CN106944118B - Bismuth vanadate composite photocatalyst jointly modified by silver and phosphorus hybrid graphite phase carbon nitride nanosheets and preparation method and application thereof - Google Patents
Bismuth vanadate composite photocatalyst jointly modified by silver and phosphorus hybrid graphite phase carbon nitride nanosheets and preparation method and application thereof Download PDFInfo
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- CN106944118B CN106944118B CN201710142533.7A CN201710142533A CN106944118B CN 106944118 B CN106944118 B CN 106944118B CN 201710142533 A CN201710142533 A CN 201710142533A CN 106944118 B CN106944118 B CN 106944118B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 150
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 150
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000002135 nanosheet Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 124
- 239000004332 silver Substances 0.000 title claims abstract description 92
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 91
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- 229910052698 phosphorus Inorganic materials 0.000 title claims description 49
- 239000011574 phosphorus Substances 0.000 title claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 44
- 229910002804 graphite Inorganic materials 0.000 title claims description 43
- 239000010439 graphite Substances 0.000 title claims description 43
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- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 76
- 229960003405 ciprofloxacin Drugs 0.000 claims description 38
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 20
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 18
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 238000013032 photocatalytic reaction Methods 0.000 claims description 13
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000007540 photo-reduction reaction Methods 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- 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
- SUHOOTKUPISOBE-UHFFFAOYSA-N O-phosphoethanolamine Chemical compound NCCOP(O)(O)=O SUHOOTKUPISOBE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 83
- 230000001699 photocatalysis Effects 0.000 abstract description 30
- 229910002915 BiVO4 Inorganic materials 0.000 abstract description 14
- 238000011068 loading method Methods 0.000 abstract description 2
- 101001027838 Pseudonaja textilis Venom prothrombin activator pseutarin-C non-catalytic subunit Proteins 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Abstract
The invention discloses a bismuth vanadate composite photocatalyst jointly modified by silver and phosphorized graphite-phase carbon nitride nanosheets, and a preparation method and application thereof4，PCNS/BiVO4The surface is modified with simple substance silver. The preparation method comprises the steps of preparing suspension and preparing PCNS/BiVO4And silver loading. The composite photocatalyst has the advantages of high photocatalytic activity, good stability and the like, and the preparation method has the advantages of simple preparation process, simple and convenient operation, low cost and the like. The composite photocatalyst can be used for treating antibiotic wastewater, and has the advantages of simple application method, low cost, high antibiotic removal rate, stable photocatalytic performance, good reusability and the like.
Description
Technical Field
The invention belongs to the technical field of functional composite photocatalysts, and particularly relates to a bismuth vanadate composite photocatalyst jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets, and a preparation method and application thereof.
Background
In recent years, the human society has been rapidly developed, and the living standard of human has been greatly improved. However, the environmental problems are becoming more serious, and it is difficult for the conventional environmental remediation technology to meet the social needs. Therefore, the search for an energy-saving and efficient environment treatment and restoration technology has received extensive attention and research at home and abroad. In the last decade, the photocatalytic technology is rapidly developed, and the research range is continuously expanded. And due to the full development of nano materials and nano technology based on the nano materials, the semiconductor photocatalysis technology for treating inorganic or organic pollutants in the environment is also a promising environment remediation technology. Particularly, the development of visible light responding semiconductor photocatalysis materials further promotes the development and application of semiconductor photocatalysis technology in the field of environmental remediation.
Bismuth vanadate (BiVO) as visible light-responsive catalyst4) Has received a wide range of attention. The bismuth-based material has a proper energy band width, good photochemical stability and visible light response capability. However, since the pure bismuth vanadate material generally has a high recombination rate of photo-generated electrons and holes, most of the photo-generated electrons and holes converted from light energy are consumed in the catalyst, and cannot act on effective photocatalysisThe process. Therefore, it is very necessary to modify the bismuth vanadate material to improve the photocatalytic performance of the material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bismuth vanadate composite photocatalyst jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets, which is high in photocatalytic activity and good in stability, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a bismuth vanadate composite photocatalyst jointly modified by silver and phosphorous hybridized graphite-phase carbon nitride nanosheets comprises bismuth vanadate particles, wherein the bismuth vanadate particles are modified on the surfaces of the phosphorous hybridized graphite-phase carbon nitride nanosheets to form a bismuth vanadate-loaded phosphorous hybridized graphite-phase carbon nitride nanosheet composite material, and the surfaces of the bismuth vanadate-loaded phosphorous hybridized graphite-phase carbon nitride nanosheet composite material are modified with elemental silver.
