CN110420653A - A kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and the preparation method and application thereof - Google Patents
A kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and the preparation method and application thereof Download PDFInfo
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- CN110420653A CN110420653A CN201910822208.4A CN201910822208A CN110420653A CN 110420653 A CN110420653 A CN 110420653A CN 201910822208 A CN201910822208 A CN 201910822208A CN 110420653 A CN110420653 A CN 110420653A
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- Prior art keywords
- hydro
- thermal
- catalyst
- silver
- thermal charcoal
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- 239000003610 charcoal Substances 0.000 title claims abstract description 119
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 230000003115 biocidal effect Effects 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 27
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- -1 Phosphate anion Chemical class 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 27
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000005215 recombination Methods 0.000 abstract description 8
- 230000006798 recombination Effects 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229960005404 sulfamethoxazole Drugs 0.000 description 34
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 34
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- NDYNABNWLRVCDO-UHFFFAOYSA-N phosphoric acid silver Chemical compound [Ag].P(O)(O)(O)=O NDYNABNWLRVCDO-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 11
- 229910000161 silver phosphate Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 3
- 229940071536 silver acetate Drugs 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960000468 sulfalene Drugs 0.000 description 2
- KXRZBTAEDBELFD-UHFFFAOYSA-N sulfamethopyrazine Chemical compound COC1=NC=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 KXRZBTAEDBELFD-UHFFFAOYSA-N 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019083 Osmanthus fragrans Nutrition 0.000 description 1
- 244000242564 Osmanthus fragrans Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- AMHXQVUODFNFGR-UHFFFAOYSA-K [Ag+3].[O-]P([O-])([O-])=O Chemical class [Ag+3].[O-]P([O-])([O-])=O AMHXQVUODFNFGR-UHFFFAOYSA-K 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229960004306 sulfadiazine Drugs 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to water treatment fields more particularly to a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and the preparation method and application thereof.Silver orthophosphate provided by the invention/hydro-thermal charcoal composite photo-catalyst, including hydro-thermal charcoal and the silver orthophosphate for being scattered in the hydro-thermal biology carbon surface.The charcoal that the present invention is prepared using hydro-thermal method as carrier, have richer defect and oxygen-containing functional group, with silver orthophosphate it is compound after, the introducing of hydro-thermal charcoal changes the crystalline structure of silver orthophosphate, is conducive to the absorption to pollutant；On the other hand, the separative efficiency for accelerating photo-generate electron-hole in photochemical catalyst increases the stability in application process, and improves photocatalysis performance.The result shows that, silver orthophosphate of the invention/hydro-thermal charcoal composite photo-catalyst, have many advantages, such as that absorbing ability is strong, photo-generate electron-hole recombination rate is low, photocatalysis performance is good, stability is good, can be used in the antibiotic in photocatalysis removal polluted-water, and there is good cyclical stability.
Description
Technical field
The present invention relates to water-treatment technology field more particularly to a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and
Preparation method and application.
Background technique
In recent years, antibiotics organic pollutant receives the extensive concern of people to the pollution of water body.China's antibiotic
Usage amount reached the 30% of drug consumption amount, and antibiotic can not be completely absorbed and degrade in use, greatly
Part is discharged into natural environment, polluted surface water and underground water.The recall rate of antibiotic is gradually frequent in environment water, and
Concentration is higher.In natural water body, the pollution concentration of sulphadiazine is up to 1160 μ g/L, and in Sewage Environment, sulfalene is disliked
The pollution concentration of azoles is up to 2390 μ g/L, it is seen that antibiotic early has become a kind of emerging pollutant.And antibiotic pollutant has
The features such as high toxicity, difficulty are biodegradable, are easily enriched with, causes to seriously endanger to the ecosystem.
Processing method traditional at present mainly has physical partition method, chemical oxidization method and biological degradation method etc..Physics point
Only pollutant is separated from water body from method, is not eliminated, subsequent processes are more complicated, easily cause during processing
Secondary pollution；Chemical oxidization method needs irreversibly to consume oxidant, is needed in some cases using a large amount of oxidant ability
Exhaustive oxidation not only increases processing cost, and is easy to appear safety problem in oxidant use process；Biological degradation method
Not only process cycle is longer, but also in use to environmental requirement harshness.The drawbacks of for above method, it is necessary to seek
Other are simple and easy, degradation is thorough, low-cost resolving ideas.
