CN108404926B - Amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst and preparation method and application thereof - Google Patents
Amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst and preparation method and application thereof Download PDFInfo
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 74
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 66
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 58
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 57
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 22
- 239000011651 chromium Substances 0.000 claims abstract description 22
- 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 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 19
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- 239000002245 particle Substances 0.000 claims abstract description 7
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of nano composite materials, and particularly discloses an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing a glycerol solution of bismuth nitrate, graphene powder, an ammonium metavanadate aqueous solution and an iron nitrate solution to obtain a precursor solution, carrying out hydrothermal reaction, adding an ascorbic acid solution, standing under the protection of inert gas, alternately washing with absolute ethyl alcohol and deionized water, and drying to obtain the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst. The amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst prepared by the method has the particle size of less than 50nm, has a large specific surface area, has photocatalytic activity far exceeding that of pure bismuth vanadate or ferric vanadate, can be used for deep treatment of photocatalytic reduction of Cr (VI) and chromium-containing wastewater, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst and a preparation method and application thereof.
Background
With the rapid development of global economy, the environmental pollution problem is increasingly prominent, and the heavy metal pollution is particularly serious. Wherein, the chromium (usually Cr (VI)) containing organic wastewater pollution mainly comes from industrial pigment wastewater, leather preparation wastewater, electroplating wastewater and the like, the biochemical degree of the wastewater is low, the treatment difficulty is large, and the catalyst used in the prior advanced oxidation technology can only treat the organic pollutants singly, but does not have the capability of treating heavy metals such as hexavalent chromium and the like. In the traditional technical research, a semiconductor photocatalysis technology represented by taking titanium dioxide as a core is widely applied to the field of environmental pollution treatment, but the band gap width of the titanium dioxide is 3.2eV, the titanium dioxide only reacts under the irradiation of ultraviolet light, and the practicability is poor. Therefore, in order to solve the pollution problem of the chromium-containing organic wastewater, a novel photocatalyst capable of effectively degrading Cr (VI) under visible light is urgently needed to be developed.
Bismuth vanadate as a semiconductor with visible light response activity mainly has three crystal forms: tetragonal zircon type (zt), tetragonal scheelite type (s-t), monoclinic scheelite type (s-m). The monoclinic phase bismuth vanadate has the forbidden band width of about 2.40eV, can generate photoproduction electrons and photoproduction holes under visible light, and has excellent chemical stability in aqueous solution, no toxicity or harm and low preparation cost. The bismuth vanadate has wide development prospect in the technical fields of organic pollutant degradation, hydrogen and oxygen production by water photolysis and the like. However, the pure phase bismuth vanadate has the defects of easy recombination of photon-generated carriers and poor surface adsorption capability.
The carbon atoms in graphene are arranged in the plane of the monoatomic layer in the form of six-membered rings, and the C atom having four valence electrons contributes one unbound valence electron. The valence electrons form conjugated delocalized large bonds in a direction perpendicular to a plane in a two-dimensional crystal structure of a monoatomic layer, so that electrons can freely move in the crystal, and graphene has excellent electron conduction performance. In addition, the graphene also has excellent mechanical properties, high light transmittance and high specific surface area, and can be used for preparing various functionalized graphene composite materials. Due to the outstanding performance and the easy processability of the graphene, the graphene has a good application prospect in the field of photocatalysis, and the excellent conductivity can be used for conducting photo-generated electrons to the surface of a material more quickly, so that photo-generated electron-hole pairs are effectively separated, and the recombination rate of the photo-generated electron-hole pairs is reduced.
Has already been studiedThe method proves that the preferential growth of the {010} crystal face of the bismuth vanadate crystal can be promoted to a certain extent by loading a small amount of graphene on the surface of the bismuth vanadate, and the preferential growth of the crystal face is beneficial to improving the separation efficiency of photo-generated electron-hole pairs. Meanwhile, a great amount of sp-derived materials exist on the surface of the graphene2The connected conjugated carbon network can localize electrons, so that the bismuth vanadate composite material has good conductivity and can further accelerate the conduction of photon-generated carriers on the surface of the bismuth vanadate composite material. However, most of the bismuth vanadate-graphene composite materials reported at present are regular crystalline structures, the particle size is more than 100-200 nm, the specific surface area is small, and the photocatalytic performance of the bismuth vanadate-graphene composite materials still needs to be improved; the amorphous composite material in the amorphous state generally has the defects of large grain size, poor adsorption capacity, difficulty in separation of photon-generated carriers and low photocatalytic efficiency due to easy recombination of electron hole pairs.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst, wherein the particle size of the composite photocatalyst prepared by the method is less than 50nm, the composite photocatalyst has a high specific surface area, and the photocatalytic activity of the composite photocatalyst is far higher than that of pure bismuth vanadate or ferric vanadate.