In the bismuth vanadate composite photocatalyst jointly modified by the silver and phospho-hybrid graphite-phase carbon nitride nanosheets, the mass ratio of the bismuth vanadate particles to the phospho-hybrid graphite-phase carbon nitride nanosheets is preferably 1: 0.7-1.2; the mass ratio of the simple substance silver to the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material is 0.01-0.03: 1.
As a general technical concept, the invention also provides a preparation method of the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite phase carbon nitride nanosheets, which comprises the following steps:
s1, mixing the phosphorus hybrid graphite phase carbon nitride nanosheets with a nitric acid solution containing ammonium vanadate and bismuth nitrate, performing ultrasonic dispersion, and stirring to obtain a suspension;
s2, mixing the suspension obtained in the step S1 with urea for hydrothermal reaction to obtain a bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material;
and S3, mixing the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material obtained in the step S2 with a methyl orange solution containing silver nitrate for photoreduction to obtain the bismuth vanadate composite photocatalyst jointly modified by silver and phospho-hybrid graphite-phase carbon nitride nanosheets.
In the preparation method, preferably, the phospha graphite phase carbon nitride nanosheet is prepared by heating blocky phospha carbon nitride to 500-520 ℃ at a rate of 2-5 ℃/min for 2-4 h.
In the above preparation method, preferably, the preparation method of the block-shaped phospha-carbon nitride comprises the following steps:
(1) dissolving 2-aminoethyl phosphoric acid and melamine into water to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1), and evaporating water to obtain mixed crystals;
(3) in the nitrogen atmosphere, the mixed crystal obtained in the step (2) is heated to 500-520 ℃ and roasted for 2-3 h, and then heated to 520-550 ℃ and roasted for 3-5 h to obtain the massive phosphorized carbon nitride.
In the preparation method, preferably, in the step (1), the mass ratio of the 2-aminoethyl phosphoric acid to the melamine is 1: 50-70; the mass volume ratio of the melamine to the water is 1 g-3 g: 60 mL-150 mL;
and/or in the step (2), the heating temperature is 70-90 ℃;
and/or, in the step (3), heating at a heating rate of 2-6 ℃/min.
In the above preparation method, preferably, in step S1, the mass-to-volume ratio of the phosphorus-hybrid graphite-phase carbon nitride nanosheets to the nitric acid solution containing bismuth nitrate and ammonium vanadate is 20 mg to 60 mg: 1 mL; the molar ratio of the bismuth nitrate to the ammonium vanadate in the nitric acid solution containing the bismuth nitrate and the ammonium vanadate is 1: 1; the ultrasonic dispersion time is 20-60 min;
and/or in the step S2, the mass-volume ratio of the urea to the suspension is 30 mg-70 mg: 1 mL; the hydrothermal reaction is carried out under the condition of stirring; the temperature of the hydrothermal reaction is 70-90 ℃; the time of the hydrothermal reaction is 18-24 h; the rotating speed of the stirring is 400 rpm-600 rpm.
And/or in the step S3, the mass-to-volume ratio of the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite to the silver nitrate-containing methyl orange solution is 0.3-0.5 g: 20 mL; the concentration of silver nitrate in the methyl orange solution containing silver nitrate is 0.24 g/L-0.48 g/L; the solubility of methyl orange in the silver nitrate-containing methyl orange solution is 10 mg/L-30 mg/L; the photoreduction time is 1-2 h.
In the above preparation method, preferably, in step S1, the nitric acid solution of bismuth nitrate and ammonium vanadate is prepared by dissolving bismuth nitrate and ammonium vanadate in nitric acid solution; the concentration of bismuth nitrate in the nitric acid solution containing bismuth nitrate and ammonium vanadate is 0.2-0.3 mol/L, and the concentration of ammonium vanadate is 0.2-0.3 mol/L; the concentration of the nitric acid solution is 1M-2M.
As a general technical concept, the invention also provides an application of the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets or the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets prepared by the preparation method in treatment of antibiotic wastewater, and the application is characterized by comprising the following steps: and mixing the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite carbon nitride nanosheets with the antibiotic wastewater to perform photocatalytic reaction, thereby finishing the treatment of the antibiotic wastewater.
