CN111686768B - Photocatalytic reduction of Cr 6+ MIL-125/Ag/BiOBr composite catalyst, preparation method and application thereof - Google Patents
Photocatalytic reduction of Cr 6+ MIL-125/Ag/BiOBr composite catalyst, preparation method and application thereof Download PDFInfo
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- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 10
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Abstract
The invention provides a BiOBr composite catalyst, which is modified with Ag on the surface 0 MIL-125 of (B) is compounded on a BiOBr carrier to obtain a BiOBr composite catalyst; the micro morphology of the BiOBr composite catalyst is a curved nano-sheet; the diameter of the nano-sheet is 600-1200 nm; the nano sheet has 3-5 layers, each layer has a plurality of defect holes, each layer is composed of a plurality of nano particles, and the particle size of the nano particles is 10-30 nm. Compared with the prior art, the invention has the following advantages: the MIL-125/Ag/BiOBr composite nano material has large specific surface area and strong adsorption capacity; compared with BiOBr modified by other modification methods, the MIL-125/Ag/BiOBr composite nano material has better visible light absorption performance and can reduce Cr by photocatalysis 6+ The stability is very high; the preparation method of the MIL-125/Ag/BiOBr composite nano material is simple, easy to operate and suitable for industrial production.
Description
Technical Field
The invention is thatRelates to photocatalytic reduction of Cr 6+ MIL-125/Ag/BiOBr composite catalyst, belongs to the technical field of environmental chemical photocatalytic water treatment, and particularly relates to visible light treatment of Cr 6+ And (5) waste water.
Background
Diseases and death events caused by heavy metal pollution are frequent in countries around the world. Such as pain and water diseases in Japan, cadmium rice events in China, lead poisoning events in Shaanxi 174 children, etc. According to the mutation rate toxicity evaluation and research result of Lin Liqin, the toxicity and the lethal effect of heavy metals are inferior to those of pesticides and the like. Therefore, the research of the corresponding removal method is becoming a hot spot increasingly in face of the pollutants with strong toxicity and harm such as heavy metals. The photocatalysis technology is an environment-friendly, efficient and secondary pollution-free advanced oxidation technology, has wide application prospect in the fields of energy development and environmental pollution treatment, and attracts wide attention and research of domestic and foreign scholars.
At present, the photocatalyst which is more used is TiO 2 However, tiO 2 The semiconductor is a wide forbidden band semiconductor, can only absorb ultraviolet light, and electrons and holes are easy to combine, so that the wide forbidden band semiconductor is restricted from being applied to the industry on a large scale. In recent years, researchers have been working to develop novel efficient, visible light responsive photocatalyst materials, including metal hydroxides, multi-element metal oxides, layered compounds, structured oxides, etc., wherein the layered compounds bismuth oxyhalide (bisx, x= F, cl, br, I) have unique layered structures that significantly reduce their electron and hole recombination rates.
Bismuth oxybromide (BiOBr) is an important photocatalyst in bismuth oxyhalide series, and is a research hotspot in the field of photocatalysis gradually because of good absorption in the visible light region, relatively stable property under illumination, proper forbidden bandwidth, excellent photocatalytic performance and relatively strong pollutant degradation capability under the visible light condition. But when used alone, the catalytic effect and stability are not ideal. In order to further improve the photo-catalytic activity and stability of the BiOBr, the BiOBr can be modified by adopting methods such as metal doping, nonmetal doping, semiconductor doping and the like. For example, shuai Fu, wei Yuan, xianmine Liu, et al.A novel 0D/2D WS 2 A WS is reported in journal of Colloid and Interface Science 569 (2020) 150-163, per BiOBr heterostructure with rich oxygen vacancies for enhanced broad-spectrum photocatalytic performance 2 The BiOBr catalyst has weak stability, and the photocatalyst is easy to deactivate after being used for several times.
Disclosure of Invention
The invention aims to provide a visible light response Cr-pair 6+ The preparation process of the MIL-125/Ag/BiOBr composite nano catalyst has high efficient reducing capacity, simple preparation, good stability and difficult corrosion.
