CN107262131A - A kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method and application of heterojunction material - Google Patents
A kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method and application of heterojunction material Download PDFInfo
- Publication number
- CN107262131A CN107262131A CN201710580053.9A CN201710580053A CN107262131A CN 107262131 A CN107262131 A CN 107262131A CN 201710580053 A CN201710580053 A CN 201710580053A CN 107262131 A CN107262131 A CN 107262131A
- Authority
- CN
- China
- Prior art keywords
- visible light
- responded
- preparation
- heterojunction material
- calcined
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004098 Tetracycline Substances 0.000 claims abstract description 13
- 229960002180 tetracycline Drugs 0.000 claims abstract description 13
- 229930101283 tetracycline Natural products 0.000 claims abstract description 13
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 13
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method of heterojunction material, belongs to technical field of semiconductor, comprises the following steps：Step 1) prepare sheet g C3N4；Step 2) prepare Bi3O4Cl nanometer sheets；Step 3) take Bi3O4Cl nanometer sheets and sheet g C3N4It is fully ground in Subcommittee-to alms bowls, is calcined under Muffle furnace, finally gives Bi3O4Cl/g‑C3N4.A kind of visible light-responded Bi of the present invention3O4Cl/g‑C3N4The preparation method of heterojunction material, using grinding roasting method synthesizing perite (Bi3O4Cl) with carbonitride (g C3N4) heterojunction photocatalyst, simply, reaction cost is low for technique, is easy to batch production, nontoxic, meets environment-friendly requirement；It is a further object of the present invention to provide visible light-responded Bi3O4Cl/g‑C3N4The application of heterojunction material, for tetracycline of being degraded under visible ray, tetracycline of degrading under visible light shows excellent photocatalytic activity.
Description
Technical field
The invention belongs to technical field of semiconductor, and in particular to a kind of visible light-responded Bi3O4Cl/g-C3N4It is heterogeneous
The preparation method and application for tying material.
Background technology
In recent years, as economic continues to develop, the energy, environmental problem in global range are also increasingly severe.Especially
Large-scale application of the antibiotic in terms of medical personal care articles and animal husbandry, making the pollution of antibiotic in water body environment has turned into
The hot issue of current research.Current photocatalysis technology is a kind of emerging pollutant abatement technology, with efficiency high, reaction condition
Gentle the advantages of.
Early in 1972, Japanese scholars Fujishima and Honda was to illumination TiO2Electrode causes water decomposition to produce hydrogen
It was found that, Photocatalitic Technique of Semiconductor is developed in Hydrogen Energy and carry out rapidly with the applied basic research in terms of environmental improvement.
But in solar spectrum, ultraviolet light only accounts for 5%, and the ratio of visible ray is up to 43%, therefore, in order to overcome conventional Ti O2Light
Catalyst is only capable of responding the shortcoming of ultraviolet light, develop can the visible light-responded semiconductor light-catalyst of practical application be current
The hot issue of photocatalysis research field.
g-C3N4As a kind of non-metal semiconductive catalyst, its energy gap is 2.7eV, due to its good chemistry with
The features such as heat endurance, cheap cost, safety non-toxic, gradually causes the favor of researcher in photocatalysis field.This
Outside, due to its excellent physical property and photoelectric characteristic, there is quite varied application in many fields.But, it is single
g-C3N4Can be unsatisfactory by the photocatalytic activity under light, this be probably due to g-C3N4It is limited to the absorption region of visible ray,
And photo-generated carrier is easier to be combined, and causes photocatalytic activity low.On the other hand, chlorine oxygen bismuth (Bi3O4Cl), as one kind
Important metal oxide, now research finds a small amount of Bi3O4Cl be able to can significantly increase with semiconductors coupling formation hetero-junctions
Strong photocatalysis performance, for example：Bi3O4Cl/AgCl, Bi3O4Cl/BiOCl and WO3/Bi3O4Cl etc., however, up to the present not having also
There is Bi3O4Cl and g-C3N4It is compounded to form the preparation of hetero-junctions and the report of photocatalytic applications.