In the above application, preferably, the addition amount of the bismuth vanadate composite photocatalyst modified by both silver and phospho-hybrid graphite-phase carbon nitride nanosheets is 1.0 g to 2.0 g of the bismuth vanadate composite photocatalyst modified by both silver and phospho-hybrid graphite-phase carbon nitride nanosheets added to each liter of the antibiotic wastewater;
and/or the antibiotic in the antibiotic wastewater is ciprofloxacin; the initial concentration of the antibiotics in the antibiotic wastewater is 10 mg/L-20 mg/L;
and/or the light source of the photocatalytic reaction is a xenon lamp light source;
and/or the time of the photocatalytic reaction is 2-4 h.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a bismuth vanadate composite photocatalyst jointly modified by silver and phosphorous hybrid graphite-phase carbon nitride nanosheets, which comprises bismuth vanadate particles, wherein the bismuth vanadate particles are modified on the surfaces of the phosphorous hybrid graphite-phase carbon nitride nanosheets to form a bismuth vanadate-loaded phosphorous hybrid graphite-phase carbon nitride nanosheet composite material, and the surfaces of the bismuth vanadate-loaded phosphorous hybrid graphite-phase carbon nitride nanosheet composite material are modified with simple substance silver. In the phosphorus hybridization graphite phase carbon nitride nanosheet adopted by the invention, the doping of phosphorus atoms can improve the absorption capacity of graphite phase carbon nitride in visible light, and can further improve the photocatalytic effect of the graphite phase carbon nitride material; meanwhile, the surface of the fossilized graphite-phase carbon nitride nanosheet is uneven, the specific surface area is further increased, the contact between the material and a reactant can be promoted, the nucleation growth of bismuth vanadate on the fossilized graphite-phase carbon nitride nanosheet can be facilitated, the contact of the formed composite material is tighter, and the stability is higher. The invention loads bismuth vanadate particles on the phospho-hybrid graphite-phase carbon nitride nanosheets due to BiVO4And the material is tightly combined with the phosphorus hybrid graphite phase carbon nitride nanosheet to form a heterojunction, so that separation of photo-generated electrons and holes is facilitated, and the recombination of the photo-generated electrons and the holes is reduced, thereby improving the photocatalytic performance of the material. According to the invention, the phosphorized graphite phase carbon nitride nanosheet has the advantages of simple preparation, high stability, environmental friendliness and the like, and the bismuth vanadate particles are modified on the surface of the phosphorized graphite phase carbon nitride nanosheet, so that the phosphorized graphite phase carbon nitride nanosheet has the advantages of high visible light absorption degree, good photocatalytic efficiency and the like. In the invention, the simple substance silver is an excellent electronic conductor, a plasma resonance effect (SPR) exists, the simple substance silver is modified on the surface of the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material, the plasma resonance effect of the silver can be fully utilized, and the bismuth vanadate composite photocatalyst modified by the silver and the phospho-hybrid graphite-phase carbon nitride nanosheets together has certain absorption capacity on near infrared light, so that the response degree of the material in the near infrared light is improved, and the bismuth vanadate composite photocatalyst is compoundedThe photocatalytic response range of the photocatalyst is expanded from a visible light region to a near-infrared light region, so that the light energy utilization rate of the composite photocatalyst is enhanced, and the capability of the composite photocatalyst in photocatalytic degradation of pollutants is greatly improved; meanwhile, due to the introduction of the simple substance silver, the composite photocatalyst has good photoproduction electron and hole separation capability, the electron-hole recombination is reduced, and the photocatalytic performance of the composite photocatalyst is improved by reducing the loss of effective electrons and holes in the photocatalytic process. Therefore, the common modification of the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets has a synergistic promotion effect on the improvement of the photocatalytic activity of the bismuth vanadate, and the common modification of the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets enables the composite photocatalyst of the invention to have higher photocatalytic activity and better stability.
2. The invention also provides a preparation method of the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets, wherein bismuth vanadate particles are attached to the surfaces of the phosphorus hybrid graphite-phase carbon nitride nanosheets by a hydrothermal reaction method, so that the preparation method has the advantages of simple preparation process, simplicity and convenience in operation, cost and the like, the bismuth vanadate and the phosphorus hybrid graphite-phase carbon nitride nanosheets can be fully contacted and compounded only through simple hydrothermal reaction, and the formed composite material is stable and firm. In the invention, the simple substance silver is attached to the surface of the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material by a photoreduction method, the method has the advantages of simple operation, uniform dispersion of the simple substance silver, no need of adding an additional auxiliary solvent and the like, and the formed composite material has good stability. Therefore, the preparation method has the advantages of simple preparation process, simple and convenient operation, low cost and the like.
3. The bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite carbon nitride nanosheets can be used for treating antibiotic wastewater, and has the advantages of simple application method, low cost, high antibiotic removal rate, stable photocatalytic performance, good reusability and the like.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) co-modified by silver and phospho hybrid graphite-phase carbon nitride nanosheets prepared in example 1 of the present invention4) And bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) In which (a) is BiVO4And (b) is Ag @ PCNS/BiVO4。
FIG. 2 is a diagram of a bismuth vanadate-loaded phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) XRD pattern of (a).