Photocatalysis technology belongs to one kind of advanced oxidation processes, due to its feature efficiently, green, environmentally friendly, receives research
The concern of person.Especially it is excellent to have that secondary pollution is few, reaction condition is mild, easy to operate, low energy consumption etc. for visible light catalytic technology
Point is a kind of preferred energy conservation and environmental protection method for solving environmental pollution.Silver orthophosphate itself can be by the material of excited by visible light as one kind
Material is concerned in photocatalysis field.But there is photo-generate electron-hole recombination rate height, stability in silver orthophosphate in application process
Difference, the disadvantages of photocatalysis performance is weak.
Summary of the invention
The purpose of the present invention is to provide a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and preparation method thereof with answer
With, composite photo-catalyst provided by the invention is strong with absorbing ability, photo-generate electron-hole recombination rate is low, photocatalysis performance is good,
The advantages that stability is good can be widely applied for the antibiotic in photocatalysis removal polluted-water.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, including hydro-thermal charcoal and it is scattered in
The silver orthophosphate of the hydro-thermal biology carbon surface.
Preferably, the mass percentage of the silver orthophosphate is 45.6~83.4%, and the quality percentage of hydro-thermal charcoal contains
Amount is 16.6~54.4%.
The present invention provides silver orthophosphate described in above scheme/hydro-thermal charcoal composite photo-catalyst preparation methods, including
Following steps:
Hydro-thermal reaction is carried out after branch powder is distributed in water, obtains hydro-thermal charcoal；
After the dispersion liquid of the hydro-thermal charcoal is mixed with soluble silver salt, be added into mixed system phosphorous acid group from
The solution of son carries out precipitation reaction, obtains silver orthophosphate/hydro-thermal charcoal composite photo-catalyst.
Preferably, the temperature of the hydro-thermal reaction is 180~200 DEG C, and soaking time is 5~8h.
Preferably, when carrying out the hydro-thermal reaction, the solid-to-liquid ratio of branch powder and water is (4~6) g:(60~80) mL.
Preferably, the soluble silver salt is provided in the form of silver salt solution, and the concentration of silver ion is in silver salt solution
0.02~0.03mol/L；The concentration of phosphate anion is 0.1~0.15mol/L in the solution of phosphorus-containing acid ion；It is described solvable
Property silver salt in the solution of silver ion and phosphorus-containing acid ion the molar ratio of phosphate anion be 3:1.
Preferably, the theoretical mass ratio that generates of the hydro-thermal charcoal and silver orthophosphate is (0.05~0.3): 0.25.
Preferably, the time of the precipitation reaction is 1~2h.
The present invention provides make described in silver orthophosphate described in above scheme/hydro-thermal charcoal composite photo-catalyst or above scheme
Application of the silver orthophosphate that the Preparation Method is prepared/hydro-thermal charcoal composite photo-catalyst in visible light catalytic removal antibiotic.
Preferably, it is described application the following steps are included:
By silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and antibiotic water mixing, under visible light conditions into
Row light-catalyzed reaction.
The present invention provides a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, including hydro-thermal charcoal and it is scattered in
The silver orthophosphate of the hydro-thermal biology carbon surface.The present invention is using charcoal prepared by hydro-thermal method as carrier, the life of hydro-thermal method preparation
Object charcoal have richer defect and oxygen-containing functional group, with silver orthophosphate it is compound after, on the one hand, the introducing of hydro-thermal charcoal changes
The crystalline structure of silver orthophosphate is conducive to the absorption to pollutant；On the other hand, photo-generate electron-hole in photochemical catalyst is accelerated
Separative efficiency, reduce the recombination probability of photo-generate electron-hole, increase the stability in application process, and improve light
Catalytic performance.Embodiment the result shows that, silver orthophosphate of the invention/hydro-thermal charcoal composite photo-catalyst, have absorbing ability
By force, the advantages that photo-generate electron-hole recombination rate is low, photocatalysis performance is good, stability is good, can be widely applied for photocatalysis and goes to decontaminate
The antibiotic in water body is contaminated, and there is good cyclical stability.