To achieve this object, the present invention provides:
a BiOBr composite catalyst with Ag modified surface 0 MIL-125 of (B) is compounded on a BiOBr carrier to obtain a BiOBr composite catalyst; the micro morphology of the BiOBr composite catalyst is a curved nano-sheet; the diameter of the nano-sheet is 600-1200 nm; the nano sheet has 3-5 layers, each layer has a plurality of defect holes, each layer is composed of a plurality of nano particles, and the particle size of the nano particles is 10-30 nm.
Preferably, a hydrothermal method is adopted to prepare BiOBr and MIL-125 respectively; then adopting a photoreduction method to reduce Ag 0 Modifying the surface of MIL-125 to obtain MIL-125/Ag complex; finally, the MIL-125/Ag complex is loaded on the BiOBr to obtain the BiOBr composite catalyst.
Preferably, the method comprises the steps of:
(1) CTAB was added dropwise to Bi (NO 3 ) 3 ·5H 2 Mixing and stirring the mixture in the O-EG solution for 30min; then adding 25wt% sodium carbonate solution to pH=3-6, stirring at room temperature for 30min to obtain solution I; transferring the obtained solution I into a hydrothermal reaction kettle, and reacting for 4-10 h at 130-180 ℃; after the reaction, respectively cleaning, filtering and drying the precipitate to obtain white BiOBr powder;
Bi(NO 3 ) 3 ·5H 2 bi (NO) in O-EG solution 3 ) 3 ·5H 2 The mass ratio of O to EG is 1:20, a step of;
CTAB and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1:1, a step of;
(2) The mass ratio is 1:2:4:35 Ti (O-iPr) 4 、H 2 BDC、CH 3 Mixing OH and DMF and stirring for 1h to obtain solution II; transferring the solution II into a hydrothermal reaction kettle, and reacting for 30-60 h at 130-180 ℃; after the reaction, respectively cleaning, filtering and drying the precipitate to obtain MIL-125 powder;
(3) Mixing MIL-125 and AgNO prepared in step (2) 3 Dispersed to 5% PEG-H 2 Transferring the O solution into a water-cooled reactor, and irradiating under a 500Xe lamp for 0.5-2 h to obtain a solution III;
5% PEG with H 2 The volume ratio of O is 1:100, and the mass ratio of MIL-125 to water is 2:1, a step of;
AgNO 3 the mass ratio of MIL-125 is 1:25, a step of selecting a specific type of material;
(4) Dispersing the BiOBr prepared in the step (1) into a solution III, and stirring for 2-8 hours at the temperature of 40-80 ℃; cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum oven at 50-100 ℃ for 12-24 hours to obtain the BiOBr composite catalyst;
the mass of BiOBr and MIL-125 is 1: 20-1: 5.
the invention also provides a BiOBr composite catalyst for reducing Cr in photocatalysis 6+ Is applied to: biOBr composite catalyst and Cr 6+ The mass ratio of the substrate is 5:1, cr 6+ The concentration of the substrate solution is 50mg/L, and the light source is a xenon lamp.
Compared with the prior art, the invention has the following advantages:
(1) The MIL-125/Ag/BiOBr composite nano material has large specific surface area and strong adsorption capacity;
(2) Compared with BiOBr modified by other modification methods, the MIL-125/Ag/BiOBr composite nano material has better visible light absorption performance and can reduce Cr by photocatalysis 6+ The stability is very high;
(3) The preparation method of the MIL-125/Ag/BiOBr composite nano material is simple, easy to operate and suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of MIL-125/Ag/BiOBr composite catalyst in example 1.
FIG. 2 is a graph showing the physical adsorption and specific surface area comparison of MIL-125/Ag/BiOBr composite catalyst and pure BiOBr and MIL-125 in example 1.
FIG. 3 is a graph showing the comparison of the effect of MIL-125/Ag/BiOBr composite catalyst and pure BiOBr photocatalytic degradation of potassium dichromate in example 1.
FIG. 4 is a graph showing the effect of recycling photocatalytic degradation of potassium dichromate by the MIL-125/Ag/BiOBr composite catalyst in example 1.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
Photocatalytic reduction of Cr 6+ The MIL-125/Ag/BiOBr composite catalyst consists of porous multilayer nano-sheet units consisting of particles with an average particle size of 15nm, and the diameter of the nano-sheet units is 900nm.
