanol as a solvent to prepare BiVO by an ultrasonic-assisted chemical adsorption method4/2D g-C3N4The Z-type heterojunction photocatalyst comprises the following specific steps:
s1 preparation of BiVO by hydrothermal reaction method4：
With Bi (NO)3)3·5H2Dissolving O as raw material in HNO with the concentration of 2mol/L3Fully stirring the solution to form solution A; by NH4VO3Dissolving the raw materials in 2mol/L NaOH solution, and fully stirring to form solution B; bi (NO)3)3·5H2O and NH4VO3The molar ratio is 1: 1; slowly pouring the solution B into the solution A, continuously stirring to form a yellow mixture suspension, adjusting the pH value to 7-9 by using a NaOH solution with the concentration of 2mol/L, fully stirring, and then, adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle, reacting for 12h at 180 ℃ for hydrothermal reaction, cooling the kettle to room temperature, washing samples with water and ethanol respectively, and drying at 80 ℃ for 6-12h to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Will be provided with C3N3(NH2)3The crucible is put into a muffle furnace, calcined to 550 ℃ at the heating rate of 4 ℃/min, calcined for 4 hours, cooled to room temperature, ground, and the obtained sample is bulk phase g-C3N4；
S3, hot peeling to obtain 2D g-C3N4：
Taking the bulk phase g-C obtained in the step S23N4Performing thermal stripping in an air atmosphere, and calcining at 550 ℃ for 2-4 h at a heating rate of 4-5 ℃/min to obtain 2D g-C3N4Control of thermal Peel to obtain 2D g-C3N4Mass is thermal peeling precursor phase g-C3N44-6% of the mass, and the best thermal stripping effect is achieved;
s4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
2D g-C3N4Dispersed in a beaker containing methanol, 2D g-C3N4The relation between the addition amount and the methanol addition amount is 10 mg-90 mg/100mL, ultrasonic reaction is carried out at room temperature, the ultrasonic reaction time is 1-2 h, the ultrasonic power is 100-150W, and then BiVO is added4Continuing to perform ultrasonic treatment for 1h, stirring in a fume hood for 24h, volatilizing methanol, collecting the obtained product, and drying at 60 ℃ for 12h to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
Example 1
S1 preparation of BiVO by hydrothermal reaction method4：
0.58g of bismuth nitrate (Bi (NO) was weighed3)3·5H2O) dissolved in 10mL of HNO with a concentration of 2mol/L3The solution was stirred well for 30min to form solution A. 0.14g of ammonium metavanadate (NH) was weighed out4VO3) Dissolved in 10mL of 2mol/L NaOH solution, and fully stirred for 30min to form a B solution. Slowly pouring the solution B into the solution A, continuously stirring to form yellow mixture suspension, adjusting the pH value to 7 by using NaOH solution, then fully stirring for 30min, and adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle, screwing and sealing the hydrothermal kettle, putting the hydrothermal kettle into a 180 ℃ oven, carrying out hydrothermal treatment for 12 hours, cooling the reaction kettle to room temperature, washing a sample with water and ethanol, taking a lower-layer yellow precipitate, and drying at 80 ℃ for 6 hours to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Putting a crucible containing 1g of melamine into a muffle furnace, calcining at the heating rate of 4 ℃/min to 550 ℃, calcining for 4h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4。
S3, hot peeling to obtain 2D g-C3N4：
The obtained bulk phase g-C3N4Placing the mixture into a muffle furnace in the air atmosphere, calcining the mixture to 550 ℃ at the heating rate of 4 ℃/min, and calcining the mixture for 2 hours to obtain 2D g-C3N4；
S4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
50mg of 2D g-C3N4Dispersed in a beaker containing 100mL of methanol, and the beaker was placed in an ultrasonic bath for 1h to obtain uniform g-C3N4A dispersion. Then, 50mg of BiVO was added4Sonication was continued for 1h and stirring in a fume hood for 24 h. After methanol volatilization, the obtained product is collected and dried for 12 hours at the temperature of 60 ℃ to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
FIG. 1 is BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4XRD (X-ray diffraction) pattern of Z-type heterojunction photocatalyst, BiVO (BiVO) in the pattern4Diffraction peak and BiVO4The monoclinic phase (JCPDSNo.14-0688) is corresponding to the crystal phase, and the characteristic diffraction peak is sharp, which shows that the sample prepared by the method is monoclinic phase BiVO with good crystallinity4. 2D g-C in the map3N4The two diffraction peaks at 27.46 DEG and 21.60 DEG are assigned to 2D g-C3N4(JCPDSNo.87-1526) which is a layer-by-layer stacking of carbon nitride and a regular arrangement in the plane of the triazine ring. For the prepared BiVO4/2D g-C3N4An XRD pattern of the Z-type heterojunction photocatalyst comprises monoclinic phase BiVO4And 2D g-C3N4All diffraction peaks of (a) indicate that the composite material consists of BiVO only4And 2D g-C3N4Two substances, no other impurities are present.