In addition, charcoal of the invention is prepared using discarded branch as raw material by hydro-thermal method, pass through straightforward procedure reality
The resource utilization of agricultural wastes is showed.
The present invention provides above-mentioned silver orthophosphate/hydro-thermal charcoal composite photo-catalyst preparation method, have simple process,
The low advantage of preparation cost.
The present invention also provides above-mentioned silver orthophosphate/hydro-thermal charcoal composite photo-catalysts to remove antibiotic in visible light catalytic
In application, using different types of antibiotic in visible light photocatalytic degradation water body, method is easy to operate, and reaction condition is mild,
The in-situ immobilization to polluted-water can be achieved.
In addition, application of the invention also has, simple process, processing cost is low, treatment effeciency is high, low energy consumption, highly-safe
The advantages that.
Detailed description of the invention
Fig. 1 is the SEM figure of photochemical catalyst made from embodiment 1；
Fig. 2 is pure phosphoric acid silver and different proportion silver orthophosphate/hydro-thermal charcoal composite photo-catalyst XRD diagram；
Fig. 3 is hydro-thermal charcoal, pure phosphoric acid silver and different proportion silver orthophosphate/hydro-thermal charcoal composite photo-catalyst UV-
Vis figure；
Fig. 4 is hydro-thermal charcoal, pure phosphoric acid silver and 0.1C/Ag3PO4The EIS of composite photo-catalyst schemes；
Fig. 5 is a series of degradation effect figure of the photochemical catalysts prepared by the present invention to sulfamethoxazole (SMX)；
Fig. 6 is pure phosphoric acid silver and 0.1C/Ag in the embodiment of the present invention 43PO4Photochemical catalyst reprocesses sulfamethoxazole SMX
Corresponding degradation effect figure when solution；
Fig. 7 is silver orthophosphate/hydro-thermal charcoal (0.1C/Ag in the embodiment of the present invention 53PO4) composite photo-catalyst is in photocatalysis
In the process to the degradation effect figure of sulfamethoxazole SMX in water after addition capturing agent.
Specific embodiment
The present invention provides a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, including hydro-thermal charcoal and it is scattered in
The silver orthophosphate of the hydro-thermal biology carbon surface.
In the present invention, the hydro-thermal charcoal refers to the charcoal being prepared using hydro-thermal method.In the present invention,
The mass percentage of the silver orthophosphate is preferably 45.6~83.4%, and the mass percentage of hydro-thermal charcoal is preferably 16.6
~54.4%.
In the present invention, the silver orthophosphate is preferably shaped to cube, and partial size is preferably 200~400nm.
For the present invention using charcoal prepared by hydro-thermal method as carrier, the charcoal of hydro-thermal method preparation has richer defect
And oxygen-containing functional group, with silver orthophosphate it is compound after, on the one hand, the introducing of hydro-thermal charcoal changes the crystalline structure of silver orthophosphate, has
Conducive to the absorption to pollutant；On the other hand, the separative efficiency for accelerating photo-generate electron-hole in photochemical catalyst, reduces light
The recombination probability of raw electron-hole, increases the stability in application process, and improve photocatalysis performance.Therefore, of the invention
Silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, have that absorbing ability is strong, photo-generate electron-hole recombination rate is low, photocatalytic
Can be good, stability is good the advantages that, can be widely applied for the antibiotic in photocatalysis removal polluted-water.
The present invention provides silver orthophosphate described in above scheme/hydro-thermal charcoal composite photo-catalyst preparation methods, including
Following steps:
Hydro-thermal reaction is carried out after branch powder is distributed in water, obtains hydro-thermal charcoal；
After the dispersion liquid of the hydro-thermal charcoal is mixed with soluble silver salt, be added into mixed system phosphorous acid group from
The solution of son carries out precipitation reaction, obtains silver orthophosphate/hydro-thermal charcoal composite photo-catalyst.
Branch powder is distributed in water by the present invention, obtains the dispersion liquid of branch powder.
The present invention does not have particular/special requirement, the branch well known in the art that can prepare charcoal to the type of branch.