The preparation method of the MIL-125/Ag/BiOBr composite catalyst specifically comprises the following steps:
(1) Will be combined with Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: CTAB of 1 was added dropwise to Bi (NO 3 ) 3 ·5H 2 Bi (NO) in O-EG solution 3 ) 3 ·5H 2 The mass ratio of O to EG is 1: mixing and stirring for 30min; then, adding 25wt% sodium carbonate solution to pH=3-6, stirring at room temperature for 30min; finally, transferring the solution into a hydrothermal reaction kettle, and reacting for 4-10 hours at 130-180 ℃; after the reaction, the precipitate was washed, filtered and dried, respectively, to obtain white BiOBr powder.
(2) The mass ratio is 1:2:4:35 Ti (O-iPr) 4 、H 2 BDC、CH 3 Mixing OH and DMF and stirring for 1h; transferring the solution into a hydrothermal reaction kettle, and reacting for 30-60 h at 130-180 ℃; after the reaction, the precipitate is respectively washed, filtered and dried to obtain MIL-125 powder.
(3) Mixing MIL-125 prepared in the step (2) with MIL-125 in a mass ratio of 1:25 AgNO 3 Dispersed to 5% PEG-H 2 In O solution, 5% PEG and H 2 The volume ratio of O is 1:100, and the mass ratio of MIL-125 to water is 2:1, a step of; then the floating liquid is transferred into a water-cooled reactor, and irradiated under a 500Xe lamp for 0.5 to 2 hours.
(4) The mass of MIL-125 is 1: 20-1: 5 (prepared from (1)) and dispersing into the solution (3), and stirring at 40-80 ℃ for 2-8 h; after cooling to room temperature, washing three times with deionized water and absolute ethyl alcohol respectively, and drying in a vacuum oven at 50-100 ℃ for 12-24 h.
Application of MIL-125/Ag/BiOBr composite catalyst
MIL-125/Ag/BiOBr catalyst and Cr 6+ The mass ratio of the substrate is 5:1, cr 6+ The concentration of the substrate solution is 50mg/L, and the light source is a xenon lamp.
The invention provides a method for reducing Cr by photocatalysis 6+ MIL-125/Ag/BiOBr composite catalyst, preparation method and application thereof. MIL-125/Ag/BiOBr composite catalyst is composed of porous multilayer nanosheet units composed of particles with average particle size of 15nm, and the diameter of the nanosheet units is 900nm. The preparation method of the MIL-125/Ag/BiOBr composite catalyst comprises the following steps: firstly, respectively preparing BiOBr and MIL-125 by adopting a hydrothermal method; then adopting a photoreduction method to reduce Ag 0 Modifying the surface of MIL-125; finally, biOBr is used for modifying MIL-125/Ag. MIL-125/Ag/BiOBr composite catalyst realizes target pollutant Cr under irradiation of visible light 6+ And (5) high-efficiency reduction. The MIL-125/Ag/BiOBr composite nano material has large specific surface area and strong adsorption capacity; the photocatalyst has better visible light absorption performance, and greatly improves the photocatalytic oxidative degradation of organic pollutants; and the preparation method of MIL-125/Ag/BiOBr is simpler and is easy to operate.
Example 1
The preparation method of the MIL-125/Ag/BiOBr composite catalyst specifically comprises the following steps:
(1) Will be combined with Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: CTAB of 1 was added dropwise to Bi (NO 3 ) 3 ·5H 2 Bi (NO) in O-EG solution 3 ) 3 ·5H 2 The mass ratio of O to EG is 1: mixing and stirring for 30min; then, 25wt% sodium carbonate solution was added to ph=3 and stirred at room temperature for 30min; finally, the above-mentionedTransferring the solution into a hydrothermal reaction kettle, and reacting for 10 hours at 130 ℃; after the reaction, the precipitate was washed, filtered and dried, respectively, to obtain white BiOBr powder.
(2) The mass ratio is 1:2:4:35 Ti (O-iPr) 4 、H 2 BDC、CH 3 Mixing OH and DMF and stirring for 1h; transferring the solution into a hydrothermal reaction kettle, and reacting at 130 ℃ for 60 hours; after the reaction, the precipitate is respectively washed, filtered and dried to obtain MIL-125 powder.
(3) Mixing MIL-125 prepared in the step (2) with MIL-125 in a mass ratio of 1:25 AgNO 3 Dispersed to 5% PEG-H 2 In O solution, 5% PEG and H 2 The volume ratio of O is 1:100, and the mass ratio of MIL-125 to water is 2:1, a step of; the above-mentioned suspension was then transferred to a water-cooled reactor and irradiated under a 500Xe lamp for 0.5h.