FIG. 2 is BiVO prepared in example 14/2D g-C3N4SEM atlas of Z-type heterojunction photocatalyst with sheet junction2D g-C of structure3N4Distributed in BiVO4On the particles, the two are shown to be compounded to form a Z-type heterojunction structure.
FIG. 3 is BiVO prepared in example 14/2D g-C3N4High resolution spectrum of Z-type heterojunction photocatalyst, wherein the interplanar spacing of about 0.309nm corresponds to BiVO4The (121) crystal plane of (2). In contrast, with BiVO4Closely connected regions of weaker crystallinity and blurred crystal lattice belong to 2D g-C3N4And (4) phase(s). Shows BiVO4And 2D g-C3N4A tight interface is formed. Theoretically, the compact interface can be used as a carrier channel, which is beneficial to carrier transfer and improves the photocatalytic performance.
FIG. 4 is BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4And the Z-type heterojunction photocatalyst is an effect diagram for degrading rhodamine B under the irradiation of visible light. In the figure, the area A is dark environment, the area B is irradiated by visible light, and BiVO is measured from the irradiation of the visible light4/2D g-C3N4After the Z-type heterojunction is subjected to catalytic reaction for 40min, the degradation rate of rhodamine B solution reaches 93.0 percent, which indicates that BiVO4/2D g-C3N4The Z-type heterojunction has excellent photocatalytic activity under visible light. Furthermore, BiVO is shown by comparison4/2D g-C3N4The photocatalytic activity of the Z-type heterojunction is obviously superior to that of BiVO4And 2D g-C3N4。
FIGS. 5a and 5b are BiVO prepared in example 14、2D g-C3N4And BiVO4/2D g-C3N4Electron spin resonance image of Z-type heterojunction photocatalyst. Shows. O2-And OH is the main active species in the photocatalytic process. In addition, bind BiVO4And 2D g-C3N4The band structure of (A) proves that the BiVO is formed4/2D g-C3N4A Z-type heterojunction.
