CN111604066A - Graphene modified Er doped CeO2Photocatalytic degradation material of BiOBr heterojunction - Google Patents
Graphene modified Er doped CeO2Photocatalytic degradation material of BiOBr heterojunction Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
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- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 title description 5
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 29
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 21
- 229960001759 cerium oxalate Drugs 0.000 claims abstract description 19
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims abstract description 19
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims abstract description 18
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
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- 150000003522 tetracyclines Chemical class 0.000 abstract description 10
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- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 2
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of photocatalysis, and discloses graphene modified Er doped CeO2‑BiThe photocatalytic degradation material of the OBr heterojunction takes sodium borohydride as a reducing agent to obtain reduced graphene oxide, effectively reduces oxygen-containing groups, takes cerium nitrate and erbium nitrate as raw materials to obtain shuttle-type Er doped cerium oxalate, and forms a large number of pore structures through calcination to obtain the porous shuttle-type Er doped CeO2The contact area with sunlight is increased, erbium ions replace cerium ion lattice sites, oxygen vacancy defects are generated in crystal lattices, the crystal lattices can be used as photo-generated electrons to capture traps, the recombination of photo-generated electrons and holes is delayed, bismuth nitrate is used as a bismuth source, graphene modified petal-shaped BiOBr is obtained, the petal-shaped BiOBr is formed by stacking sheets, a large number of slit-shaped holes exist, and Er is doped with CeO2A heterojunction structure is formed with the BiOBr, so that the recombination of photo-generated electrons and holes is effectively inhibited, and the graphene modified Er doped with CeO2The BiOBr heterojunction has excellent performance of photocatalytic degradation of tetracycline.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
Background
The usage amount of antibiotics in China is very large, so that a large amount of wastewater containing antibiotics can be generated every year to cause environmental pollution, a large amount of antibiotics can be detected in water environments with different matrixes, most of the antibiotics have biotoxicity and are difficult to degrade by adopting a biological method, drug-resistant and drug-resistant genes can be generated in the environment, the treatment difficulty of diseases is increased, the health and ecological safety of human beings are seriously threatened, and the tetracycline is very large in usage amount and is widely applied to the medical industry and the breeding industry, so that the chemical property is stable, the toxicity is strong, great influences can be easily generated on human beings and organisms, and the antibiotics must be treated.
At present, common treatment technologies of antibiotics include a biological method, a photocatalytic oxidation method, an adsorption method and the like, wherein the photocatalytic oxidation method has the advantages of utilizing sunlight, thoroughly treating pollutants, recycling materials and the like, and can treat antibiotic wastewater relatively in an environment-friendly manner.
Among numerous photocatalysts, BiOBr has the advantages of proper forbidden band width, capability of being excited by visible light, simple preparation process, good chemical stability and the like, and is widely applied to the aspects of hydrogen production by water photolysis and organic matter photocatalytic degradation and the like, but the photoproduction electron-hole recombination speed of single BiOBr is too high, the quantum efficiency is very low, and the efficiency of organic pollutants such as tetracycline and the like photocatalytic degradation is low, therefore, the graphene modified Er doped with CeO is adopted2The method of the BiOBr heterojunction overcomes the above drawbacks.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a graphene modified Er doped CeO2The material is a photocatalytic degradation material of a BiOBr heterojunction, and solves the problems that the photo-generated electrons and holes of BiOBr photocatalysis are easy to compound and the photocatalytic activity is greatly reduced.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: graphene modified Er doped CeO2-photocatalytic degradation material of BiOBr heterojunction, said graphene modified Er doped CeO2The preparation method of the photocatalytic degradation material of the BiOBr heterojunction comprises the following steps:
(1) adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 8-10, adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 15-25:100, placing the beaker into a water bath device, carrying out heat treatment at 70-90 ℃ for 30-90min, filtering, washing and drying to obtain reduced graphene oxide;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 5-10min to disperse uniformly, adding oxalic acid, performing continuous ultrasonic treatment for 2-6h to react, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-shaped Er doped cerium oxalate in a tubular furnace, and calcining to obtain the porous shuttle-shaped Er doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, performing ultrasonic treatment for 1-3h to disperse uniformly, adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, performing ultrasonic treatment for 30-90min to disperse uniformly, adding potassium bromide, stirring uniformly, placing in a reaction kettle, reacting at 140-180 ℃ for 6-18h, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2Carrying out ultrasonic dispersion for 2-4h, standing for 4-8h, centrifuging, washing and drying to obtain graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
Preferably, the water bath device in the step (1) comprises a main body, wherein a positioning block is movably connected to the left side of the main body, a roller is movably connected to the middle of the positioning block, an arc-shaped clamping plate is movably connected to the rear side of the positioning block, a screw rod is movably connected to the right side of the arc-shaped clamping plate, a nut is movably connected to the top of the screw rod, a heating coil is movably connected to the middle of the main body, a temperature sensor is movably connected to the bottom of the main body, and a control.