(4) The mass of MIL-125 is 1:20 BiOBr ((1) prepared) was dispersed in the solution of (3) and stirred at 40℃for 8h; after cooling to room temperature, washing three times with deionized water and absolute ethanol each, drying in a vacuum oven at 50 ℃ for 24h.
Example 2
The preparation method of the MIL-125/Ag/BiOBr composite catalyst specifically comprises the following steps:
(1) Will be combined with Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: CTAB of 1 was added dropwise to Bi (NO 3 ) 3 ·5H 2 Bi (NO) in O-EG solution 3 ) 3 ·5H 2 The mass ratio of O to EG is 1: mixing and stirring for 30min; then, 25wt% sodium carbonate solution was added to ph=6, and stirred at room temperature for 30min; finally, transferring the solution into a hydrothermal reaction kettle, and reacting for 4 hours at 180 ℃; after the reaction, the precipitate was washed, filtered and dried, respectively, to obtain white BiOBr powder.
(2) The mass ratio is 1:2:4:35 Ti (O-iPr) 4 、H 2 BDC、CH 3 Mixing OH and DMF and stirring for 1h; transferring the solution into a hydrothermal reaction kettle, and reacting for 30 hours at 180 ℃; after the reaction, the precipitate is respectively washed, filtered and dried to obtain MIL-125 powder.
(3) Mixing MIL-125 prepared in step (2) withMIL-125 mass ratio is 1:25 AgNO 3 Dispersed to 5% PEG-H 2 In O solution, 5% PEG and H 2 The volume ratio of O is 1:100, and the mass ratio of MIL-125 to water is 2:1, a step of; the above-mentioned suspension was then transferred to a water-cooled reactor and irradiated under a 500Xe lamp for 2 hours.
(4) The mass of MIL-125 is 1:5 (prepared from (1)) was dispersed in the solution (3) and stirred at 80 ℃ for 2h; after cooling to room temperature, washing three times with deionized water and absolute ethanol each, drying in a vacuum oven at 100 ℃ for 12h.
Example 3
The preparation method of the MIL-125/Ag/BiOBr composite catalyst specifically comprises the following steps:
(1) Will be combined with Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1: CTAB of 1 was added dropwise to Bi (NO 3 ) 3 ·5H 2 Bi (NO) in O-EG solution 3 ) 3 ·5H 2 The mass ratio of O to EG is 1: mixing and stirring for 30min; then, 25wt% sodium carbonate solution was added to ph=4 and stirred at room temperature for 30min; finally, transferring the solution into a hydrothermal reaction kettle, and reacting for 6 hours at 150 ℃; after the reaction, the precipitate was washed, filtered and dried, respectively, to obtain white BiOBr powder.
(2) The mass ratio is 1:2:4:35 Ti (O-iPr) 4 、H 2 BDC、CH 3 Mixing OH and DMF and stirring for 1h; transferring the solution into a hydrothermal reaction kettle, and reacting for 45 hours at 150 ℃; after the reaction, the precipitate is respectively washed, filtered and dried to obtain MIL-125 powder.
(3) Mixing MIL-125 prepared in the step (2) with MIL-125 in a mass ratio of 1:25 AgNO 3 Dispersed to 5% PEG-H 2 In O solution, 5% PEG and H 2 The volume ratio of O is 1:100, and the mass ratio of MIL-125 to water is 2:1, a step of; the above-mentioned suspension was then transferred to a water-cooled reactor and irradiated under a 500Xe lamp for 1 hour.
(4) The mass of MIL-125 is 1:10 BiOBr ((1) prepared) was dispersed in the solution of (3) and stirred at 60℃for 6h; after cooling to room temperature, washing three times with deionized water and absolute ethanol each, drying in a vacuum oven at 80 ℃ for 18h.
Application example 1
Placing 0.05g of MIL-125/Ag/BiOBr composite nano material in the embodiment 1 into a potassium dichromate solution, performing ultrasonic dispersion for 30min, then magnetically stirring for 60min in the dark, taking 2mL of the solution after stirring, centrifuging for 5min at 3000r/min, measuring absorbance, irradiating by using a xenon lamp as a light source, sampling once every 30min, centrifuging, measuring absorbance, and calculating the content of pollutants by absorbance. The removal rate of potassium dichromate was calculated by absorbance.