FIG. 3 is a diagram of a bismuth vanadate-loaded phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) FTIR profile of (1).
FIG. 4 is a bismuth vanadate supported phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) Ultraviolet-visible (UV-vis) diffuse reflectance pattern of (a).
FIG. 5 is a bismuth vanadate supported phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) In the visible light region (420 nm)<λ<760 nm) during photocatalytic degradationThe relationship between the changes is shown schematically.
FIG. 6 is a bismuth vanadate supported phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) In the near infrared region (lambda)>760 nm) under the photocatalysis degradation process, and the relation schematic diagram of the change of the concentration of the ciprofloxacin along with the photocatalysis time.
FIG. 7 shows a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) co-modified by silver and phosphor hybrid graphite-phase carbon nitride nanosheets in example 3 of the present invention4) And the effect chart of the removal rate of ciprofloxacin when wastewater is circularly treated.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The raw materials and instruments used in the following examples are all commercially available; wherein the light source system is PLS-SXE 300C xenon lamp, available from Beijing Pofely Tech Co.
Example 1
A bismuth vanadate composite photocatalyst jointly modified by silver and phosphorous hybridized graphite-phase carbon nitride nanosheets comprises bismuth vanadate particles, wherein the bismuth vanadate particles are modified on the surfaces of the phosphorous hybridized graphite-phase carbon nitride nanosheets to form a bismuth vanadate-loaded phosphorous hybridized graphite-phase carbon nitride nanosheet composite material, and elemental silver is modified on the surfaces of the bismuth vanadate-loaded phosphorous hybridized graphite-phase carbon nitride nanosheet composite material.
In this embodiment, the elemental silver and bismuth vanadate particles can be uniformly dispersed on the surface of the fossilized graphite-phase carbon nitride nanosheet.
In this embodiment, bismuth vanadate particles are modified on the surface of the fossilized graphite-phase carbon nitride nanosheets by a hydrothermal reaction method to form a bismuth vanadate-loaded fossilized graphite-phase carbon nitride nanosheet composite, wherein the mass ratio of the fossilized graphite-phase carbon nitride nanosheets to the bismuth vanadate particles is 1: 1, and the bismuth vanadate particles are nanoparticles.
In this embodiment, elemental silver is modified on the surface of the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material by a photoreduction method, wherein the mass ratio of the elemental silver to the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material is 0.01: 1, and the elemental silver is elemental silver particles.
The bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite-phase carbon nitride nanosheets of the embodiment4) The preparation method comprises the following steps:
(1) dissolving 0.2 g of 2-aminoethyl phosphoric acid and 12.0 g of melamine in 600 mL of deionized water, and fully stirring to obtain a mixed solution; heating the mixed solution at 80 ℃ to completely evaporate water in the mixed solution to obtain white mixed crystals; placing the mixed crystal in a quartz boat sealed by tin foil paper, and roasting in a tube furnace, wherein the specific process is as follows: under the condition of nitrogen atmosphere, heating from room temperature to 500 ℃ at the heating rate of 2 ℃/min for sintering for 3h, then heating to 550 ℃ at the same heating rate, continuing sintering for 5h, and naturally cooling to obtain the required blocky phosphorus hybridized carbon nitride.
(2) And (2) weighing 2.0 g of the blocky phosphitic carbon nitride obtained in the step (1), placing the blocky phosphitic carbon nitride into an open ceramic crucible, sintering the blocky phosphitic carbon nitride in a muffle furnace, raising the temperature from room temperature to 500 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, and cooling the blocky phosphitic carbon nitride to the room temperature to obtain the required phosphitic graphite phase carbon nitride nanosheet (PCNS).
(3) 0.28 g of NH was taken4VO3And 1.16 g of Bi (NO)3)3·5H2O, HNO dissolved in 10 mL of 2M3Mixing the two solutions in a solution, and fully dissolving to obtain a nitric acid solution containing ammonium vanadate and bismuth nitrate; and (3) adding 800 mg of the phosphorus hybrid graphite phase carbon nitride nanosheet obtained in the step (2) into a nitric acid solution containing ammonium vanadate and bismuth nitrate, performing ultrasonic treatment for 30 min, continuously stirring for 60min, and fully mixing to obtain a uniform suspension.