Preferably, the mass ratio of the cerium nitrate, the erbium nitrate, the polyvinylpyrrolidone and the oxalic acid in the step (2) is 100:1-5:160-200: 50-65.
Preferably, the calcination process in the step (3) is roasting at 350-450 ℃ for 1-3h in an air atmosphere.
Preferably, the mass ratio of the reduced graphene oxide, the hexadecyl trimethyl ammonium bromide, the bismuth nitrate, the urea and the potassium bromide in the step (4) is 1-6:70-80:100:65-75: 55-65.
Preferably, the porous shuttle-type Er is doped with CeO in the step (5)2And the mass ratio of the graphene modified petal-shaped BiOBr is 10-20: 100.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the graphene modified Er doped CeO2The photocatalytic degradation material of the BiOBr heterojunction takes sodium borohydride as a reducing agent to obtain reduced graphene oxide, effectively reduces oxygen-containing groups, has no impurity atoms introduced, effectively improves the conductivity, takes cerium nitrate as a cerium source and erbium nitrate as an erbium source, obtains shuttle-shaped Er doped cerium oxalate under the action of polyvinylpyrrolidone and oxalic acid, and the shuttle-shaped Er doped cerium oxalate is calcined to escape lost gaseous water and carbon dioxide to form a large number of pore structures to obtain porous shuttle-shaped Er doped CeO2The specific surface area is obviously increased, the contact area with sunlight is improved, the photocatalytic efficiency is enhanced, the radius of cerium ions is close to that of erbium ions, the erbium ions replace lattice sites of the cerium ions, oxygen vacancy defects are generated in crystal lattices, the cerium ions can be used as capture traps of photoproduction electrons, the combination of the photoproduction electrons and holes is delayed, and the photocatalytic efficiency is effectively improved.
The graphene modified Er doped CeO2-photocatalytic degradation material of BiOBr heterojunction, using bismuth nitrate as bismuth source, adding reduced graphene oxide, and performing hydrothermal reaction to obtain graphene-modified petal-shaped BiOBr, wherein the petal-shaped BiOBr is formed by stacking sheets and storingIn a large number of slit-shaped cavities, the surfaces of petals are not smooth, the structure is favorable for infiltration of tetracycline solution, the efficiency of degrading tetracycline by photocatalysis is improved, and the n-type semiconductor Er is doped with CeO2Forming a p-n heterojunction structure with a p-type semiconductor BiOBr, CeO2The photo-generated electrons on the conduction band are transferred to the BiOBr conduction band, and the holes on the BiOBr valence band are transferred to CeO with lower potential2On the valence band, the recombination of photogenerated electrons and holes is effectively inhibited, and the Er is modified to be doped with CeO2Graphene on the surface of the BiOBr heterojunction can be used as a photo-generated electron capture center of a catalyst, photo-generated electrons are continuously transferred to the graphene, the separation of the photo-generated electrons and holes is accelerated, the recombination of the photo-generated electrons and holes is delayed, holes generated by electron transition, the photo-generated electrons and O in a solution are delayed2The generated superoxide anions can effectively perform oxidation-reduction reaction with tetracycline to perform a degradation process, so that graphene modified Er doped CeO2The BiOBr heterojunction has excellent performance of photocatalytic degradation of tetracycline.
Drawings
FIG. 1 is a schematic sectional view of a water bath apparatus from above;
fig. 2 is a schematic view of a screw structure.