The content of the invention
Goal of the invention：It is an object of the invention to provide a kind of visible light-responded Bi3O4Cl/g-C3N4Heterojunction material
Preparation method, using grinding roasting method synthesizing perite (Bi3O4Cl) with carbonitride (g-C3N4) heterojunction photocatalyst；This hair
Bright another object is to provide visible light-responded Bi3O4Cl/g-C3N4The application of heterojunction material, for degrading four under visible ray
Ring element.
Technical scheme：To achieve the above object, the present invention provides following technical scheme：
A kind of visible light-responded Bi3O4Cl/g-C3N4The preparation method of heterojunction material, comprises the following steps：
Step 1) urea is placed in after drying in oven, grinding it is put into crucible, heating calcining for the first time, calcining is put after terminating
Enter in salpeter solution, drying is washed with water after stirring, regrinding is put into crucible, second of heating calcining finally gives sheet
g-C3N4；
Step 2) by Bi (NO3)3·5H2O ultrasonic disperses obtain solution A in ethylene glycol after stirring ultrasound；By NH4Cl is molten
Solution B is obtained in deionized water, solution B is slowly added in above-mentioned solution A, white turbid liquid is generated and is transferred in reactor, water
Thermal response, question response kettle is cooled to room temperature, and sample is washed with water and ethanol, and drying obtains solid powder C；Finally, solid powder C is put
Enter Muffle furnace, heating roasting finally gives Bi3O4Cl nanometer sheets；
Step 3) take Bi3O4Cl nanometer sheets and sheet g-C3N4It is fully ground, is calcined under Muffle furnace, finally in Subcommittee-to alms bowls
Obtain Bi3O4Cl/g-C3N4。
Step 1) in, described first time heating calcining is that 4h is calcined at 550 DEG C, 2 DEG C/min of heating rate.
Step 1) in, second described of heating calcining is that 4h is calcined at 500 DEG C, 5 DEG C/min of heating rate.
Step 2) in, described hydro-thermal reaction is the hydro-thermal reaction 12h at 160 DEG C；Described heating roasting is in 400-
In 500 DEG C of Muffle furnaces, 5h is calcined under 5 DEG C/min of heating rate.
Step 2) in, described Bi (NO3)3·5H2O and NH4Cl mol ratio is 3:1.
Step 3) in, the roasting under Muffle furnace is in 400 DEG C of Muffle furnaces, to be calcined 2h steps 3) in, it is described
Bi3O4Cl and g-C3N4Mass ratio be 10%-25%.
Described visible light-responded Bi3O4Cl/g-C3N4Prepared by the preparation method of heterojunction material visible light-responded
Bi3O4Cl/g-C3N4Heterojunction material is degraded the application of tetracycline under visible light.
Inventive principle：In order to improve photocatalytic activity, by Bi3O4Cl and g-C3N4Build heterojunction composite photocatalyst, phase
Than in pure Bi3O4Cl and g-C3N4, Bi3O4Cl/g-C3N4Composite effectively overcomes monomer Bi3O4Cl and g-C3N4Electricity
The high shortcoming of the recombination rate in son-hole, improves the separative efficiency of electron-hole and then improves photocatalytic activity.Utilize X-
Diffraction ray (XRD) is analyzed the structure of product, by target contaminant of tetracycline carry out performance test, by it is ultraviolet-
Visible spectrophotometer measures absorbance, to assess its photocatalytic activity.
Beneficial effect：Compared with prior art, a kind of visible light-responded Bi of the present invention3O4Cl/g-C3N4Heterojunction material
Preparation method, using grinding roasting method synthesizing perite (Bi3O4Cl) with carbonitride (g-C3N4) heterojunction photocatalyst, technique
Simply, reaction cost is low, is easy to batch production, nontoxic, meets environment-friendly requirement；It is a further object of the present invention to provide
Visible light-responded Bi3O4Cl/g-C3N4The application of heterojunction material, for tetracycline of being degraded under visible ray, degrades under visible light
Tetracycline shows excellent photocatalytic activity.