The invention also aims to provide an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst.
The invention also aims to provide application of the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst in advanced treatment of chromium-containing wastewater and/or Cr (VI) photocatalytic reduction.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst comprises the following steps:
s1, preparing a glycerol solution of bismuth nitrate, adding graphene powder, and carrying out ultrasonic stirring for 10-15 min;
s2, preparing an ammonium metavanadate aqueous solution and an iron nitrate solution; uniformly mixing the glycerol solution of the bismuth nitrate treated in the step S1 with the ferric nitrate solution, adding an ammonium metavanadate aqueous solution after clarification, stirring for 15-30 min, adjusting the pH value to 4-7 to obtain a precursor solution, standing and aging for 1-2 h;
s3, placing the precursor solution obtained in the step S2 at a constant temperature of 158-162 ℃ for hydrothermal reaction for 10-20 h to obtain a bright yellow suspension;
s4, standing the bright yellow suspension obtained in the step S3 for 10-30 min, discarding 1/2 volume of supernatant, adding ascorbic acid solution, and standing for 0.5-1 h under the protection of inert gas; and alternately washing the composite photocatalyst by using absolute ethyl alcohol and deionized water for 3 times, and drying the composite photocatalyst at the temperature of 60 ℃ for 10-20 hours to obtain the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst.
Since the amorphous composite material in an amorphous state has a problem that a photogenerated carrier is difficult to separate, methods for improving the separation efficiency of the photogenerated carrier include noble metal deposition, formation of a heterojunction by recombination with other semiconductors, and the like. According to the invention, the ferric vanadate with the band gap of 2.05eV is added in a proper proportion in the preparation process, the valence band and the conduction band of the ferric vanadate are matched with the bismuth vanadate, and a heterojunction can be formed between the valence band and the conduction band of the ferric vanadate.
The more specific principle is as follows: the bismuth vanadate energy band contains a conduction band consisting of a hybrid orbital composed of Bi 6s and O2 p and a V3 d orbital, so that the energy band gap is reduced, and the absorption of light extends to the visible light region. Ferric vanadate has a narrower band gap, and the absorbed spectral band extends to a larger visible region. Compared with pure bismuth vanadate or ferric vanadate, an amorphous sample generated by hydrothermal reaction of a precursor solution containing bismuth vanadate and ferric vanadate in an environment with glycerol is formed by the interface effect (mainly the separation of photo-generated electron-hole pairs is accelerated by a built-in electric field between interfaces) of an amorphous bismuth vanadate/ferric vanadate heterojunction, the energy band gap at the contact interface of the amorphous bismuth vanadate/ferric vanadate heterojunction and the photo-generated electron-hole pairs is reduced to 1.85eV, the light absorption area is further expanded to a near infrared area, light in the range of 500-800 nm is strongly absorbed, the photo-generated electron-hole pairs are greatly transferred to the surface of a composite photocatalyst material, the contact probability of the photo-generated electron and the photo-generated hole and pollutants is improved, and the photocatalytic activity of the composite material is improved; secondly, the size of the nano particles of the amorphous state sample is one number smaller than that of the crystalline state sampleThe specific surface area of the bismuth vanadate or the ferric vanadate is larger than that of the bismuth vanadate or the ferric vanadate in a crystalline state, and the bismuth vanadate or the ferric vanadate has more active sites and can contact with pollutants in a water body more. Wherein, the composite photocatalyst material surface adsorbs Cr2O7 2-As a photo-generated electron acceptor, the photo-generated electron acceptor is reduced into low-toxicity Cr (III), further promotes the separation of photo-generated electron hole pairs, promotes the photo-generated holes to contact more micromolecular organic matters adsorbed on the surface of the material, and oxidizes and degrades the micromolecular organic matters.