1. A main body; 2. positioning blocks; 3. a roller; 4. an arc-shaped splint; 5. a screw; 6. a nut; 7. a heating coil; 8. a temperature sensor; 9. and a control module.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: graphene modified Er doped CeO2-photocatalytic degradation material of BiOBr heterojunction, said graphene modified Er doped CeO2The preparation method of the photocatalytic degradation material of the BiOBr heterojunction comprises the following steps:
(1) adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 8-10, adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 15-25:100, the beaker is placed in a water bath device, the water bath device comprises a main body, the left side of the main body is movably connected with a positioning block, the middle of the positioning block is movably connected with a rolling shaft, the rear side of the positioning block is movably connected with an arc-shaped clamping plate, the right side of the arc-shaped clamping plate is movably connected with a screw rod, the top of the screw rod is movably connected with a nut, the middle of the main body is movably connected with a heating coil, the bottom of the main body is movably connected with a, carrying out heat treatment at 70-90 ℃ for 30-90min, filtering, washing and drying to obtain reduced graphene oxide;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 5-10min to uniformly disperse, adding oxalic acid, wherein the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:1-5:160 and 200:50-65, continuing the ultrasonic treatment for 2-6h for reaction, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-type Er doped cerium oxalate in a tubular furnace for calcination, wherein the calcination process is to calcine the mixture for 1 to 3 hours at the temperature of 350-2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, performing ultrasonic treatment for 1-3 hours to uniformly disperse, then adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, performing ultrasonic treatment for 30-90 minutes to uniformly disperse, then adding potassium bromide, wherein the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 1-6:70-80:100:65-75:55-65, stirring uniformly, then placing into a reaction kettle, reacting for 6-18 hours at 140-180 ℃, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2The graphene modified petal-shaped BiOBr is dispersed uniformly by ultrasonic for 2-4h at a mass ratio of 10-20:100, and then is kept stand for 4-8h, centrifuged, washed and dried to obtain the graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
Example 1
(1) Adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 8, and then adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 15:100, placing the beaker in a water bath device, wherein the water bath device comprises a main body, the left side of the main body is movably connected with a positioning block, the middle of the positioning block is movably connected with a rolling shaft, the rear side of the positioning block is movably connected with an arc-shaped clamping plate, the right side of the arc-shaped clamping plate is movably connected with a screw rod, the top of the screw rod is movably connected with a nut, the middle of the main body is movably connected with a heating coil, the bottom of the main body is movably connected with a temperature sensor, the right side of the main body is movably connected;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 5min to uniformly disperse, adding oxalic acid, wherein the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:1:160:50, continuing performing ultrasonic treatment for 2h to perform reaction, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-type Er-doped cerium oxalate in a tubular furnace, and calcining for 1h at 350 ℃ in the air atmosphere to obtain the porous shuttle-type Er-doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, uniformly dispersing by ultrasonic for 1 hour, then adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, uniformly dispersing by ultrasonic for 30min, and then adding potassium bromide, wherein the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 1:70:100:65:55, uniformly stirring, then placing into a reaction kettle, reacting for 6 hours at 140 ℃, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2The graphene modified petal-shaped BiOBr is dispersed uniformly by ultrasonic for 2 hours at a mass ratio of 10:100, and then is subjected to standing for 4 hours, centrifugation, washing and drying to obtain the graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
Example 2
(1) Adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 9, and then adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 20:100, placing the beaker in a water bath device, wherein the water bath device comprises a main body, the left side of the main body is movably connected with a positioning block, the middle of the positioning block is movably connected with a rolling shaft, the rear side of the positioning block is movably connected with an arc-shaped clamping plate, the right side of the arc-shaped clamping plate is movably connected with a screw rod, the top of the screw rod is movably connected with a nut, the middle of the main body is movably connected with a heating coil, the bottom of the main body is movably connected with a temperature sensor, the right side of the main body is movably connected;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 7.5min to uniformly disperse, adding oxalic acid, wherein the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:3:180:57.5, continuing performing ultrasonic treatment for 4h to perform reaction, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-type Er-doped cerium oxalate in a tubular furnace, and calcining for 2h at 400 ℃ in the air atmosphere to obtain the porous shuttle-type Er-doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, performing ultrasonic treatment for 2 hours to disperse uniformly, adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, performing ultrasonic treatment for 60 minutes to disperse uniformly, adding potassium bromide, stirring uniformly, placing the mixture into a reaction kettle, reacting for 12 hours at 160 ℃, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr, wherein the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 3.5:75:100:70: 60;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2The graphene modified petal-shaped BiOBr is dispersed uniformly by ultrasonic for 3 hours at a mass ratio of 15:100, and then is subjected to standing for 6 hours, centrifugation, washing and drying to obtain the graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
Example 3
(1) Adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 10, and then adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 19:100, placing the beaker in a water bath device, wherein the water bath device comprises a main body, the left side of the main body is movably connected with a positioning block, the middle of the positioning block is movably connected with a rolling shaft, the rear side of the positioning block is movably connected with an arc-shaped clamping plate, the right side of the arc-shaped clamping plate is movably connected with a screw rod, the top of the screw rod is movably connected with a nut, the middle of the main body is movably connected with a heating coil, the bottom of the main body is movably connected with a temperature sensor, the right side of the main body is movably connected;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 7min to uniformly disperse, adding oxalic acid, wherein the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:2:170:58, continuing performing ultrasonic treatment for 3h to perform reaction, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-type Er-doped cerium oxalate in a tubular furnace, and calcining for 2h at 390 ℃ in the air atmosphere to obtain the porous shuttle-type Er-doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, uniformly dispersing by ultrasonic for 1 hour, then adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, uniformly dispersing by ultrasonic for 70min, and then adding potassium bromide, wherein the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 3:74:100:69:58, uniformly stirring, then placing into a reaction kettle, reacting for 10 hours at 170 ℃, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2And the graphene modified petal-shaped BiOBr is dispersed uniformly by ultrasonic for 3 hours at a mass ratio of 14:100, and then is subjected to standing for 5 hours, centrifugation, washing and drying to obtain the graphene modified Er doped CeO2Photocatalytic reduction of BiOBr heterojunctionsAnd (5) decomposing the material.
