CN111330648A - MIL-101(Fe)/g-C3N4Composite visible light photocatalyst and preparation method and application thereof - Google Patents
MIL-101(Fe)/g-C3N4Composite visible light photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000013179 MIL-101(Fe) Substances 0.000 title claims abstract description 82
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000003203 everyday effect Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 24
- 239000011651 chromium Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 10
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- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
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- 238000012546 transfer Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses an MIL-101(Fe)/g-C3N4Composite visible light photocatalyst, preparation method and application thereof in two-dimensional flaky g-C3N4MIL-101(Fe) with a regular octahedral structure grows on the surface in situ, and the specific process is as follows: g to C3N4Dispersed in FeCl3And DMF under sufficient stirring to obtain Fe3+In g-C3N4The surface reaches adsorption balance, then terephthalic acid is added for ultrasonic treatment, the solvothermal reaction is carried out, and MIL-101(Fe)/g-C is obtained after solid-liquid separation, purification and drying3N4. MIL-101(Fe)/g-C of the present invention3N4The composite material does not need to additionally add other sacrifice under the condition of visible lightThe agent can be used for synchronously carrying out Cr (VI) reduction and BPA oxidative degradation in wastewater, thereby reducing the treatment difficulty and the treatment cost.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to MIL-101(Fe)/g-C3N4A composite visible light photocatalyst, a preparation method thereof and application thereof in reducing Cr (VI) and synchronously degrading bisphenol A.
Background
The pollution of water resources by heavy metals and organic pollutants has become one of the largest environmental challenges facing the world today. Among the heavy metals, hexavalent chromium cr (vi) is a common pollutant in surface and groundwater that is discharged from numerous industrial processes (e.g., electroplating, tanning, metallurgy, metal finishing, and petroleum refining). Studies have shown that concentrations of cr (vi) above 0.1ppm can have a lethal effect on aquatic organisms. In addition, cr (vi) is typically emitted along with other harmful organic pollutants, which makes treatment more challenging. Therefore, it is urgent and important to find an efficient and environmentally friendly method for simultaneously treating hexavalent chromium and organic pollutants coexisting in wastewater.
Among them, photocatalysis is considered to be a very promising method because it achieves a one-time removal of contaminants from water under light irradiation. To date, increasing attention has been focused on the photocatalytic reduction of cr (vi) or the photocatalytic oxidative degradation of organic contaminants. However, most of these photocatalytic studies have focused on a single treatment for hexavalent chromium or organic contaminants. Some researchers have studied the use of r-GO (reduced graphene oxide) to support TiO2Or ZnO, and reducing Cr (VI) and oxidizing organic pollutants simultaneously. However, because the band gap of these photocatalysts is too wide, their use in ultraviolet irradiation is limited.
From sustainable developmentFrom the viewpoint of (1), it is of great significance to develop efficient visible light driven photocatalysts to simultaneously treat coexisting pollutants in wastewater. MOF (metal organic framework materials) photocatalysts have been developed in the past decades, but because of their low solar energy conversion efficiency, low electrical conductivity, and e-/h+The composite is fast, and the photocatalytic performance of the composite is still not ideal enough. The existing research finds that the problems can be compensated by the composite of the MOF material and other noble metals or metal oxides to form a heterojunction, but the cost of the method is high.
In recent years, studies have found that3N4/MIL-53(Fe)[1]、g-C3N4/MIL-101(Fe)[2]Etc. due to their preparation method, g-C is naturally mixed3N4And MOF materials are subjected to simple physical recombination, and are not beneficial to the transfer of photogenerated electron-hole pairs, so that the stability of the materials is not ideal, and the materials are only applied to the reduction of Cr (VI) alone or the degradation of bisphenol A alone, and the synergistic treatment of the Cr (VI) and the bisphenol A is not involved.
[1]Metal organic framework g-C3N4/MIL-53(Fe)heterojunctions withenhanced photocatalytic activity for Cr(VI)reduction under visible light；Applied Surface Science,Volume 425,15December 2017,Pages 107-116.
[2]A g-C3N4/MIL-101(Fe)heterostructure composite for highly efficientBPA degradation withpersulfate under visible light irradiation；JournalofMaterials Chemistry A,Issue 46,2018.
Disclosure of Invention
In order to solve the problems in the prior art, the first purpose of the invention is to provide MIL-101(Fe)/g-C for reducing Cr (VI) and synchronously degrading BPA3N4The visible light photocatalyst is compounded, and the visible light photocatalyst are compounded in an in-situ growth mode to form a heterojunction, so that the photocatalytic performance of the visible light photocatalyst is improved.