Therefore, the method takes graphene as a conductive film and a growth template, mixes an iron nitrate solution, a glycerol solution of bismuth nitrate and an ammonium metavanadate aqueous solution according to a certain molar ratio, and prepares an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst with the particle size of less than 50nm through a conventional hydrothermal reaction, and utilizes a bismuth vanadate/ferric vanadate heterojunction structure (p-n heterojunction) and a graphene conductive layer to promote the separation and conduction of photogenerated carriers, so that the separation rate of photogenerated electron-hole pairs generated by excitation under the irradiation of visible light is greatly improved; the specific large specific surface area of the amorphous and amorphous structure is also utilized, so that the contact surface of the composite photocatalyst and Cr (VI) in a water body is increased, the composite photocatalyst has more photocatalytic activity sites than a common crystalline material, and the photocatalytic performance of the composite photocatalyst is greatly improved.
Preferably, in the glycerol solution of bismuth nitrate, the concentration of bismuth nitrate is 30-60 mmol/L, the concentration of the ammonium metavanadate aqueous solution is 60-100 mmol/L, the concentration of the ferric nitrate solution is 30-60 mmol/L, and the concentration of the ascorbic acid solution is 0.2 mol/L.
More preferably, the concentration of bismuth nitrate in the glycerol solution of bismuth nitrate is 40 mmol/L, the concentration of the ammonium metavanadate aqueous solution is 80 mmol/L, and the concentration of the ferric nitrate solution is 40 mmol/L.
Preferably, the volume ratio of the glycerol solution of bismuth nitrate, the ammonium metavanadate aqueous solution, the ferric nitrate solution and the ascorbic acid solution is 5-20: 10-20: 4-8: 2-5, and more preferably, the volumes of the glycerol solution of bismuth nitrate, the ammonium metavanadate aqueous solution, the ferric nitrate solution and the ascorbic acid solution are 50-200 m L, 100-200 m L, 40-80 m L and 20-50 m L respectively.
Preferably, the mass ratio of the bismuth nitrate to the graphene powder in S1 is 1.94: 0.004-0.032.
Preferably, the temperature for preparing the ammonium metavanadate aqueous solution in the S2 is 60-90 ℃. More preferably, the temperature for preparing the ammonium metavanadate aqueous solution in the S2 is 70-80 ℃.
Preferably, the specific step of adjusting the pH value in S2 is to adjust the pH value to 6 with ammonia water.
Preferably, the hydrothermal reaction described in S3 is carried out in a stainless steel autoclave with Teflon lining.
Preferably, the hydrothermal reaction time in S3 is 12 h.
The bismuth nitrate is Bi (NO)3)3•5H2O, Fe (NO) being ferric nitrate3)3•9H2O, bismuth vanadate is BiVO4The ferric vanadate is FeVO4。
The invention also claims an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst, which is prepared by the method and has the particle size of less than 50 nm; wherein the molar ratio of bismuth vanadate to ferric vanadate is 1-4: 1, the mass percent of the graphene is 0.5-2.4%.
The composite photocatalyst has strong absorption in both ultraviolet and visible light areas, and the molar ratio of bismuth vanadate to ferric vanadate in the composite photocatalyst is 1: 1. 2: 1. 3: 1. 4: the energy band gap of 1 is respectively 2.23eV, 1.98eV, 2.09eV and 2.06eV, which are less than the energy band gap (2.40 eV) of bismuth vanadate; wherein the molar ratio of bismuth vanadate to ferric vanadate is 2: the band gap energy of the composite photocatalyst of 1 is minimum and is smaller than that of pure ferric vanadate (2.05 eV), so that the prepared composite photocatalyst has good visible light response performance.
In the experiment of photocatalysis of hexavalent chromium-containing composite pollutants, the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst provided by the invention has the following characteristics: the molar ratio of the ferric vanadate is 1: the composite material sample of 1 has the best effect of reducing hexavalent chromium by photocatalysis, and the removal rate of Cr (VI) in 180min reaches 90%.
Therefore, the invention also claims the application of the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst in advanced treatment of chromium-containing wastewater and/or Cr (VI) photocatalytic reduction.