Brief description of the drawings
Fig. 1 is embodiment 1-3 Bi3O4Cl/g-C3N4XRD diffraction spectrograms；
Fig. 2 is the Bi prepared by embodiment 23O4Cl/g-C3N4The x-ray photoelectron spectroscopy figure (XPS) of hetero-junctions；
Fig. 3 is Bi3O4Cl/g-C3N4Degradation time-degradation rate of the photochemical catalyst in visible light photocatalytic degradation tetracycline
Graph of a relation.
Embodiment
The present invention is further described with specific embodiment below in conjunction with the accompanying drawings.
A kind of visible light-responded Bi3O4Cl/g-C3N4The preparation method of heterojunction material, comprises the following steps：
Step 1) urea is placed in after drying in oven, grinding it is put into crucible, heating calcining for the first time, calcining is put after terminating
Enter in salpeter solution, drying is washed with water after stirring, regrinding is put into crucible, second of heating calcining finally gives sheet
g-C3N4；
Step 2) by Bi (NO3)3·5H2O ultrasonic disperses obtain solution A in ethylene glycol after stirring ultrasound；By NH4Cl is molten
Solution B is obtained in deionized water, solution B is slowly added in above-mentioned solution A, white turbid liquid is generated and is transferred in reactor, water
Thermal response, question response kettle is cooled to room temperature, and sample is washed with water and ethanol, and drying obtains solid powder C；Finally, solid powder C is put
Enter Muffle furnace, heating roasting finally gives Bi3O4Cl nanometer sheets；
Step 3) take Bi3O4Cl nanometer sheets and sheet g-C3N4It is fully ground, is calcined under Muffle furnace, finally in Subcommittee-to alms bowls
Obtain Bi3O4Cl/g-C3N4。
Step 1) in, heating calcining for the first time is that 4h is calcined at 550 DEG C, 2 DEG C/min of heating rate；Second of heating is forged
Burning is that 4h is calcined at 500 DEG C, 5 DEG C/min of heating rate.
Step 2) in, hydro-thermal reaction is the hydro-thermal reaction 12h at 160 DEG C；The roasting that heats up is in 400-500 DEG C of Muffle furnace
It is interior, it is calcined 5h under 5 DEG C/min of heating rate；Described Bi (NO3)3·5H2O and NH4Cl mol ratio is 3:1.
Step 3) in, roasting is in 400 DEG C of Muffle furnaces, to be calcined 2h under Muffle furnace；Bi3O4Cl and g-C3N4Quality
Than for 10%-25%.
Embodiment 1
Step 1：10g urea is placed in 80 DEG C of drying in oven 24h, crucible is put into after grinding, is calcined at 550 DEG C
4h, 2 DEG C/min of heating rate.Calcining is put into 1mol/L salpeter solutions after terminating, and stirs 24h, drying is washed with water, grinds again
Mill is put into crucible, and 4h, 5 DEG C/min of heating rate are calcined at 500 DEG C.Finally give the g-C of sheet3N4。
Step 2：First by 0.485g Bi (NO3)3·5H2O ultrasonic disperses stir ultrasound 10min in 10mL ethylene glycol,
Obtain solution A.
Secondly by 0.018g NH4Cl, which is dissolved in 25mL deionized waters, obtains solution B, and solution B is slowly added into above-mentioned solution
In A, generate white turbid liquid and be transferred in 50mL reactors, 160 DEG C of hydro-thermal 12h.Question response kettle is cooled to room temperature, is washed with water and ethanol
Sample, drying obtains solid powder C.
Finally, solid powder C is calcined 5h under 500 DEG C of Muffle furnaces, 5 DEG C/min of heating rate.Finally give Bi3O4Cl
Nanometer sheet.
Step 3：Take 0.197g Bi3O4Cl and 1.97gg-C3N4It is fully ground in Subcommittee-to alms bowls at 30min, 400 DEG C of Muffle furnace
It is calcined 2h.Finally give 10wt%Bi3O4Cl/g-C3N4。
Embodiment 2
Step 1：10g urea is placed in 80 DEG C of drying in oven 24h, crucible is put into after grinding, is calcined at 550 DEG C
4h, 2 DEG C/min of heating rate.Calcining is put into 1mol/L salpeter solutions after terminating, and stirs 24h, drying is washed with water, grinds again
Mill is put into crucible, and 4h, 5 DEG C/min of heating rate are calcined at 500 DEG C.Finally give the g-C of sheet3N4。
Step 2：First by 0.485g Bi (NO3)3·5H2O ultrasonic disperses stir ultrasound 10min in 10mL ethylene glycol,
Obtain solution A.