(4) Adding 1.0 g of urea into the suspension obtained in the step (3), and mixingAfter uniform combination, placing the mixture in a water bath with the temperature of 90 ℃, continuously stirring the mixture at the rotation speed of 500 rpm for hydrothermal reaction for 24 hours, then cleaning and filtering the product of the hydrothermal reaction by using a large amount of ultrapure water, placing the obtained material in a vacuum drying oven with the temperature of 60 ℃ for drying for 12 hours to obtain the bismuth vanadate-loaded phospho-hybrid graphite carbon nitride nanosheet composite material (PCNS/BiVO)4）。
(5) Placing 0.3g of the bismuth vanadate loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material prepared in the step (4) into 20mL of methyl orange solution containing silver nitrate, wherein the concentration of the silver nitrate in the methyl orange solution containing the silver nitrate is 0.24 g/L, the concentration of the methyl orange is 20 mg/L, ultrasonically dispersing for 10 min, uniformly mixing, then carrying out photoreduction for 2h under the irradiation of a xenon lamp light source to load simple substance silver on the surface of the bismuth vanadate loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material, collecting, cleaning and drying to obtain a silver and phospho-hybrid graphite-phase carbon nitride co-modified bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO)4）。
Comparative example 1
A preparation method of bismuth vanadate nanoparticles comprises the following steps:
1.41 g of NH were weighed4VO3And 5.82 g of Bi (NO)3)3·5H2O, HNO dissolved in 50 mL of 2M3Mixing the two solutions, dissolving, adding 2.5 g urea, stirring continuously in 90 deg.C water bath for hydrothermal reaction for 24 hr, washing the product with deionized water, vacuum filtering, and drying in 60 deg.C vacuum drying oven for 12 hr to obtain bismuth vanadate nanoparticles (BiVO)4）。
Bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite-phase carbon nitride nanosheets prepared in example 14) And bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) SEM analysis was performed, and the results are shown in FIG. 1. FIG. 1 shows a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiV) co-modified by silver and phosphor hybrid graphite-phase carbon nitride nanosheets prepared in example 1 of the present inventionO4) And bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) In which (a) is BiVO4(b) is Ag @ PCNS/BiVO4. As can be seen from FIG. 1, the bismuth vanadate nanoparticles prepared in comparative example 1 are large and have smooth surfaces, while the silver and phospho hybrid graphite-phase carbon nitride nanosheets prepared in example 1 of the present invention jointly modify a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO)4) The composite photocatalyst has small particles, and the good dispersibility of the composite photocatalyst can be seen from figure 1, so that the agglomeration phenomenon of bismuth vanadate in the preparation process can be reduced, and the three substances of silver and phosphorus doped graphite carbon nitride nanosheets and bismuth vanadate particles are well compounded.
The bismuth vanadate-loaded phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 14) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) XRD analysis was performed separately, and the results are shown in FIG. 2. FIG. 2 is a diagram of a bismuth vanadate-loaded phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) XRD pattern of (a). As can be seen from FIG. 2, the bismuth vanadate nanoparticles prepared in comparative example 1 exhibited strong diffraction peaks due to the strong crystal diffraction intensity of bismuth vanadate, which is observed in PCNS/BiVO4And Ag @ PCNS/BiVO4The diffraction pattern of (a) can show the diffraction peak of the phosphorus hybridized carbon nitride nanosheet, which indicates that the PCNS is present in both composites. However, the content of the simple substance silver is very small, so that the silver-based silver4No obvious spectrum representing the simple substance silver appears in the diffraction spectrum of the silver. XRD result shows that the bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphor hybrid graphite carbon nitride nanosheets4) Was successfully prepared.
Bismuth vanadate prepared in example 1Supported phospho-hybrid graphite-phase carbon nitride nanosheet composite (PCNS/BiVO)4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) Fourier infrared characterization (FTIR) was performed, respectively. FIG. 3 is a diagram of a bismuth vanadate-loaded phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) FTIR profile of (1). As can be seen from FIG. 3, the temperature is 1200--1The position (b) represents a C-N heterocycle representing the presence of a substance of the carbon nitride type, wherein 740 cm-1Denotes VO4The presence of bismuth vanadate laterally reflects the presence of bismuth vanadate in all three species. From this result, it is known that a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) modified by both silver and phospho-hybrid graphite-phase carbon nitride nanosheets4) The preparation is successful.
Bismuth vanadate supported phosphohybrid graphite phase carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 14) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) The results of the UV-diffuse spectral reflectance analysis are shown in FIG. 4. FIG. 4 is a bismuth vanadate supported phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) Ultraviolet-visible (UV-vis) diffuse reflectance pattern of (a). As can be seen from FIG. 4, due to the loading of the phosphorus-hybrid graphite-phase carbon nitride nanosheets, the absorption capacity of bismuth vanadate in the visible light region is improved, and the supported simple substance silver forms a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and the phosphorus-hybrid graphite-phase carbon nitride nanosheets4) Then, the absorption of the catalyst in a visible light region is further enhanced, which reflects the existence of the plasma resonance effect of the simple substance silver under the illumination condition, and further verifies the existence of the silver in the composite catalyst.