Example 2
S1 preparation of BiVO by hydrothermal reaction method4：
0.58g of bismuth nitrate (Bi (NO) was weighed3)3·5H2O) dissolved in 10mL of HNO with a concentration of 2mol/L3The solution was stirred well for 30min to form solution A. 0.14g of ammonium metavanadate (NH) was weighed out4VO3) Dissolved in 10mL of 2mol/L NaOH solution, and fully stirred for 30min to form a B solution. Slowly pouring the solution B into the solution A, continuously stirring to form yellow mixture suspension, adjusting the pH value to 7 by using NaOH solution, then fully stirring for 30min, and adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle, screwing and sealing the hydrothermal kettle, putting the hydrothermal kettle into a 180 ℃ oven, carrying out hydrothermal treatment for 12 hours, cooling the reaction kettle to room temperature, washing a sample with water and ethanol, taking a lower-layer yellow precipitate, and drying at 80 ℃ for 6 hours to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Putting a crucible containing 1g of melamine into a muffle furnace, calcining at the heating rate of 4 ℃/min to 550 ℃, calcining for 2h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4。
S3, hot peeling to obtain 2D g-C3N4：
The obtained bulk phase g-C3N4Placing the mixture into a muffle furnace in the air atmosphere, calcining the mixture to 550 ℃ at the heating rate of 4 ℃/min, and calcining the mixture for 2 hours to obtain 2D g-C3N4；
S4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
10mg of 2D g-C3N4Dispersed in a beaker containing 100mL of methanol, and the beaker was placed in an ultrasonic bath for 1h to obtain uniform g-C3N4A dispersion. Thereafter, 90mgBiVO was added4Sonication was continued for 1h and stirring in a fume hood for 24 h. After methanol volatilization, the obtained product is collected and dried for 12 hours at the temperature of 60 ℃ to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
Example 3
S1 preparation of BiVO by hydrothermal reaction method4：
0.58g of bismuth nitrate (Bi (NO) was weighed3)3·5H2O) dissolved in 10mL of HNO with a concentration of 2mol/L3The solution was stirred well for 30min to form solution A. 0.14g of ammonium metavanadate (NH) was weighed out4VO3) Dissolved in 10mL of 2mol/L NaOH solution, and fully stirred for 30min to form a B solution. Slowly pouring the solution B into the solution A, continuously stirring to form yellow mixture suspension, adjusting the pH value to 7 by using NaOH solution, then fully stirring for 30min, and adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle, screwing and sealing the hydrothermal kettle, putting the hydrothermal kettle into a 180 ℃ oven, carrying out hydrothermal treatment for 12 hours, cooling the reaction kettle to room temperature, washing a sample with water and ethanol, taking a lower-layer yellow precipitate, and drying at 80 ℃ for 6 hours to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Putting a crucible containing 1g of melamine into a muffle furnace, calcining at the heating rate of 4 ℃/min to 550 ℃, calcining for 4h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4。
S3, hot peeling to obtain 2D g-C3N4：
The obtained bulk phase g-C3N4Placing the mixture into a muffle furnace in the air atmosphere, calcining the mixture to 550 ℃ at the heating rate of 4 ℃/min, and calcining the mixture for 2 hours to obtain 2D g-C3N4；
S4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
30mg of 2D g-C3N4Dispersed in a beaker containing 100mL of methanol, and the beaker was placed in an ultrasonic bath for 1h to obtain uniform g-C3N4A dispersion. Thereafter, 70mgBiVO was added4Sonication was continued for 1h and stirring in a fume hood for 24 h. After methanol volatilization, the obtained product is collected and dried for 12 hours at the temperature of 60 ℃ to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
Example 4
S1 preparation of BiVO by hydrothermal reaction method4：
0.58g of bismuth nitrate (Bi (NO) was weighed3)3·5H2O) dissolved in 10mL of HNO with a concentration of 2mol/L3The solution was stirred well for 30min to form solution A. 0.14g of ammonium metavanadate (NH) was weighed out4VO3) Dissolved in 10mL of 2mol/L NaOH solution, and fully stirred for 30min to form a B solution. Slowly pouring the solution B into the solution A, continuously stirring to form yellow mixture suspension, adjusting the pH value to 7 by using NaOH solution, then fully stirring for 30min, and adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle, screwing and sealing the hydrothermal kettle, putting the hydrothermal kettle into a 180 ℃ oven, carrying out hydrothermal treatment for 12 hours, cooling the reaction kettle to room temperature, washing a sample with water and ethanol, taking a lower-layer yellow precipitate, and drying at 80 ℃ for 6 hours to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Putting a crucible containing 1g of melamine into a muffle furnace, calcining at the heating rate of 4 ℃/min to 550 ℃, calcining for 4h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4。