Example 4
(1) Adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 10, and then adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 25:100, placing the beaker in a water bath device, wherein the water bath device comprises a main body, the left side of the main body is movably connected with a positioning block, the middle of the positioning block is movably connected with a rolling shaft, the rear side of the positioning block is movably connected with an arc-shaped clamping plate, the right side of the arc-shaped clamping plate is movably connected with a screw rod, the top of the screw rod is movably connected with a nut, the middle of the main body is movably connected with a heating coil, the bottom of the main body is movably connected with a temperature sensor, the right side of the main body is movably connected;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 10min to uniformly disperse, adding oxalic acid, wherein the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:5:200:65, continuing performing ultrasonic treatment for 6h to perform reaction, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-type Er-doped cerium oxalate in a tubular furnace, and calcining for 3h at 450 ℃ in the air atmosphere to obtain the porous shuttle-type Er-doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, performing ultrasonic treatment for 3 hours to uniformly disperse, then adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, performing ultrasonic treatment for 90 minutes to uniformly disperse, then adding potassium bromide, wherein the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 6:80:100:75:65, uniformly stirring, then placing into a reaction kettle, reacting at 180 ℃ for 18 hours, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2The graphene modified petal-shaped BiOBr is prepared by the steps of ultrasonically dispersing uniformly for 4 hours at a mass ratio of 20:100, standing for 8 hours and centrifugingWashing and drying to obtain graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
Comparative example 1
(1) Adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 8, and then adding sodium borohydride serving as a reducing agent, wherein the mass ratio of the graphene oxide to the sodium borohydride is 10:100, placing the beaker in a water bath device, wherein the water bath device comprises a main body, the left side of the main body is movably connected with a positioning block, the middle of the positioning block is movably connected with a rolling shaft, the rear side of the positioning block is movably connected with an arc-shaped clamping plate, the right side of the arc-shaped clamping plate is movably connected with a screw rod, the top of the screw rod is movably connected with a nut, the middle of the main body is movably connected with a heating coil, the bottom of the main body is movably connected with a temperature sensor, the right side of the main body is;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 5min to uniformly disperse, adding oxalic acid, wherein the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:6:150:50, performing ultrasonic treatment for 2h, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-type Er-doped cerium oxalate in a tubular furnace, and calcining for 1h at 350 ℃ in the air atmosphere to obtain the porous shuttle-type Er-doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, uniformly dispersing by ultrasonic for 1 hour, then adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, uniformly dispersing by ultrasonic for 30min, and then adding potassium bromide, wherein the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 1:60:100:60:50, uniformly stirring, then placing into a reaction kettle, reacting for 6 hours at 140 ℃, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2Graphene modificationPetal-shaped BiOBr with the mass ratio of 8:100, uniformly dispersing by ultrasonic for 2h, standing for 4h, centrifuging, washing and drying to obtain graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
The preparation method comprises the steps of taking tetracycline as a degradation substrate, carrying out the degradation in a photocatalytic reactor, using a 500W xenon lamp as a light source, using circulating cooling water to keep the reaction temperature constant at 20 ℃, using a glass reaction tube as a reaction tube, and carrying out modification on Er doped CeO by graphene obtained in examples and comparative examples2Putting a photocatalytic degradation material of a BiOBr heterojunction into a test tube, adding 10mg/L tetracycline solution, controlling the concentration of the photocatalytic degradation material to be 1.0 g/L, stirring for 30min under a dark condition, turning on a xenon lamp for 5h, taking 2mL of turbid liquid, filtering by using a 0.22 um filter membrane, measuring the concentration of tetracycline by using a high performance liquid chromatograph as obtained filtrate, wherein the volume ratio of methanol to pure water is 70:30 as a mobile phase, the flow rate is 1mL/min, the detection wavelength of an ultraviolet detector is 285nm, the sample injection amount is 5 muL, and the test standard is GB/T23762 2009.