Example 2
Bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite-phase carbon nitride nanosheets4) The application of the antibiotic wastewater treatment agent comprises the following steps:
(1) 100 mg of the bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets prepared in example 1 was weighed4) Adding the ciprofloxacin into 100 ml ciprofloxacin waste water with the initial concentration of 10 mg/L in a dark environment, adsorbing for 30 min, and then placing the ciprofloxacin waste water into a photocatalytic reaction device.
(2) A300W xenon lamp is used as a light source, and a photocatalytic reaction is carried out for 120min in a visible light region (lambda is more than 420 nm and less than 760 nm), so that the ciprofloxacin wastewater is treated.
Measuring the absorbance values of the reaction solution at 277nm wavelength when the illumination time is 0, 20min, 40min, 60min, 80min, 100min and 120min, combining with the standard curve to obtain ciprofloxacin concentrations C corresponding to different illumination times, and calculating according to the formula (D = (C =)0-C）/C0X 100% where C0As the initial concentration of ciprofloxacin) the removal rate D of ciprofloxacin was calculated for different light irradiation times, and the results are shown in fig. 5.
In addition, 100 mg of the PCNS/BiVO prepared in example 1 was weighed out separately4And BiVO prepared in comparative example 14The ciprofloxacin wastewater treatment steps are repeated, so that the removal rate of the ciprofloxacin in the wastewater by the two photocatalysts in different illumination time is respectively obtained, and the result is shown in figure 5. Meanwhile, in order to eliminate the influence of the degradation of the ciprofloxacin wastewater on the degradation effect, a control group without any catalyst is also arranged, and the ciprofloxacin wastewater is directly irradiated under a light source, and the result is shown in fig. 5.
FIG. 5 shows bismuth vanadate supported phospho-hybrid graphitic carbon nitride nanoparticles prepared in example 1 of the present inventionSheet composite (PCNS/BiVO)4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) In the visible light region (420 nm)<λ<760 nm) under the photocatalysis degradation process, and the relation schematic diagram of the change of the concentration of the ciprofloxacin along with the photocatalysis time. As can be seen from FIG. 5, the bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphor hybrid graphite phase carbon nitride nanosheets of the invention4) The removal rate of ciprofloxacin in 120min can reach 92.68 percent, compared with simple BiVO4(61.59%) and PCNS/BiVO4The composite material (82.18%) is high, and the photocatalytic efficiency is remarkably improved, namely the composite photocatalyst has higher catalytic rate and better removal effect. Thus, the composite photocatalyst of the invention has BiVO ratio4And PCNS/BiVO4The composite material has higher photocatalytic activity.
Example 3
Bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite-phase carbon nitride nanosheets4) The application of the antibiotic wastewater treatment agent comprises the following steps:
(1) 100 mg of the bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets prepared in example 1 was weighed4) Adding the ciprofloxacin into 100 ml ciprofloxacin waste water with the initial concentration of 10 mg/L in a dark environment, adsorbing for 30 min, and then placing the ciprofloxacin waste water into a photocatalytic reaction device.
(2) A300W xenon lamp is used as a light source, and a photocatalytic reaction is carried out for 120min in a near infrared region (lambda is larger than 760 nm), so that the ciprofloxacin wastewater is treated.
Measuring the absorbance values of the reaction solution at 277nm wavelength when the illumination time is 0, 20min, 40min, 60min, 80min, 100min and 120min, combining with the standard curve to obtain the concentration C of ciprofloxacin corresponding to different illumination times, and calculating according to the formula (D = (C =)0-C）/C0X 100% where C0For initial concentration of ciprofloxacin) for different illumination timesThe results of the removal rate D of ciprofloxacin are shown in FIG. 6.
In addition, 100 mg of the PCNS/BiVO prepared in example 1 was weighed out separately4And BiVO prepared in comparative example 14The above-mentioned ciprofloxacin wastewater treatment steps were repeated to obtain the removal rates of ciprofloxacin in wastewater by the two photocatalysts at different times, and the results are shown in fig. 6. Meanwhile, in order to eliminate the influence of the degradation of the ciprofloxacin wastewater on the degradation effect, a control group without any catalyst is also arranged, and the ciprofloxacin wastewater is directly irradiated under a light source, and the result is shown in fig. 6.