The second purpose of the invention is to provide MIL-101(Fe)/g-C3N4The preparation method of the composite visible light photocatalyst is characterized in that3N4Surface in situMIL-101(Fe) was grown.
The third purpose of the invention is to provide MIL-101(Fe)/g-C3N4The composite visible light photocatalyst is applied to the synchronous operation of Cr (VI) reduction and BPA oxidative degradation in wastewater, and shows excellent photocatalytic performance.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
MIL-101(Fe)/g-C3N4Composite visible light photocatalyst in two-dimensional sheet g-C3N4MIL-101(Fe) with a regular octahedron structure grows on the surface in situ.
Existing MIL-101(Fe)/g-C3N4Composite material g-C3N4Simply covering the MIL-101(Fe) surface, and mixing the MIL-101(Fe) and the g-C before and after compounding3N4The size of the composite material is not changed greatly, the composite material is only loosely combined together by common physical force, the stability of the composite material is not high, and the composite material of the invention is in g-C3N4MIL-101(Fe) grows on the surface in situ, the MIL-101(Fe) is obviously reduced before and after the materials are compounded, the compounding of the MIL-101(Fe) and the materials is not simple physical action, and the stability of the composite material is higher.
Further, the particle size of MIL-101(Fe) is 0.8-1.2 μm, MIL-101(Fe) and g-C3N4The mass ratio of (A) to (B) is 3.0-4.0: 1.0.
the invention also provides the MIL-101(Fe)/g-C3N4A preparation method of a composite visible light photocatalyst, which is prepared by mixing g-C3N4Dispersed in FeCl3And DMF under sufficient stirring to obtain Fe3+In g-C3N4The surface reaches adsorption balance, then terephthalic acid is added for ultrasonic treatment, the solvothermal reaction is carried out, and MIL-101(Fe)/g-C is obtained after solid-liquid separation, purification and drying3N4。
Further, said g-C3N4The preparation process comprises the following steps: adding melamine into a crucible, placing the crucible in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining for 4 hours for the first time, placing the crucible in the muffle furnace again after cooling and grinding along with the furnace,heating to 530 ℃ at the heating rate of 10 ℃/min and calcining for 3 hours to obtain the g-C3N4. g-C of the invention3N4Two times of calcination are adopted in the preparation process, instead of simple ultrasonic crushing after one time of calcination, more uniform and fine g-C can be obtained3N4And (3) nanoparticles.
Further, FeCl3·6H2The dosage ratio of O, terephthalic acid and DMF is 26 mmol: 13 mmol: 320 mL.
Further, the ultrasonic treatment conditions are as follows: the conditions of the ultrasonic treatment were: the frequency is 40kHz, the power is 500W, and the time is 30-40 min.
Further, the conditions of the solvothermal reaction are as follows: the temperature is 120-140 ℃ and the time is 15-18 h.
Further, the purification process comprises the following steps: the solid product after solid-liquid separation was stirred in methanol solution for three days, and the methanol solution was changed every day.
Further, vacuum drying is adopted for drying, the temperature is 100 ℃, and the time is 20 hours.
The invention prepares MIL-101(Fe)/g-C3N4In the process, FeCl is firstly added3·6H2O and g-C3N4Fully stirring and mixing to obtain Fe3+In g-C3N4Adding H after the surface reaches saturated adsorption2The BDC is subjected to solvothermal reaction instead of FeCl3·6H2O、H2BDC together with g-C3N4Mixing and directly carrying out the solvothermal reaction. The former can make Fe by electrostatic adsorption, metal coordination, etc3+Is firmly adsorbed on g-C3N4Surface to Fe3+/g-C3N4After stable adsorption, H is added2The BDC is subjected to solvothermal reaction, so that the MIL-101(Fe) can be more firmly grown on g-C3N4Surface, resulting in MIL-101(Fe)/g-C3N4The heterojunction is more favorable for electrons and holes in MIL-101(Fe) and g-C3N4The transfer between; the latter of which will be FeCl3·6H2O、H2BDC together with g-C3N4Mixing and then directly carrying out solvothermal reaction to obtain Fe3+Priority and H2Chelate coordination of BDC to g-C3N4The binding force is weak, thus obtaining MIL-101(Fe)/g-C3N4Are only loosely bound together by ordinary physical forces, which are not favorable for electrons and holes in MIL-101(Fe) and g-C3N4To be transferred between.