Claims (6)
1. Graphene modified Er doped CeO2-a photocatalytic degradation material of a BiOBr heterojunction, characterized in that: the graphene modified Er doped with CeO2The preparation method of the photocatalytic degradation material of the BiOBr heterojunction comprises the following steps:
(1) adding deionized water and graphene oxide into a beaker to prepare a colloidal solution, dropwise adding a sodium carbonate aqueous solution, adjusting the pH to 8-10, adding a reducing agent sodium borohydride, wherein the mass ratio of the graphene oxide to the sodium borohydride is 15-25:100, placing the beaker into a water bath device, carrying out heat treatment at 70-90 ℃ for 30-90min, filtering, washing and drying to obtain reduced graphene oxide;
(2) adding deionized water, ethylene glycol, cerium nitrate, erbium nitrate and polyvinylpyrrolidone into a beaker, performing ultrasonic treatment for 5-10min to disperse uniformly, adding oxalic acid, performing ultrasonic reaction for 2-6h, centrifuging, washing and drying to obtain shuttle-type Er-doped cerium oxalate;
(3) placing the shuttle-shaped Er doped cerium oxalate in a tubular furnace, and calcining to obtain the porous shuttle-shaped Er doped CeO2；
(4) Adding ethylene glycol and reduced graphene oxide into a beaker, performing ultrasonic treatment for 1-3h to disperse uniformly, adding hexadecyl trimethyl ammonium bromide, bismuth nitrate and urea, performing ultrasonic treatment for 30-90min to disperse uniformly, adding potassium bromide, stirring uniformly, placing in a reaction kettle, reacting at 140-180 ℃ for 6-18h, cooling, centrifuging, washing and drying to obtain graphene modified petal-shaped BiOBr;
(5) adding deionized water and porous shuttle-shaped Er-doped CeO into a beaker2Carrying out ultrasonic dispersion for 2-4h, standing for 4-8h, centrifuging, washing and drying to obtain graphene modified Er doped CeO2-photocatalytic degradation material of the BiOBr heterojunction.
2. The graphene-modified Er-doped CeO composite material of claim 12-a photocatalytic degradation material of a BiOBr heterojunction, characterized in that: the water bath device in the step (1) comprises a main body, wherein a positioning block is movably connected to the left side of the main body, a roller is movably connected to the middle of the positioning block, an arc-shaped clamping plate is movably connected to the rear side of the positioning block, a screw rod is movably connected to the right side of the arc-shaped clamping plate, a nut is movably connected to the top of the screw rod, a heating coil is movably connected to the middle of the main body, a temperature sensor is movably connected to the bottom of the main body, and a.
3. The graphene-modified Er-doped CeO composite material of claim 12-a photocatalytic degradation material of a BiOBr heterojunction, characterized in that: in the step (2), the mass ratio of the cerium nitrate to the erbium nitrate to the polyvinylpyrrolidone to the oxalic acid is 100:1-5:160-200: 50-65.
4. The graphene-modified Er-doped CeO composite material of claim 12-a photocatalytic degradation material of a BiOBr heterojunction, characterized in that: the calcination process in the step (3) is roasting at the temperature of 350-1-3h。
5. The graphene-modified Er-doped CeO composite material of claim 12-a photocatalytic degradation material of a BiOBr heterojunction, characterized in that: in the step (4), the mass ratio of the reduced graphene oxide to the hexadecyl trimethyl ammonium bromide to the bismuth nitrate to the urea to the potassium bromide is 1-6:70-80:100:65-75: 55-65.
6. The graphene-modified Er-doped CeO composite material of claim 12-a photocatalytic degradation material of a BiOBr heterojunction, characterized in that: the porous shuttle type Er doped CeO in the step (5)2And the mass ratio of the graphene modified petal-shaped BiOBr is 10-20: 100.
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| CN113136602A (en) * | 2021-04-19 | 2021-07-20 | 西北师范大学 | Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode |
| CN113209993A (en) * | 2021-05-12 | 2021-08-06 | 南昌航空大学 | Preparation method of La-doped petal-shaped BiOBr photocatalytic material |
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| CN113136602A (en) * | 2021-04-19 | 2021-07-20 | 西北师范大学 | Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode |
| CN113209993A (en) * | 2021-05-12 | 2021-08-06 | 南昌航空大学 | Preparation method of La-doped petal-shaped BiOBr photocatalytic material |
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