S3, hot peeling to obtain 2D g-C3N4：
The obtained bulk phase g-C3N4Placing the mixture into a muffle furnace in the air atmosphere, calcining the mixture to 550 ℃ at the heating rate of 4 ℃/min, and calcining the mixture for 2 hours to obtain 2D g-C3N4；
S4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
70mg of 2D g-C3N4Dispersed in a beaker containing 100mL of methanol, and the beaker was placed in an ultrasonic bath for 1h to obtain uniform g-C3N4A dispersion. Then, 30mgBiVO was added4Sonication was continued for 1h and stirring in a fume hood for 24 h. After methanol volatilization, the obtained product is collected and dried for 12 hours at the temperature of 60 ℃ to obtain BiVO4/2D g-C3N4Z-type heterojunction photocatalyst。
Example 5
S1 preparation of BiVO by hydrothermal reaction method4：
0.58g of bismuth nitrate (Bi (NO) was weighed3)3·5H2O) dissolved in 10mL of HNO with a concentration of 2mol/L3The solution was stirred well for 30min to form solution A. 0.14g of ammonium metavanadate (NH) was weighed out4VO3) Dissolved in 10mL of 2mol/L NaOH solution, and fully stirred for 30min to form a B solution. Slowly pouring the solution B into the solution A, continuously stirring to form yellow mixture suspension, adjusting the pH value to 7 by using NaOH solution, then fully stirring for 30min, and adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle, screwing and sealing the hydrothermal kettle, putting the hydrothermal kettle into a 180 ℃ oven, carrying out hydrothermal treatment for 12 hours, cooling the reaction kettle to room temperature, washing a sample with water and ethanol, taking a lower-layer yellow precipitate, and drying at 80 ℃ for 6 hours to obtain yellow BiVO4A sample;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Putting a crucible containing 1g of melamine into a muffle furnace, calcining at the heating rate of 4 ℃/min to 550 ℃, calcining for 4h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4；
S3, hot peeling to obtain 2D g-C3N4：
The obtained bulk phase g-C3N4Placing the mixture into a muffle furnace in the air atmosphere, calcining the mixture to 550 ℃ at the heating rate of 4 ℃/min, and calcining the mixture for 2 hours to obtain 2D g-C3N4；
S4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
90mg of 2D g-C3N4Dispersed in a beaker containing 100mL of methanol, and the beaker was placed in an ultrasonic bath for 1h to obtain uniform g-C3N4A dispersion. Then, 10mgBiVO was added4Sonication was continued for 1h and stirring in a fume hood for 24 h. After methanol volatilization, the obtained product is collected and dried for 12 hours at the temperature of 60 ℃ to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
In conclusion, BiVO prepared by the invention4/2D g-C3N4The Z-type heterojunction photocatalyst has more efficient photocatalytic activity. Has wide application prospect in the fields of environmental pollution control, energy sources and the like.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. BiVO4/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: the method specifically comprises the following steps:
s1 preparation of BiVO by hydrothermal reaction method4：
With Bi (NO)3)3·5H2Dissolving O as raw material in HNO with the concentration of 2mol/L3Fully stirring the solution to form solution A; by NH4VO3Dissolving the raw materials in 2mol/L NaOH solution, and fully stirring to form solution B; slowly pouring the solution B into the solution A, continuously stirring to form a yellow mixture suspension, adjusting the pH value to 7-9 by using a NaOH solution with the concentration of 2mol/L, fully stirring, and then, adding the prepared BiVO4Pouring the precursor solution into a hydrothermal kettle for hydrothermal reaction, respectively washing the sample with water and ethanol after the reaction kettle is cooled to room temperature, and drying to obtain yellow BiVO4A sample; the hydrothermal reaction is carried out for 12 hours at 180 ℃, the drying temperature is 80 ℃, and the drying time is 6-12 hours;
s2 preparation of bulk phase g-C by thermal polymerization3N4：
Will be provided with C3N3(NH2)3Is put into the crucibleCalcining in a muffle furnace at a heating rate of 4 ℃/min to 550 ℃ for 4h, cooling to room temperature, grinding to obtain a sample of bulk phase g-C3N4；
S3, hot peeling to obtain 2D g-C3N4：
Taking the bulk phase g-C obtained in the step S23N4Performing thermal stripping in an air atmosphere, and calcining at 550 ℃ for 2-4 h at a heating rate of 4-5 ℃/min to obtain 2D g-C3N4(ii) a Obtained 2D g-C3N4Mass is thermal peeling precursor phase g-C3N44-6% of the mass;
s4 preparation of BiVO by ultrasonic-assisted chemical adsorption method4/2D g-C3N4Z-type heterojunction photocatalyst:
2D g-C3N4Dispersing in methanol solution, ultrasonic reacting at room temperature, adding BiVO4Continuing to perform ultrasonic treatment for 1h, stirring in a fume hood for 24h, volatilizing methanol, collecting the obtained product, and drying at 60 ℃ for 12h to obtain BiVO4/2D g-C3N4A Z-type heterojunction photocatalyst.