The invention also provides the MIL-101(Fe)/g-C3N4The composite visible light photocatalyst is applied to synchronously treating Cr (VI) reduction and BPA oxidative degradation in wastewater under the condition of visible light.
Further, the concentration ratio of Cr (VI) to BPA in the wastewater is 1.0: 0.5 to 1.5.
Different from the prior MIL-101(Fe) and g-C3N4MIL-101(Fe)/g-C obtained by simple physical compounding3N4The composite material is only used for degrading BPA independently in application, and persulfate is additionally added in the degradation process. The composite material of the invention is structurally MIL-101(Fe) and g-C3N4By in situ complexation at g-C3N4MIL-101(Fe) grows on the surface in situ, the composite effect is firmer, the material structure is more stable, the transfer of electrons and holes between MIL-101(Fe) and g-C3N4 is facilitated, the rapid and effective separation of photo-generated electron-hole pairs is realized, and the photocatalytic performance is improved. In application, MIL-101(Fe)/g-C synthesized in situ3N4The composite material is used for synchronously carrying out Cr (VI) reduction and BPA oxidative degradation, g-C3N4Photo-generated electrons on the surface can be effectively and rapidly transferred to the MIL-101(Fe) surface to reduce Cr (VI), and meanwhile, holes on the MIL-101(Fe) surface can be effectively and rapidly transferred to g-C3N4The surface and the oxidized BPA are mutually matched, and other sacrificial agents are not required to be additionally added, so that the simultaneous treatment of two pollutants is realized, and the treatment difficulty and the treatment cost are reduced.
Compared with the prior art, the invention has the advantages that:
(1) MIL-101(Fe)/g-C of the present invention3N4Composite material prepared by mixing at g-C3N4MIL-101(Fe) grows in situ on the surface to be compounded to form a heterojunction, so that the composite effect is firmer, the material structure is more stable, and electrons and holes are more favorably formed in the MIL-101(Fe) and g-C3N4The transfer between the two components realizes the quick and effective separation of the photoproduction electron hole pairs, and improves the photocatalysis performance.
(2) MIL-101(Fe)/g-C of the present invention3N4The composite material can be used for synchronously carrying out Cr (VI) reduction and BPA oxidative degradation in wastewater under the condition of visible light without adding other sacrificial agents, thereby reducing the treatment difficulty and the treatment cost.
Drawings
Fig. 1 is an XRD pattern of samples prepared in example 1 of the present invention, comparative example 1 and comparative example 2.
Fig. 2 is a TEM image of samples prepared in example 1, comparative example 2 and comparative example 3 of the present invention.
FIG. 3 is an XPS chart of samples prepared in example 1 of the present invention and comparative example 2.
FIG. 4 is a graph of UV-DRS of samples prepared in example 1, comparative example 2 and comparative example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, specific examples and comparative examples, but the present invention is not limited to the following embodiments.
Example 1
(1) Adding melamine into a loose crucible covered with a cover, placing the crucible in a muffle furnace, calcining for the first time at 550 ℃ for 4h (the heating rate is 5 ℃/min), taking out the obtained product, cooling to room temperature, grinding, placing the obtained product in the muffle furnace again at 530 ℃ for calcining for 3 h (the heating rate is 10 ℃/min) to obtain g-C3N4；
(2) 1mmol g-C3N4Dispersed in 6.5mmol FeCl3And 80ml of DMF and stirred for half an hour to reach adsorption equilibrium, and then 3.25mmol of H was added to the solution2BDC and ultrasonic processing for half an hour, carrying out solvent heat treatment after ultrasonic dispersion, wherein the reaction condition is that the temperature is 120 ℃, the time is 15 hours, and when the temperature is cooled to the roomCollecting the obtained orange solid product by centrifugation (3000 rpm) after warming, stirring the product in 200mL methanol solution for three days, wherein the methanol solution needs to be changed every day, centrifuging, and vacuum drying at 100 deg.C for 20 hr to obtain MIL-101(Fe)/g-C3N4。
Comparative example 1
Adding melamine into a loose crucible covered with a cover, placing the crucible in a muffle furnace, calcining for the first time at 550 ℃ for 4h (the heating rate is 5 ℃/min), taking out the obtained product, cooling to room temperature, grinding, placing the obtained product in the muffle furnace again at 530 ℃ for calcining for 3 h (the heating rate is 10 ℃/min) to obtain g-C3N4。
Comparative example 2
FeCl is added3·6H2O、H2BDC and DMF are mixed according to a ratio of 26 mmol: 13 mmol: and (2) fully mixing 320mL, carrying out ultrasonic treatment, reacting for 15h at 120 ℃ in a Teflon-lined stainless steel autoclave, cooling to room temperature, carrying out centrifugal separation at the rotating speed of 3000rpm to obtain a yellow solid, stirring the yellow solid in 200mL of methanol solution for three days (replacing the solution once a day), carrying out centrifugal separation, and carrying out vacuum drying at 100 ℃ for 20h to obtain MIL-101 (Fe).