In a specific embodiment of the present invention, the branch is preferably discarded osmanthus fragrans branch.The present invention preferably to the branch according to
It is secondary to carry out cleaning dry, broken and sieving, obtain branch powder.The present invention specific embodiment party dry, broken to the cleaning
Method is no particular/special requirement, using cleaning well known in the art drying and crumbling method.In the present invention, the sieving is excellent
It was selected as the sieve of 100 mesh, extracting screen underflow.
The present invention preferably passes through stirring and branch powder is distributed in water.In the present invention, the revolving speed of the stirring is preferred
For 300~500rpm, the time of the stirring is preferably 1~3h.In the present invention, the solid-to-liquid ratio of the branch powder and water is excellent
It is selected as (4~6) g:(60~80) mL.
After obtaining the dispersion liquid of branch powder, the dispersion liquid of the branch powder is carried out hydro-thermal reaction by the present invention, is obtained
Hydro-thermal charcoal.
In the present invention, the temperature of the hydro-thermal reaction is preferably 180~200 DEG C, and more preferably 190~200 DEG C；It is described
The soaking time of hydro-thermal reaction is preferably 5~8h, more preferably 5~6h.The present invention preferably is selected from room temperature to hydro-thermal reaction
Temperature, heating rate are preferably 4~10 DEG C/min.Branch powder is carbonized in hydrothermal reaction process of the present invention, obtains
Hydro-thermal charcoal.
After hydro-thermal reaction, the present invention it is also preferable to include hydro-thermal reaction product system is successively centrifuged, solid product it is dry
Dry and grinding, obtains hydro-thermal charcoal.In the present invention, the revolving speed of the centrifugation is preferably 5000~8000rpm, and the present invention is logical
It crosses centrifugation and realizes the washing being separated by solid-liquid separation with solid.In the present invention, the temperature of the drying is preferably 100 DEG C, the present invention couple
The time of the drying does not have particular/special requirement, stops drying when being completely dried.The present invention is to the mode of the grinding without spy
Different to require, in the present invention, the time of the grinding is preferably 5~10min.The partial size of hydro-thermal charcoal is preferably after grinding
0.5~1mm.
After obtaining hydro-thermal charcoal, the present invention mixes the dispersion liquid of the hydro-thermal charcoal with soluble silver salt, to mixed
The solution of phosphorus-containing acid ion is added in zoarium system, carries out precipitation reaction, obtains silver orthophosphate/hydro-thermal charcoal composite photocatalyst
Agent.
The present invention preferably passes through ultrasound and hydro-thermal charcoal is dispersed in water, obtains the dispersion liquid of hydro-thermal charcoal.This hair
The bright dosage to the water does not have particular/special requirement, and hydro-thermal charcoal can be uniformly dispersed.In the present invention, the hydro-thermal
The theoretical mass ratio that generates of charcoal and silver orthophosphate is preferably (0.05~0.3): 0.25.In the present invention, it is described ultrasound
Power is preferably 500~800W, and the time of the ultrasound is preferably 2~5h.
In the present invention, the soluble silver salt is preferably silver nitrate or silver acetate, more preferably silver acetate；It is described solvable
Property silver salt is provided in the form of silver salt solution, and the concentration of silver ion is preferably 0.02~0.03mol/L in silver salt solution, more preferably
For 0.03mol/L.In the present invention, the solution of the phosphorus-containing acid ion is preferably disodium phosphate soln or phosphoric acid solution；
The concentration of phosphate anion is preferably 0.1~0.15mol/L in the solution of the phosphorus-containing acid ion, more preferably 0.1~
0.15mol/L.In the present invention, phosphate anion in the solution of silver ion and phosphorus-containing acid ion in the soluble silver salt
Molar ratio is preferably 3:1.
In the present invention, the hybrid mode of the dispersion liquid of the hydro-thermal charcoal and soluble silver salt preferably stirs mixed
It closes.In the present invention, the revolving speed of the stirring is preferably 300~500rpm, and the time of stirring is preferably 0.5~1.5h.
After obtaining the dispersion liquid of hydro-thermal charcoal and the mixed system of soluble silver salt, the present invention is into the mixed system
The solution of phosphorus-containing acid ion is added, carries out precipitation reaction, obtains silver orthophosphate/hydro-thermal charcoal composite photo-catalyst.