Secondly by 0.018g NH4Cl, which is dissolved in 25mL deionized waters, obtains solution B, and solution B is slowly added into above-mentioned solution
In A, generate white turbid liquid and be transferred in 50mL reactors, 160 DEG C of hydro-thermal 12h.Question response kettle is cooled to room temperature, is washed with water and ethanol
Sample, drying obtains solid powder C.
Finally, solid powder C is calcined 5h under 500 DEG C of Muffle furnaces, 5 DEG C/min of heating rate.Finally give Bi3O4Cl
Nanometer sheet.
Step 3：Take 0.394g Bi3O4Cl and 1.97gg-C3N4It is fully ground in Subcommittee-to alms bowls at 30min, 400 DEG C of Muffle furnace
It is calcined 2h.Finally give 20wt%Bi3O4Cl/g-C3N4。
Embodiment 3
Step 1：10g urea is placed in 80 DEG C of drying in oven 24h, crucible is put into after grinding, is calcined at 550 DEG C
4h, 2 DEG C/min of heating rate.Calcining is put into 1mol/L salpeter solutions after terminating, and stirs 24h, drying is washed with water, grinds again
Mill is put into crucible, and 4h, 5 DEG C/min of heating rate are calcined at 500 DEG C.Finally give the g-C of sheet3N4。
Step 2：First by 0.485g Bi (NO3)3·5H2O ultrasonic disperses stir ultrasound 10min in 10mL ethylene glycol,
Obtain solution A.
Secondly by 0.018g NH4Cl, which is dissolved in 25mL deionized waters, obtains solution B, and solution B is slowly added into above-mentioned solution
In A, generate white turbid liquid and be transferred in 50mL reactors, 160 DEG C of hydro-thermal 12h.Question response kettle is cooled to room temperature, is washed with water and ethanol
Sample, drying obtains solid powder C.
Finally, solid powder C is calcined 5h under 500 DEG C of Muffle furnaces, 5 DEG C/min of heating rate.Finally give Bi3O4Cl
Nanometer sheet.
Step 3：Take 0.4925g Bi3O4Cl and 1.97gg-C3N430min, 400 DEG C of Muffle furnace are fully ground in Subcommittee-to alms bowls
Lower roasting 2h.Finally give 25wt%Bi3O4Cl/g-C3N4。
As shown in figure 1, it can be seen that pure Bi from XRD test result3O4Cl diffraction maximum and standard diagram
(JCPDS, No.36-0760) is corresponding.As the g-C of load different proportion3N4When, in Bi3O4Cl/g-C3N4In compound, we
Both it is observed that Bi3O4Cl characteristic peak, can also be observed that g-C3N4Characteristic peak, therefore we can illustrate by XRD
Bi3O4Cl/g-C3N4The successful preparation of composite photo-catalyst.
As shown in Fig. 2 the composition of chemical element can be determined.Pure Bi can be significantly found from Fig. 23O4Can only in Cl
Enough it was observed that Bi, Cl and O signal peak are detected, in pure g-C3N4We are also merely able to the simple feature for observing C and N
Peak, and in Bi3O4Cl/g-C3N4Bi, Cl, O and C in compound, N signal can be clearly detected, it was demonstrated that
Bi3O4Cl/g-C3N4The successful preparation of composite photo-catalyst.
As shown in figure 3, tetracycline can be stabilized in radiation of visible light in itself, pure g-C3N4And Bi3O4Cl is visible
Degradation rate only has 30% and 50% under light, but Bi3O4Cl/g-C3N4Composite can significantly improve photocatalysis effect.When negative
Carry 15%Bi3O4During Cl, the active highest of degraded tetracycline, degradation rate can reach 76% under 60min.