Comparative example 3
1mmol g-C3N4Dispersed in 6.5mmol FeCl3、3.25mmol H2Carrying out ultrasonic treatment for half an hour in a mixed solution of BDC and 80mL DMF, carrying out solvent heat treatment under the reaction conditions of 120 ℃ and 15 hours, collecting a light orange solid product by a centrifugal separation method (the rotating speed is 3000rpm) after the temperature is cooled to room temperature, stirring the product in 200mL methanol solution for three days, replacing the methanol solution every day, carrying out centrifugal separation, and carrying out vacuum drying at 100 ℃ for 20 hours to obtain MIL-101(Fe) + g-C3N4。
As shown in FIG. 1, MIL-101(Fe)/g-C3N4The characteristic peak is similar to that of pure MIL-101(Fe), which shows that the crystal form of the MIL-101(Fe) is reserved in the synthesized product, and g-C3N4The characteristic peak of (A) is shifted by about 2 degrees in the product, indicating MIL-101(Fe)/g-C3N4The composite material is not MIL-101(Fe)And g-C3N4Simple physical action of (2).
As shown in FIG. 2, MIL-101(Fe)/g-C3N4MIL-101(Fe) (particle size 1.0 μm) in the composite material is distributed in g-C3N4The surface and the grain diameter are smaller than those of pure MIL-101(Fe) (the grain diameter is 2.0 mu m), and the two are tightly and firmly compounded. MIL-101(Fe) + g-C3N4The size of MIL-101(Fe) in the composite material is consistent with that of pure MIL-101(Fe) (2.0 mu m), and g-C3N4The surface contact is loose.
As shown in FIG. 3, MIL-101(Fe)/g-C3N4Has one more N1s peak than MIL-101(Fe), indicating MIL-101(Fe) and g-C3N4The composite effect is good.
As shown in FIG. 4, MIL-101(Fe)/g-C3N4The visible light absorption capacity of the composition is compared with that of MIL-101(Fe) and g-C3N4And MIL-101(Fe) + g-C3N4The obvious enhancement is obtained.
And (3) testing the catalytic performance:
(1) 20mg of MIL-101(Fe)/g-C obtained in example 13N4The composite photocatalyst is added into a solution with the concentration of 40mLCr (VI) being 20mg/L and the concentration of BPA being 10mg/L, the pH value is adjusted to 6.8, under the irradiation of simulated visible light by a 150 watt halogen cold light source loaded with a 420nm filter, the reduction efficiency of Cr (VI) is 68 percent after 4 hours, and the degradation efficiency of BPA is 94.8 percent.
(2) 20mg of MIL-101(Fe)/g-C obtained in example 13N4The composite photocatalyst is added into a solution with the concentration of 40mLCr (VI) being 20mg/L and the concentration of BPA being 20mg/L, the pH value is adjusted to be 6.8, under the irradiation of simulated visible light by a 150 watt halogen cold light source loaded with a 420nm filter, the reduction efficiency of Cr (VI) is 97.1 percent after 4 hours, and the degradation efficiency of BPA is 87.7 percent.
(3) 20mg of MIL-101(Fe)/g-C obtained in example 13N4The composite photocatalyst is added into a solution with the concentration of 40mLCr (VI) being 20mg/L and the concentration of BPA being 30mg/L, the pH value is adjusted to be 6.8, under the irradiation of simulated visible light by a 150 watt halogen cold light source loaded with a 420nm filter, the reduction efficiency of Cr (VI) is 98.8 percent after 4 hours, and the degradation efficiency of BPA is 76.2 percent.