2. BiVO according to claim 14/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: bi (NO) added in step S13)3·5H2O and NH4VO3The molar ratio is 1: 1.
3. BiVO according to claim 14/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: in the step S4, the time of the ultrasonic reaction is 1-2 h, and the ultrasonic power is 100-150W.
4. BiVO according to claim 14/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: 2D g-C in step S43N4The relation between the addition amount and the methanol addition amount is 10 mg-90 mg/100 mL.
5. BiVO according to claim 1 or 44/2D g-C3N4The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps: BiVO in step S44The addition amount is 2D g-C3N4The mass ratio of the addition amount is (0.1-10): 1.
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| CN114849690B (en) * | 2022-06-09 | 2023-06-16 | 武汉理工大学 | S-shaped SbVO 4 /g-C 3 N 4 Composite photocatalyst, preparation method and application thereof |
| CN115025805B (en) * | 2022-07-08 | 2023-07-25 | 成都大学 | BiVO (binary organic acid) 4 /g-C 3 N 4 AgBr ternary composite photocatalyst and preparation method thereof |
| CN116474809A (en) * | 2023-04-12 | 2023-07-25 | 江苏大学 | Preparation method and application of bismuth nanoparticle modified carbon nitride photocatalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990485A (en) * | 2014-05-27 | 2014-08-20 | 天津大学 | Carbon nitride nano particle modified pucherite composite photocatalyst and preparation method thereof |
| KR101725059B1 (en) * | 2015-11-27 | 2017-04-26 | 이화여자대학교 산학협력단 | System for photocatalytic activation |
| CN107051567A (en) * | 2017-03-22 | 2017-08-18 | 陕西科技大学 | A kind of carbonitride/(040) crystal face pucherite hetero-junctions and its preparation method and application |
| CN109622013A (en) * | 2018-12-07 | 2019-04-16 | 陕西科技大学 | One type graphite phase carbon nitride-(110) crystal face pucherite Z-type heterojunction photocatalyst and its preparation method and application |
-
2019
- 2019-04-30 CN CN201910395741.7A patent/CN109985657B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103990485A (en) * | 2014-05-27 | 2014-08-20 | 天津大学 | Carbon nitride nano particle modified pucherite composite photocatalyst and preparation method thereof |
| KR101725059B1 (en) * | 2015-11-27 | 2017-04-26 | 이화여자대학교 산학협력단 | System for photocatalytic activation |
| CN107051567A (en) * | 2017-03-22 | 2017-08-18 | 陕西科技大学 | A kind of carbonitride/(040) crystal face pucherite hetero-junctions and its preparation method and application |
| CN109622013A (en) * | 2018-12-07 | 2019-04-16 | 陕西科技大学 | One type graphite phase carbon nitride-(110) crystal face pucherite Z-type heterojunction photocatalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| BiVO4/g-C3N4composite visible-light photocatalyst for effective elimination of aqueous organic pollutants;Jie Zhao等;《Journal of Molecular Catalysis A: Chemical》;20160825;第424卷;摘要，第2.1节 * |
| Enhancement of visible-light photocatalytic activities of BiVO4 coupled with g-C3N4 prepared using different precursors;Peipei Cui等;《Environmental Science and Pollution Research》;20180920;第25卷;第32467页右栏第3段至第32468页左栏第1段 * |
| Graphene-Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities;Ping Niu等;《Advanced functional materials》;20120705;第22卷;摘要，第4节experimental section * |
| 第22卷;Man Ou等;《Journal of Alloys and Compounds》;20141202;第626卷;第2.2节 * |
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