The experimental result is shown in fig. 2, when the MIL-125/Ag/BiOBr composite nano material is used as a catalyst under the condition of visible light, the potassium dichromate removal rate is 75.6% after 5 hours degradation, so that the MIL-125/Ag/BiOBr composite nano material is used as a photocatalyst, and has stronger catalytic oxidation activity on liquid phase pollutants under the condition of visible light.
The stability test result is shown in fig. 4, the material prepared in example 1 is used as a catalyst, and after the material is repeatedly used for 7 times, the reduction of hexavalent chromium is still kept at about 75%, and the material has good photocatalytic stability.
Claims (3)
1. Photocatalytic reduction of Cr 6+ The MIL-125/Ag/BiOBr composite catalyst is characterized in that: surface is modified with Ag 0 MIL-125 is compounded on a BiOBr carrier to obtain a MIL-125/Ag/BiOBr composite catalyst; the micro morphology of the MIL-125/Ag/BiOBr composite catalyst is a curved nano-sheet; the diameter of the nano-sheet is 600-1200 nm; the nano sheet is provided with 3-5 layers, each layer is provided with a plurality of defect holes, each layer is composed of a plurality of nano particles, and the particle size of the nano particles is 10-30 nm;
the preparation method of the MIL-125/Ag/BiOBr composite catalyst comprises the following steps:
(1) CTAB was added dropwise to Bi (NO 3 ) 3 •5H 2 Mixing and stirring the mixture in the O-EG solution for 30min; then adding 25wt% sodium carbonate solution to pH=3-6, stirring at room temperature for 30min to obtain solution I; transferring the obtained solution I into a hydrothermal reaction kettle, and reacting for 4-10 h at 130-180 ℃; after the reaction, the precipitate is respectively washed, filtered and dried to obtain white BiOBr powder; bi (NO) 3 ) 3 •5H 2 Bi (NO) in O-EG solution 3 ) 3 •5H 2 The mass ratio of O to EG is 1:20, a step of; CTAB and Bi (NO) 3 ) 3 •5H 2 The molar ratio of O is 1:1, a step of;
(2) The mass ratio is 1:2:4:35 Ti (O-iPr) 4 、H 2 BDC、CH 3 Mixing OH and DMF and stirring for 1h to obtain solution II; transferring the solution II into a hydrothermal reaction kettle, and reacting for 30-60 h at 130-180 ℃; after the reaction, respectively cleaning, filtering and drying the precipitate to obtain MIL-125 powder;
(3) Mixing MIL-125 and AgNO prepared in step (2) 3 Dispersed to 5% PEG-H 2 Transferring the O solution into a water-cooled reactor, and irradiating under a 500Xe lamp for 0.5-2 h to obtain a solution III; the volume ratio of 5% PEG to H2O is 1:100, and the mass ratio of MIL-125 to water is 2:1, a step of; agNO 3 The mass ratio of MIL-125 is 1:25, a step of selecting a specific type of material;
(4) Dispersing the BiOBr prepared in the step (1) into a solution III, and stirring for 2-8 hours at the temperature of 40-80 ℃; cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying in a vacuum oven at 50-100 ℃ for 12-24 hours to obtain the MIL-125/Ag/BiOBr composite catalyst; the mass of BiOBr and MIL-125 is 1: 20-1: 5.
2. the photocatalytic reduction of Cr according to claim 1 6+ The MIL-125/Ag/BiOBr composite catalyst is characterized in that: firstly, respectively preparing BiOBr and MIL-125 by adopting a hydrothermal method; then adopting a photo-reduction method to modify Ag0 on the surface of MIL-125 to obtain MIL-125/Ag compound; finally, the MIL-125/Ag composite is loaded on BiOBr to obtain the MIL-125/Ag/BiOBr composite catalyst.
3. The photocatalytic reduction of Cr as set forth in claim 1 or claim 2 6+ The MIL-125/Ag/BiOBr composite catalyst reduces Cr in photocatalysis 6+ Is applied to: the MIL-125/Ag/BiOBr composite catalyst and Cr 6+ The mass ratio of the substrate is 5:1, cr 6+ The concentration of the substrate solution is 50mg/L, and the light source is a xenon lamp.
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