FIG. 6 is a bismuth vanadate supported phosphohybrid graphitic carbon nitride nanosheet composite (PCNS/BiVO) prepared in example 1 of the present invention4) And bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by silver and phosphorus hybrid graphite carbon nitride nanosheets4) Bismuth vanadate nanoparticles (BiVO) prepared in comparative example 14) In the near infrared region (lambda)>760 nm) under the photocatalysis degradation process, and the relation schematic diagram of the change of the concentration of the ciprofloxacin along with the photocatalysis time. As can be seen from FIG. 6, the simple substance silver loaded in the invention has plasma resonance effect (SPR) under the illumination condition, so that the composite catalyst of the invention has certain near infrared light response capability, and under the 120min near infrared illumination condition, the removal rate of ciprofloxacin can reach 17.94%, which is higher than that of simple BiVO4(6.55%) and PCNS/BiVO4The composite materials (12.81%) are all high, which shows that the bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by the silver and phospho hybridized graphite phase carbon nitride nanosheets prepared by the method4) The capability of degrading ciprofloxacin under near-infrared illumination is more excellent than that of other two materials. The results in fig. 5 and fig. 6 show that, in the visible light region and the near infrared region, the bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets prepared by the invention4) Exhibit excellent photocatalytic performance.
Example 4
Investigation of silver and phosphorus hybrid graphite phase carbon nitride nanosheets in commonModified bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO)4) Comprising the following steps:
(1) and (2) performing centrifugal separation on the reaction solution after the photocatalytic reaction in the embodiment 2, collecting the bismuth vanadate composite photocatalyst modified by the silver and the phosphorized graphite-phase carbon nitride nanosheets together, then washing the bismuth vanadate composite photocatalyst by using a large amount of water and ethanol, and drying the bismuth vanadate composite photocatalyst in an oven at the temperature of 60 ℃ for 12 hours to obtain the bismuth vanadate composite photocatalyst modified by the regenerated silver and the phosphorized graphite-phase carbon nitride nanosheets together.
(2) Weighing 100 mg of the bismuth vanadate composite photocatalyst jointly modified by the regenerated silver and the phosphorized graphite carbon nitride nanosheets prepared in the step (1), adding the bismuth vanadate composite photocatalyst into 100 ml of ciprofloxacin wastewater with the initial concentration of 10 mg/L in a light-proof environment, adsorbing for 30 min, and placing the ciprofloxacin wastewater into a photocatalytic reaction device.
(3) A300W xenon lamp is used as a light source, and the photocatalytic reaction is carried out for 120min in a visible light region (420 nm < lambda <760 nm).
(4) Repeating the steps (1) to (3) for 5 times.
After each circulation test is finished, measuring the absorbance value of the reaction solution at the 277nm wavelength, combining a standard curve to obtain the corresponding ciprofloxacin concentration C of each circulation test, and obtaining the ciprofloxacin concentration C according to the formula (D = (C)0-C）/C0X 100% where C0Initial concentration of ciprofloxacin) the removal rate D of ciprofloxacin corresponding to each cycle test was calculated, and the results are shown in fig. 7. FIG. 7 shows a bismuth vanadate composite photocatalyst (Ag @ PCNS/BiVO) co-modified by silver and phospho hybrid graphite-phase carbon nitride nanosheets according to the present invention4) And the effect chart of the removal rate of ciprofloxacin when wastewater is circularly treated. As can be seen from fig. 7, in the 5 th photocatalytic experiment, the photocatalytic removal rate of the bismuth vanadate composite photocatalyst modified by the silver and phosphorus hybrid graphite phase carbon nitride nanosheets of the present invention is still not significantly reduced, and the removal rate can still reach more than 85%, which indicates that the composite photocatalyst of the present invention has good photocatalytic stability and recycling performance.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (9)
1. A preparation method of a bismuth vanadate composite photocatalyst jointly modified by silver and phosphorus hybrid graphite-phase carbon nitride nanosheets is characterized by comprising the following steps:
s1, mixing the phosphorus hybrid graphite phase carbon nitride nanosheets with a nitric acid solution containing ammonium vanadate and bismuth nitrate, performing ultrasonic dispersion, and stirring to obtain a suspension;
s2, mixing the suspension obtained in the step S1 with urea for hydrothermal reaction to obtain a bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material;
s3, mixing the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material obtained in the step S2 with a methyl orange solution containing silver nitrate for photoreduction to obtain a bismuth vanadate composite photocatalyst jointly modified by silver and phospho-hybrid graphite-phase carbon nitride nanosheets; the mass-to-volume ratio of the bismuth vanadate supported phospho-hybrid graphite-phase carbon nitride nanosheet composite material to the methyl orange solution containing silver nitrate is 0.3-0.5 g: 20 mL; the concentration of silver nitrate in the methyl orange solution containing silver nitrate is 0.24 g/L-0.48 g/L; the solubility of methyl orange in the silver nitrate-containing methyl orange solution is 10 mg/L-30 mg/L;
the bismuth vanadate composite photocatalyst jointly modified by the silver and the phosphorized graphite-phase carbon nitride nanosheets comprises bismuth vanadate particles, wherein the bismuth vanadate particles are modified on the surfaces of the phosphorized graphite-phase carbon nitride nanosheets to form bismuth vanadate-loaded phosphorized graphite-phase carbon nitride nanosheet composite materials, and the surfaces of the bismuth vanadate-loaded phosphorized graphite-phase carbon nitride nanosheet composite materials are modified with simple substance silver; the mass ratio of the simple substance silver to the bismuth vanadate-loaded phospho-hybrid graphite-phase carbon nitride nanosheet composite material is 0.01-0.03: 1.