Compared with the prior art, the invention has the following beneficial effects:
the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst disclosed by the invention utilizes a bismuth vanadate/ferric vanadate heterojunction structure (p-n heterojunction) and a graphene conducting layer to promote the separation and conduction of photon-generated carriers, so that the separation rate of photon-generated electron-hole pairs generated by excitation under the irradiation of visible light is greatly improved; the specific large specific surface area of the amorphous and amorphous structure is also utilized, so that the contact surface of the composite photocatalyst and Cr (VI) in a water body is increased, the composite photocatalyst has more photocatalytic activity sites than that of a common crystalline material, the photocatalytic performance of the composite photocatalyst is greatly improved, and the composite photocatalyst can be used for deep treatment of Cr (VI) through photocatalytic reduction and chromium-containing wastewater and has wide application prospect.
Drawings
Fig. 1 is a diagram of a finished product of the ferric vanadate/bismuth vanadate/graphene composite photocatalyst prepared by the invention.
Fig. 2 is an XRD diffractogram of the iron vanadate/bismuth vanadate/graphene composite photocatalyst prepared in the present invention; wherein, a is the composite photocatalyst obtained in example 1, b is the composite photocatalyst obtained in example 2, and c is the composite photocatalyst obtained in example 3.
Fig. 3 is a TEM electron microscope image of the iron vanadate/bismuth vanadate/graphene composite photocatalyst prepared by the present invention.
FIG. 4 shows a UV-vis absorption spectrum of the iron vanadate/bismuth vanadate/graphene composite photocatalyst prepared by the present invention; wherein, a is the composite photocatalyst obtained in example 1, b is the composite photocatalyst obtained in example 2, and c is the composite photocatalyst obtained in example 3.
Fig. 5 is a reduction curve of the ferric vanadate/bismuth vanadate/graphene composite photocatalyst prepared in the invention for cr (vi) under visible light; wherein, a is the composite photocatalyst obtained in example 1, b is the composite photocatalyst obtained in example 2, and c is the composite photocatalyst obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to the drawings and specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
Example 1
A preparation method of an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst comprises the following steps:
1. accurately weighing 1.94g Bi (NO)3)3•5H2Adding O into 80m L glycerol, performing ultrasonic treatment and dispersion for 10min, adding 0.032g of graphene powder, and continuing performing ultrasonic treatment and stirring for 10 min;
2. accurately weigh 0.94g NH4VO3Adding into 100m L deionized water, heating in water bath at 80 deg.C, and stirring until white powder is completely dissolved;
3. 1.62g Fe (NO) was accurately weighed3)3•9H2Dissolving O in 50m L deionized water, adding the solution into the glycerol solution of bismuth nitrate obtained in the step 1, stirring to ensure that the solution is uniform and clear, dropwise adding the ammonium metavanadate aqueous solution obtained in the step 2 under magnetic stirring, then continuously stirring for 20min, adjusting the pH value to 6 by using ammonia water to obtain a precursor solution, standing at room temperature, and aging for 1 h;
4. transferring the precursor solution obtained in the step 3 into a stainless steel autoclave with a Teflon lining, and carrying out hydrothermal reaction for 12 hours at a constant temperature of 160 ℃ to obtain bright yellow suspension;
5. and (3) standing the bright yellow turbid liquid obtained in the step (4) for 20min, discarding 1/2 volumes of supernatant, adding 40m L0.2.2 mol/L ascorbic acid solution, standing for 1h under the protection of inert gas, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and drying in an oven at 60 ℃ for 10h to obtain amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst powder, wherein the mass percentage of graphene in the obtained composite photocatalyst is 1.6wt% (theoretical calculation), and the molar ratio of ferric vanadate to bismuth vanadate is 1: 1.