In the present invention, the adding manner of the solution of the phosphorus-containing acid ion is preferably added dropwise.The present invention is to the drop
The speed added does not have particular/special requirement, can guarantee that reaction sufficiently carries out and do not generate reunion.The present invention is preferably in stirring condition
The lower solution that phosphorus-containing acid ion is added.In the present invention, the revolving speed of the stirring is preferably 300~500rpm.The present invention is first
The purpose of soluble silver salt is added is first to allow Ag+It is adsorbed on charcoal, adds phosphate anion, phosphate radical and silver ion occur
Precipitation reaction generates silver orthophosphate, and Direct precipitation is in biological carbon surface.In the present invention, the time of the precipitation reaction is preferably 1
~2h；The temperature of the precipitation reaction is preferably room temperature (20~40 DEG C)；Continue to be kept stirring during the precipitation reaction.This
The time for inventing the precipitation reaction refers to the timing since the solution of phosphate anion is added and finishes.
After precipitation reaction, the present invention it is also preferable to include reaction product system is centrifuged, solid is dry and grinding, obtain
Silver orthophosphate/hydro-thermal charcoal composite photo-catalyst.In the present invention, the revolving speed of the centrifugation is preferably 4000~6000rpm；Institute
Dry preferably vacuum drying is stated, the vacuum drying temperature is preferably 60~80 DEG C；Silver orthophosphate/hydro-thermal is raw after the grinding
The partial size of object charcoal composite photo-catalyst is preferably 250~300nm.
The present invention also provides described in silver orthophosphate described in above scheme/hydro-thermal charcoal composite photo-catalyst or above scheme
The silver orthophosphate that preparation method is prepared/hydro-thermal charcoal composite photo-catalyst answering in visible light catalytic removal antibiotic
With.
In the present invention, the application preferably includes following steps: by silver orthophosphate/hydro-thermal charcoal composite photo-catalyst with
Antibiotic water mixing carries out light-catalyzed reaction under visible light conditions.In the present invention, the antibiotic is preferably sulphur
Amine first oxazole；Concentration of the antibiotic in water body is preferably 0.5~5mg/L.In the present invention, the silver orthophosphate/hydro-thermal
The dosage of charcoal composite photo-catalyst is preferably 0.05~0.3g/L.
In the present invention, the light-catalyzed reaction preferably carries out under agitation, and the rate of the stirring is preferably 300
~500rpm；The time of the light-catalyzed reaction is preferably 90~120min；The temperature of the light-catalyzed reaction is preferably 25~
30℃.The present invention does not have particular/special requirement, the visible light in any source to the source of the visible light.Of the invention specific
In embodiment, using xenon lamp as light source, and the visible light that wavelength is greater than 420nm is obtained using edge filter.
Below with reference to embodiment to silver orthophosphate provided by the invention/hydro-thermal charcoal composite photo-catalyst and preparation method thereof
It is described in detail with application, but they cannot be interpreted as limiting the scope of the present invention.
The preparation of composite photo-catalyst
Embodiment 1
Silver orthophosphate/hydro-thermal charcoal composite photo-catalyst (0.05C/Ag3PO4) preparation method, comprising the following steps:
(1) the discarded branch of cleaning-drying is smashed, is sieved with 100 mesh sieve.It takes 6g sawdust to be added in 60mL deionized water to stir
2h is transferred in hydrothermal reaction kettle, 8 DEG C/min to 200 DEG C of temperature programming, keeps 5h.It is centrifuged under gained mixture 8000rpm, clearly
It washes, is dried at 100 DEG C of temperature, grinding obtains the powdered hydro-thermal charcoal of black, is denoted as C.
(2) hydro-thermal charcoal ultrasound 4h obtained in 0.05g step (1) is distributed in 40mL deionized water, later will
The silver acetate of 60mL 0.03M is added thereto and magnetic agitation 1h, then persistently in whipping process by the phosphoric acid hydrogen of 4mL 0.15M
Two sodium solutions are added dropwise in above-mentioned solution, and 2h is stirred under 400rpm and forms precipitating.It is centrifuged under gained mixture 5000rpm,
Cleaning is dried in vacuo at 80 DEG C, and grinding gained powder obtains silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, is denoted as 0.05C/
Ag3PO4。
The 0.05C/Ag3PO4The mass percentage of middle hydro-thermal charcoal is 16.6%, the mass percentage of silver orthophosphate
It is 83.4%.