By regulating and controlling to add different Bi3O4Cl and g-C3N4Mass ratio, ground roasting method prepares Bi3O4Cl/g-C3N4
Heterojunction composite assesses its performance by degrading tetracycline under visible light, and 100mL concentration is added in light reaction bottle
For 10mg/L Ciprofloxacin, the photochemical catalyst of 50mg preparations is added.
Reaction bulb is placed in photochemical reactor, lasting stirring carries out dark reaction 30min, to reach that adsorption-desorption is put down
Weighing apparatus, excludes the influence that adsoptivity is reacted light degradation.After dark reaction is complete, turn on light, lead to condensed water, using 250W xenon lamp as light source,
Optical filter is added in light source both sides simultaneously, to ensure (λ under visible light>420nm) carry out light degradation reaction.
Then, 5mL samples are extracted with syringe at interval of 10min, centrifuge (10,000rmp, 5min), take supernatant liquor,
Analyzed by ultraviolet-uisible spectrophotometer in 537nm characteristic peaks test absorbance.We are it is seen that use 15wt%
Bi3O4Cl/g-C3N4Hetero-junctions shows optimal catalytic performance, under 60min illumination, and tetracycline degradation rate can reach 76%,
Illustrate prepared Bi3O4Cl/g-C3N4Hetero-junctions catalyst can be applied to tetracycline waste water control.
Claims (8)
1. a kind of visible light-responded Bi3O4Cl/g-C3N4The preparation method of heterojunction material, it is characterised in that：Comprise the following steps：
Step 1) urea is placed in after drying in oven, grinding it is put into crucible, heating calcining for the first time, calcining is put into nitre after terminating
Drying is washed with water in acid solution, after stirring, regrinding is put into crucible, second of heating calcining finally gives sheet g-
C3N4；
Step 2) by Bi (NO3)3·5H2O ultrasonic disperses obtain solution A in ethylene glycol after stirring ultrasound；By NH4Cl is dissolved in
Solution B is obtained in ionized water, solution B is slowly added in above-mentioned solution A, white turbid liquid is generated and is transferred in reactor, hydro-thermal is anti-
Should, question response kettle is cooled to room temperature, and sample is washed with water and ethanol, and drying obtains solid powder C；Finally, solid powder C is put into horse
Not stove, heating roasting, finally give Bi3O4Cl nanometer sheets；
Step 3) take Bi3O4Cl nanometer sheets and sheet g-C3N4It is fully ground in Subcommittee-to alms bowls, is calcined, finally gives under Muffle furnace
Bi3O4Cl/g-C3N4。
2. a kind of visible light-responded Bi according to claim 13O4Cl/g-C3N4The preparation method of heterojunction material, it is special
Levy and be：Step 1) in, described first time heating calcining is that 4h is calcined at 550 DEG C, 2 DEG C/min of heating rate.
3. a kind of visible light-responded Bi according to claim 13O4Cl/g-C3N4The preparation method of heterojunction material, it is special
Levy and be：Step 1) in, second described of heating calcining is that 4h is calcined at 500 DEG C, 5 DEG C/min of heating rate.
4. a kind of visible light-responded Bi according to claim 13O4Cl/g-C3N4The preparation method of heterojunction material, it is special
Levy and be：Step 2) in, described hydro-thermal reaction is the hydro-thermal reaction 12h at 160 DEG C；Described heating roasting is in 400-
In 500 DEG C of Muffle furnaces, 5h is calcined under 5 DEG C/min of heating rate.
5. a kind of visible light-responded Bi according to claim 13O4Cl/g-C3N4The preparation method of heterojunction material, it is special
Levy and be：Step 2) in, described Bi (NO3)3·5H2O and NH4Cl mol ratio is 3:1.
6. a kind of visible light-responded Bi according to claim 13O4Cl/g-C3N4The preparation method of heterojunction material, it is special
Levy and be：Step 3) in, the roasting under Muffle furnace is in 400 DEG C of Muffle furnaces, to be calcined 2h.
7. a kind of visible light-responded Bi according to claim 13O4Cl/g-C3N4The preparation method of heterojunction material, it is special
Levy and be：Step 3) in, described Bi3O4Cl and g-C3N4Mass ratio be 10%-25%.