Example 2
A preparation method of an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst comprises the following steps:
1. accurately weighing 1.94g Bi (NO)3)3•5H2Adding O into 80m L glycerol, performing ultrasonic treatment and dispersion for 10min, adding 0.016g of graphene powder, and continuing performing ultrasonic treatment and stirring for 10 min;
2. accurately weigh 0.94g NH4VO3Adding into 100m L deionized water, heating in water bath at 80 deg.C, and stirring until white powder is completely dissolved;
3. 1.62g Fe (NO) was accurately weighed3)3•9H2Dissolving O in 50m L deionized water, adding the solution into the glycerol solution of bismuth nitrate obtained in the step 1, stirring to ensure that the solution is uniform and clear, dropwise adding the ammonium metavanadate aqueous solution obtained in the step 2 under magnetic stirring, then continuously stirring for 20min, adjusting the pH value to 6 by using ammonia water to obtain a precursor solution, standing at room temperature, and aging for 1 h;
4. transferring the precursor solution obtained in the step 3 into a stainless steel autoclave with a Teflon lining, and carrying out hydrothermal reaction for 12 hours at a constant temperature of 160 ℃ to obtain bright yellow suspension;
5. and (3) standing the bright yellow turbid liquid obtained in the step (4) for 20min, discarding 1/2 volumes of supernatant, adding 40m L0.2.2 mol/L ascorbic acid solution, standing for 1h under the protection of inert gas, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and drying in an oven at 60 ℃ for 10h to obtain amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst powder, wherein the mass percentage of graphene in the obtained composite photocatalyst is 0.8wt% (theoretical calculation), and the molar ratio of ferric vanadate to bismuth vanadate is 1: 1.
Example 3
A preparation method of an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst comprises the following steps:
1. accurately weighing 1.94g Bi (NO)3)3•5H2Adding O into 80m L glycerol, performing ultrasonic treatment and dispersion for 10min, adding 0.032g of graphene powder, and continuing performing ultrasonic treatment and stirring for 10 min;
2. accurately weigh 1.4g NH4VO3Adding into 100m L deionized water, heating in water bath at 80 deg.C, and stirring until white powder is completely dissolved;
3. 1.62g Fe (NO) was accurately weighed3)3•9H2Dissolving O in 50m L deionized water, adding the solution into the glycerol solution of bismuth nitrate obtained in the step 1, stirring to ensure that the solution is uniform and clear, dropwise adding the ammonium metavanadate aqueous solution obtained in the step 2 under magnetic stirring, then continuously stirring for 20min, adjusting the pH value to 6 by using ammonia water to obtain a precursor solution, standing at room temperature, and aging for 1 h;
4. transferring the precursor solution obtained in the step 3 into a stainless steel autoclave with a Teflon lining, and carrying out hydrothermal reaction for 12 hours at a constant temperature of 160 ℃ to obtain bright yellow suspension;
5. and (3) standing the bright yellow turbid liquid obtained in the step (4) for 20min, discarding 1/2 volumes of supernatant, adding 40m L0.2.2 mol/L ascorbic acid solution, standing for 1h under the protection of inert gas, alternately washing for 3 times by using absolute ethyl alcohol and deionized water, and drying in an oven at 60 ℃ for 10h to obtain amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst powder, wherein the mass percentage of graphene in the obtained composite photocatalyst is 0.96wt% (theoretical calculation), and the molar ratio of ferric vanadate to bismuth vanadate is 1: 2.
The appearance of the final product obtained in examples 1-3 is shown in fig. 1, and the prepared composite photocatalyst is dark green, fluffy and easy to grind.
The X-ray diffraction pattern (XRD) of the composite photocatalyst obtained in the examples 1-3 is shown in figure 2, and shows that the composite photocatalyst has a 'steamed bread peak' at 2 Theta = 25-30 degrees, and does not show any FeVO4And BiVO4The relevant characteristic peak indicates that the sample is in an amorphous state.
A Transmission Electron Microscope (TEM) image of the composite photocatalyst is shown in FIG. 3, and it can be clearly seen from the TEM image that fine spherical nanoparticles with the particle size of less than 50nm are wrapped by graphene, and the graphene can well conduct photo-generated electrons in a photocatalytic reaction.
The solid ultraviolet-visible diffuse reflection (UV-vis) absorption spectrum of the composite photocatalyst is shown in fig. 4, and accordingly, the energy band gaps of the composite photocatalyst corresponding to embodiments 1 to 3 are respectively 2.27eV, 2.14eV, and 2.12eV, which indicates that the prepared composite photocatalyst has good visible light responsiveness.