(4) 20mg of g-C from comparative example 13N4Added into a solution with the concentration of 40mLCr (VI) being 20mg/L and the concentration of BPA being 20mg/L as a catalyst, the pH value is adjusted to be 6.8, and under the irradiation of simulated visible light by a 150 watt halogen cold light source loaded with a 420nm filter, the reduction efficiency of Cr (VI) is 18.7 percent after 4 hours, and the degradation efficiency of BPA is 20.4 percent.
(5) 20mg of MIL-101(Fe) prepared in comparative example 2 was added as a catalyst to a solution of 40mLCr (VI) at a concentration of 20mg/L and BPA at a concentration of 20mg/L, the pH was adjusted to 6.8, and the reduction efficiency of Cr (VI) was 33.6% and the degradation efficiency of BPA was 42.8% after 4 hours under simulated visible light irradiation with a 150 watt halogen cold light source loaded with a 420nm filter.
(6) 20mg of MIL-101(Fe) + g-C obtained in comparative example 33N4Added into a solution with the concentration of 40mLCr (VI) being 20mg/L and the concentration of BPA being 20mg/L as a catalyst, the pH value is adjusted to be 6.8, and under the irradiation of simulated visible light by a 150 watt halogen cold light source loaded with a 420nm filter, the reduction efficiency of Cr (VI) is 37.7 percent after 4 hours, and the degradation efficiency of BPA is 45.1 percent.
Claims (10)
1. MIL-101(Fe)/g-C3N4The composite visible light photocatalyst is characterized in that: in two-dimensional sheet form g-C3N4MIL-101(Fe) with a regular octahedron structure grows on the surface in situ.
2. The MIL-101(Fe)/g-C of claim 13N4The composite visible light photocatalyst is characterized in that: the particle size of MIL-101(Fe) is 0.8-1.2 μm, MIL-101(Fe) and g-C3N4The mass ratio of (A) to (B) is 3.0-4.0: 1.0.
3. the MIL-101(Fe)/g-C of claim 1 or 23N4The preparation method of the composite visible light photocatalyst is characterized by comprising the following steps: g to C3N4Dispersed in FeCl3And DMF under sufficient stirring to obtain Fe3+In g-C3N4The surface reaches adsorption balance, and then terephthalic acid is added for ultrasonic treatmentThen carrying out solvent thermal reaction, and obtaining MIL-101(Fe)/g-C after solid-liquid separation, purification and drying3N4。
4. The MIL-101(Fe)/g-C of claim 33N4The preparation method of the composite visible light photocatalyst is characterized by comprising the following steps: the g to C3N4The preparation process comprises the following steps: adding melamine into a crucible, placing the crucible in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining for 4 hours for the first time, cooling and grinding with the furnace, placing the crucible in the muffle furnace again, heating to 530 ℃ at the heating rate of 10 ℃/min, calcining for 3 hours to obtain the g-C3N4。
5. The MIL-101(Fe)/g-C of claim 33N4The preparation method of the composite visible light photocatalyst is characterized by comprising the following steps: FeCl3·6H2The dosage ratio of O, terephthalic acid and DMF is 26 mmol: 13 mmol: 320 mL.
6. The MIL-101(Fe)/g-C of claim 33N4The preparation method of the composite visible light photocatalyst is characterized by comprising the following steps: the conditions of the solvothermal reaction are as follows: the temperature is 120-140 ℃ and the time is 15-18 h.
7. The MIL-101(Fe)/g-C of claim 33N4The preparation method of the composite visible light photocatalyst is characterized by comprising the following steps: the ultrasonic treatment conditions are that the frequency is 40kHz, the power is 500W, and the time is 30-40 min.
8. The MIL-101(Fe)/g-C of claim 33N4The preparation method of the composite visible light photocatalyst is characterized by comprising the following steps: the purification process comprises the following steps: stirring the solid product after solid-liquid separation in a methanol solution for three days, and replacing the methanol solution every day; the drying process adopts vacuum drying at 100 ℃ for 20 h.
9. The method of any one of claims 1-2MIL-101(Fe)/g-C of3N4Composite visible light photocatalyst or MIL-101(Fe)/g-C prepared by the preparation method of any one of claims 3 to 83N4The application of the composite visible light photocatalyst is characterized in that: under the condition of visible light, Cr (VI) in the wastewater is synchronously treated, and the BPA is oxidized and degraded.
10. The MIL-101(Fe)/g-C of claim 93N4The application of the composite visible light photocatalyst is characterized in that: in the wastewater, the concentration ratio of Cr (VI) to BPA is 1.0: 0.5 to 1.5.
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