8. the visible light-responded Bi in claim 1-7 described in any one3O4Cl/g-C3N4The preparation method system of heterojunction material
Standby visible light-responded Bi3O4Cl/g-C3N4Heterojunction material is degraded the application of tetracycline under visible light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710580053.9A CN107262131A (en) | 2017-07-17 | 2017-07-17 | A kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method and application of heterojunction material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710580053.9A CN107262131A (en) | 2017-07-17 | 2017-07-17 | A kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method and application of heterojunction material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107262131A true CN107262131A (en) | 2017-10-20 |
Family
ID=60072852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710580053.9A Pending CN107262131A (en) | 2017-07-17 | 2017-07-17 | A kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method and application of heterojunction material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107262131A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043446A (en) * | 2017-12-26 | 2018-05-18 | 浙江睿升环保科技有限公司 | A kind of wide spectrum responds g-C3N4/Ta3N5Composite photocatalyst material and its preparation method and application |
| CN108607590A (en) * | 2018-03-30 | 2018-10-02 | 中国地质大学（武汉） | g-C3N4Graft the preparation method and application of BiOX microsphere photocatalyst |
| CN108620096A (en) * | 2018-04-17 | 2018-10-09 | 江苏大学 | A kind of visible light-responded Ag/Bi3O4Cl composite materials and preparation method and purposes |
| CN108654671A (en) * | 2018-05-03 | 2018-10-16 | 华南师范大学 | A kind of composite photo-catalyst and its preparation method and application |
| CN108872162A (en) * | 2018-05-09 | 2018-11-23 | 福州大学 | A kind of analysis method of the detection carcinomebryonic antigen optical electro-chemistry aptamers based on heterojunction composite |
| CN108855192A (en) * | 2018-07-18 | 2018-11-23 | 武汉理工大学 | Load the preparation method of bismuth molybdate nitrogen defect nitridation carbon composite photocatalyst |
| CN108906110A (en) * | 2018-07-26 | 2018-11-30 | 滨州学院 | A kind of preparation method and applications of photochemical catalyst |
| CN110252381A (en) * | 2019-07-31 | 2019-09-20 | 泉州师范学院 | A kind of preparation and application of 2D-2D tungstic acid/class graphite phase carbon nitride heterojunction structure photochemical catalyst |
| CN110586140A (en) * | 2019-09-30 | 2019-12-20 | 广西民族大学 | photo-Fenton catalyst and preparation method and application thereof |
| CN110605127A (en) * | 2019-08-08 | 2019-12-24 | 青岛耀创高新科技有限公司 | NiTiO3/Bi4NbO8Preparation method of Cl composite photocatalyst material |
| CN110961133A (en) * | 2019-11-29 | 2020-04-07 | 江苏大学 | Nonmetal BCN/g-C3N4Van der Waals heterojunction photocatalyst and preparation method and application thereof |
| CN111644185A (en) * | 2020-06-05 | 2020-09-11 | 南阳师范学院 | Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects |
| CN111744504A (en) * | 2020-07-02 | 2020-10-09 | 重庆大学 | Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst |
| CN112892562A (en) * | 2021-01-28 | 2021-06-04 | 辽宁大学 | Z-type Bi prepared based on in-situ synthesis method3O4Cl/Bi2MoO6Composite photocatalyst and application thereof |
| CN113058624A (en) * | 2021-03-09 | 2021-07-02 | 南阳师范学院 | Bi3O4Cl/g-C3N4Preparation method and application of 2D/2D van der Waals heterojunction |
| CN116273133A (en) * | 2023-04-21 | 2023-06-23 | 上海电力大学 | Double Z type g-C 3 N 4 /Bi 3 O 4 Cl/Cd 0.5 Zn 0.5 S heterojunction photocatalyst, and preparation and application thereof |