2. The preparation method of claim 1, wherein the phosphorus hybrid graphite phase carbon nitride nanosheets are prepared from bulk phosphorus hybrid carbon nitride by heating to 500-520 ℃ at a rate of 2-5 ℃/min for 2-4 h.
3. The method of claim 2, wherein the method of preparing the bulk phospha-nitrided carbon comprises the steps of:
(1) dissolving 2-aminoethyl phosphoric acid and melamine into water to obtain a mixed solution;
(2) heating the mixed solution obtained in the step (1), and evaporating water to obtain mixed crystals;
(3) in the nitrogen atmosphere, the mixed crystal obtained in the step (2) is heated to 500-520 ℃ and roasted for 2-3 h, and then heated to 520-550 ℃ and roasted for 3-5 h to obtain the massive phosphorized carbon nitride.
4. The preparation method according to claim 3, wherein in the step (1), the mass ratio of the 2-aminoethyl phosphoric acid to the melamine is 1: 50-70; the mass volume ratio of the melamine to the water is 1 g-3 g: 60 mL-150 mL;
and/or in the step (2), the heating temperature is 70-90 ℃;
and/or, in the step (3), heating at a heating rate of 2-6 ℃/min.
5. The preparation method according to any one of claims 1 to 4, wherein in the step S1, the mass-to-volume ratio of the phosphorus-hybrid graphite-phase carbon nitride nanosheets to the nitric acid solution containing bismuth nitrate and ammonium vanadate is 20 mg-60 mg: 1 mL; the molar ratio of the bismuth nitrate to the ammonium vanadate in the nitric acid solution containing the bismuth nitrate and the ammonium vanadate is 1: 1; the ultrasonic dispersion time is 20-60 min;
and/or in the step S2, the mass-volume ratio of the urea to the suspension is 30 mg-70 mg: 1 mL; the hydrothermal reaction is carried out under the condition of stirring; the temperature of the hydrothermal reaction is 70-90 ℃; the time of the hydrothermal reaction is 18-24 h; the rotating speed of the stirring is 400-600 rpm;
and/or in the step S3, the photoreduction time is 1-2 h.
6. The method according to claim 5, wherein in step S1, the nitric acid solution of bismuth nitrate and ammonium vanadate is prepared by dissolving bismuth nitrate and ammonium vanadate in nitric acid solution; the concentration of bismuth nitrate in the nitric acid solution containing bismuth nitrate and ammonium vanadate is 0.2-0.3 mol/L, and the concentration of ammonium vanadate is 0.2-0.3 mol/L; the concentration of the nitric acid solution is 1M-2M.
7. The preparation method according to claim 1, wherein the mass ratio of the bismuth vanadate particles to the phospho-hybrid graphite-phase carbon nitride nanosheets is 1: 0.7-1.2.
8. The application of the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite-phase carbon nitride nanosheets prepared by the preparation method of any one of claims 1 to 7 in treatment of antibiotic wastewater is characterized by comprising the following steps: and mixing the bismuth vanadate composite photocatalyst jointly modified by the silver and phosphorus hybrid graphite carbon nitride nanosheets with the antibiotic wastewater to perform photocatalytic reaction, thereby finishing the treatment of the antibiotic wastewater.
9. The use of claim 8, wherein the amount of the bismuth vanadate composite photocatalyst co-modified by silver and phospho-hybrid graphitic carbon nitride nanosheets added is 1.0 g to 2.0 g per liter of the antibiotic wastewater;
and/or the antibiotic in the antibiotic wastewater is ciprofloxacin; the initial concentration of the antibiotics in the antibiotic wastewater is 10 mg/L-20 mg/L;
and/or the light source of the photocatalytic reaction is a xenon lamp light source;
and/or the time of the photocatalytic reaction is 2-4 h.
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