Application example
0.1g of the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst prepared in the embodiments 1-3 is added to 250m of L containing 5 mg/L K2Cr2O7And 0.2% methanol by volume, and carrying out photocatalytic reaction for 180min by using low-wattage (30W) white light L ED as a visible light source.
The reduction effect of the composite photocatalyst prepared in the embodiments 1 to 3 on Cr (VI) is shown in FIG. 5: it can be seen that the composite photocatalyst prepared in example 1 has a cr (vi) removal rate of over 90% within 180min, and has a relatively high quantum efficiency. The methanol with low concentration in the solution is used as a sacrificial agent of the photo-generated holes, the photo-generated electrons and the photo-generated holes on the surface of the catalyst are inhibited from being compounded, under the combined action of the methanol and the heterojunction in the material, the separation of photo-generated electron-hole pairs is promoted, and the Cr (VI) with high toxicity is adsorbed to the surface of the composite photocatalyst and is reduced into Cr (III) with low toxicity as a photo-generated electron acceptor.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst is characterized by comprising the following steps:
s1, preparing a glycerol solution of bismuth nitrate, adding graphene powder, and carrying out ultrasonic stirring for 10-15 min;
s2, preparing an ammonium metavanadate aqueous solution and an iron nitrate solution; uniformly mixing the glycerol solution of the bismuth nitrate treated in the step S1 with the ferric nitrate solution, adding an ammonium metavanadate aqueous solution after clarification, stirring for 15-30 min, adjusting the pH value to 4-7 to obtain a precursor solution, standing and aging for 1-2 h;
s3, placing the precursor solution obtained in the step S2 at a constant temperature of 158-162 ℃ for hydrothermal reaction for 10-20 h to obtain a bright yellow suspension;
s4, standing the bright yellow suspension obtained in the step S3 for 10-30 min, discarding 1/2 volume of supernatant, adding ascorbic acid solution, and standing for 0.5-1 h under the protection of inert gas; alternately washing the obtained product for 3 times by using absolute ethyl alcohol and deionized water, and drying the product for 10-20 hours at the temperature of 60 ℃ to obtain an amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst;
the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst comprises bismuth vanadate and ferric vanadate in a molar ratio of 1-4: 1, the mass percent of the graphene is 0.5-2.4%.
2. The preparation method according to claim 1, wherein the concentration of bismuth nitrate in the glycerol solution of bismuth nitrate is 30-60 mmol/L, the concentration of the ammonium metavanadate aqueous solution is 60-100 mmol/L, the concentration of the ferric nitrate solution is 30-60 mmol/L, and the concentration of the ascorbic acid solution is 0.2 mol/L.
3. The preparation method according to claim 2, wherein the volume ratio of the glycerol solution of bismuth nitrate, the ammonium metavanadate aqueous solution, the ferric nitrate solution and the ascorbic acid solution is 5-20: 10-20: 4-8: 2 to 5.
4. The preparation method according to claim 1, wherein the mass ratio of the bismuth nitrate to the graphene powder in S1 is 1.94: 0.004-0.032.
5. The method according to claim 1, wherein the temperature of the aqueous solution of ammonium metavanadate prepared in S2 is 60-90 ℃.
6. The method according to claim 5, wherein the temperature of the aqueous solution of ammonium metavanadate prepared in S2 is 70-80 ℃.
7. The method according to claim 1, wherein the specific step of adjusting the pH value in S2 is adjusting the pH value to 6 with ammonia water.
8. The method according to claim 1, wherein the bismuth nitrate is Bi (NO)3)3·5H2O, Fe (NO) being ferric nitrate3)3·9H2O。
9. An amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst, which is prepared by the preparation method of any one of claims 1 to 8, and has a particle size of less than 50 nm; wherein the molar ratio of bismuth vanadate to ferric vanadate is 1-4: 1, the mass percent of the graphene is 0.5-2.4%.
10. Use of the amorphous ferric vanadate/bismuth vanadate/graphene composite photocatalyst according to claim 9 in advanced treatment of photocatalytic reduction of cr (vi) and/or chromium-containing wastewater.
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| CN104383910A (en) * | 2014-11-05 | 2015-03-04 | 上海交通大学 | Preparation method of pucherite/graphene compound photo-catalyst with controllable particle size |
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