| CN116273133B (en) * | 2023-04-21 | 2024-04-23 | 上海电力大学 | Double Z type g-C3N4/Bi3O4Cl/Cd0.5Zn0.5S heterojunction photocatalyst, and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732735A (en) * | 2017-01-18 | 2017-05-31 | 常州大学 | A kind of composite of photocatalytic degradation Microcystin and preparation method and application |
| CN106732715A (en) * | 2016-11-24 | 2017-05-31 | 陕西科技大学 | A kind of BiOCl/g C3N4/Bi2O3Composite granule and its preparation method and application |
-
2017
- 2017-07-17 CN CN201710580053.9A patent/CN107262131A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732715A (en) * | 2016-11-24 | 2017-05-31 | 陕西科技大学 | A kind of BiOCl/g C3N4/Bi2O3Composite granule and its preparation method and application |
| CN106732735A (en) * | 2017-01-18 | 2017-05-31 | 常州大学 | A kind of composite of photocatalytic degradation Microcystin and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 谢云超等: "水热法制备 Bi3O4Cl及其光催化降解罗丹明 B 的研究", 《水资源与水工程学报》 * |
| 黄勇: "Bi3O4Cl基复合催化剂与纳米Cu2O的制备及其光催化性能研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043446A (en) * | 2017-12-26 | 2018-05-18 | 浙江睿升环保科技有限公司 | A kind of wide spectrum responds g-C3N4/Ta3N5Composite photocatalyst material and its preparation method and application |
| CN108607590A (en) * | 2018-03-30 | 2018-10-02 | 中国地质大学（武汉） | g-C3N4Graft the preparation method and application of BiOX microsphere photocatalyst |
| CN108620096A (en) * | 2018-04-17 | 2018-10-09 | 江苏大学 | A kind of visible light-responded Ag/Bi3O4Cl composite materials and preparation method and purposes |
| CN108654671A (en) * | 2018-05-03 | 2018-10-16 | 华南师范大学 | A kind of composite photo-catalyst and its preparation method and application |
| CN108654671B (en) * | 2018-05-03 | 2021-06-22 | 华南师范大学 | Composite photocatalyst and preparation method and application thereof |
| CN108872162A (en) * | 2018-05-09 | 2018-11-23 | 福州大学 | A kind of analysis method of the detection carcinomebryonic antigen optical electro-chemistry aptamers based on heterojunction composite |
| CN108872162B (en) * | 2018-05-09 | 2020-09-01 | 福州大学 | Analysis method for detecting carcinoembryonic antigen photoelectrochemical aptamer based on heterojunction composite material |
| CN108855192A (en) * | 2018-07-18 | 2018-11-23 | 武汉理工大学 | Load the preparation method of bismuth molybdate nitrogen defect nitridation carbon composite photocatalyst |
| CN108906110A (en) * | 2018-07-26 | 2018-11-30 | 滨州学院 | A kind of preparation method and applications of photochemical catalyst |
| CN108906110B (en) * | 2018-07-26 | 2021-02-26 | 滨州学院 | Preparation method and application of photocatalyst |
| CN110252381A (en) * | 2019-07-31 | 2019-09-20 | 泉州师范学院 | A kind of preparation and application of 2D-2D tungstic acid/class graphite phase carbon nitride heterojunction structure photochemical catalyst |
| CN110605127A (en) * | 2019-08-08 | 2019-12-24 | 青岛耀创高新科技有限公司 | NiTiO3/Bi4NbO8Preparation method of Cl composite photocatalyst material |
| CN110586140A (en) * | 2019-09-30 | 2019-12-20 | 广西民族大学 | photo-Fenton catalyst and preparation method and application thereof |
| CN110586140B (en) * | 2019-09-30 | 2022-06-24 | 广西民族大学 | photo-Fenton catalyst and preparation method and application thereof |
| CN110961133A (en) * | 2019-11-29 | 2020-04-07 | 江苏大学 | Nonmetal BCN/g-C3N4Van der Waals heterojunction photocatalyst and preparation method and application thereof |
| CN110961133B (en) * | 2019-11-29 | 2022-07-22 | 江苏大学 | Nonmetal BCN/g-C3N4Van der Waals heterojunction photocatalyst and preparation method and application thereof |
| CN111644185A (en) * | 2020-06-05 | 2020-09-11 | 南阳师范学院 | Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects |
| CN111744504A (en) * | 2020-07-02 | 2020-10-09 | 重庆大学 | Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst |
| CN112892562A (en) * | 2021-01-28 | 2021-06-04 | 辽宁大学 | Z-type Bi prepared based on in-situ synthesis method3O4Cl/Bi2MoO6Composite photocatalyst and application thereof |
| CN112892562B (en) * | 2021-01-28 | 2022-06-14 | 辽宁大学 | Z-type Bi prepared based on in-situ synthesis method3O4Cl/Bi2MoO6Composite photocatalyst and application thereof |
| CN113058624A (en) * | 2021-03-09 | 2021-07-02 | 南阳师范学院 | Bi3O4Cl/g-C3N4Preparation method and application of 2D/2D van der Waals heterojunction |
| CN116273133A (en) * | 2023-04-21 | 2023-06-23 | 上海电力大学 | Double Z type g-C 3 N 4 /Bi 3 O 4 Cl/Cd 0.5 Zn 0.5 S heterojunction photocatalyst, and preparation and application thereof |
| CN116273133B (en) * | 2023-04-21 | 2024-04-23 | 上海电力大学 | Double Z type g-C3N4/Bi3O4Cl/Cd0.5Zn0.5S heterojunction photocatalyst, and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107262131A (en) | A kind of visible light-responded Bi3O4Cl/g‑C3N4The preparation method and application of heterojunction material | |
| CN104549406B (en) | Composite visible light catalyst of g-C3N4/bismuth-based oxide and preparation method and application of composite visible light catalyst | |
| CN102974373B (en) | Preparation method of visible-light photocatalytic material | |
| CN100525905C (en) | Nanometer semiconductor oxidation photocatalyst and preparation method thereof | |
| CN104801328B (en) | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature | |
| CN107890876A (en) | A kind of visible light-responded CC@SnS2/SnO2The preparation method and applications of composite catalyst | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN107649168B (en) | Method for degrading bisphenol A in water through photocatalysis and catalyst used by method | |
| CN101773841A (en) | Photocatalyst for water treatment | |
| CN107088434A (en) | A kind of g C3N4‑Cu2The preparation method and applications of O catalyst | |
| CN105195180B (en) | A kind of selenic acid bismuth photochemical catalyst and preparation method and application | |
| CN105435827B (en) | Ternary system TiO with visible light activity2/WS2/g-C3N4The preparation method of composite photo-catalyst | |
| CN105964250A (en) | Ag10Si4O13 photocatalyst with visible-light response and preparation method and application thereof | |
| CN110075905B (en) | Heterojunction photocatalyst CaSb2O6/g-C3N4Preparation method and application thereof | |
| CN102600865B (en) | Photocatalyst for degrading organic dye waste water pollutants and preparation method thereof | |
| CN107890880A (en) | A kind of preparation method of Nano-size Porous Graphite phase carbon nitride/metatitanic acid manganese composite photo-catalyst | |
| CN108940332A (en) | A kind of high activity MoS2/g-C3N4/Bi24O31Cl10The preparation method of composite photo-catalyst | |
| CN107715906A (en) | A kind of preparation method of the direct Z-type heterojunction composite photocatalyst of carbonitride/zinc titanate/titanium oxide sandwich-like | |
| CN104261466B (en) | A kind of method utilizing hydrothermal synthesis method to prepare black titanium dioxide | |
| CN105214710A (en) | A kind of nonmetal composite visible light catalyst g-C of new green environment protection 3n 4the preparation of/SiC and application thereof | |
| CN107890877A (en) | A kind of Bi3O4Cl/CdS composites and preparation method and purposes | |
| CN108144623A (en) | A kind of nanometer cobalt acid lanthanum material and preparation method thereof | |
| CN103613130B (en) | Preparation method of titanium dioxide nanowire-lead sulfide quantum dot composite material | |
| CN103721699A (en) | NaInO2 photocatalyst and preparation method thereof | |
| CN106268907B (en) | A kind of two dimension Conductive mica load carbonitride catalysis material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |
|
| RJ01 | Rejection of invention patent application after publication |