Embodiment 2
0.05C/Ag during the preparation method is the same as that of Example 13PO4, unique the difference is that by the 0.05g water in above-mentioned steps (2)
Hot charcoal quality is changed to 0.1,0.2,0.3 and 0g respectively, and obtained product is denoted as 0.1C/Ag respectively3PO4、0.2C/Ag3PO4、
0.3C/Ag3PO4And Ag3PO4。
Wherein, 0.1C/Ag3PO4、0.2C/Ag3PO4、0.3C/Ag3PO4And Ag3PO4The quality percentage of middle hydro-thermal charcoal contains
Amount is followed successively by 28.5%, 44.3%, 54.4% and 0%.
Fig. 1 is the SEM figure of photochemical catalyst obtained in present example 1, and wherein a is hydro-thermal charcoal, and b is pure phosphoric acid
Silver, c 0.1C/Ag3PO4Composite photo-catalyst.As shown in Figure 1, hydro-thermal charcoal forms porous structure；Pure phosphoric acid silver is similar
Chondritic, partial size are about 550nm；In silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, the shape of phosphoric acid Argent grain is
Cube, side length are about 300nm.As it can be seen that the addition of hydro-thermal charcoal changes the shape and particle size of phosphoric acid Argent grain.
Fig. 2 is pure phosphoric acid silver and different proportion silver orthophosphate/hydro-thermal charcoal composite photo-catalyst XRD diagram.It can by Fig. 2
Know the peak of hydro-thermal charcoal do not occur in silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, it may be possible to due to mixing for charcoal
Miscellaneous amount is fewer or the crystallinity of hydro-thermal charcoal is relatively low.And in silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, institute
The peak of the silver orthophosphate of appearance is consistent with the peak of pure phosphoric acid silver, Ag does not occur0Peak, show in recombination process not by Ag+Also
It originally is Ag0。
Fig. 3 is hydro-thermal charcoal, pure phosphoric acid silver and different proportion silver orthophosphate/hydro-thermal charcoal composite photo-catalyst UV-
Vis figure.From the figure 3, it may be seen that the ABSORPTION EDGE of pure phosphoric acid silver is in 538nm or so, and with the increase of hydro-thermal charcoal load capacity, phosphoric acid
Silver/hydro-thermal charcoal composite photo-catalyst enhances the absorbability of visible light, 0.1C/Ag3PO4ABSORPTION EDGE 823nm a left side
It is right.The band-gap energy of corresponding pure phosphoric acid silver is 2.3eV, and 0.1C/Ag3PO4Band-gap energy be reduced to 1.5eV, illustrate hydro-thermal biology
The load of charcoal effectively reduces the band-gap energy of composite photo-catalyst, effectively increases the absorbability to visible light.
Fig. 4 is hydro-thermal charcoal, pure phosphoric acid silver and 0.1C/Ag3PO4The EIS of composite photo-catalyst schemes.As shown in Figure 4, phosphorus
Sour silver/hydro-thermal charcoal composite photo-catalyst has higher photoproduction quantum separation and transfer efficiency than pure phosphoric acid silver, illustrates hydro-thermal
Charcoal is conducive to the separation and transfer of photoproduction quantum, improves photocatalysis performance.
The application of catalyst
Embodiment 3
Take silver orthophosphate/hydro-thermal charcoal composite photo-catalyst (0.05C/Ag3PO4、0.1C/Ag3PO4、0.2C/Ag3PO4、
0.3C/Ag3PO4), hydro-thermal charcoal (Hydrochar) and silver orthophosphate (Ag3PO4) each 20mg, it is respectively added to 200mL, concentration
To be uniformly mixed in sulfamethoxazole (SMX) solution of 1mg/L, sulfamethoxazole is carried out under conditions of 25 DEG C, 400rpm
It adsorbs, reaches adsorption equilibrium after 60min；Mixed liquor after being up to adsorption equilibrium is placed in xenon lamp, and (λ > 420nm, optical power are
Under 50W), light-catalyzed reaction 90min is carried out under conditions of 25 DEG C, 400rpm, completes the processing to SMX.It is any not add
SMX solution under the radiation of visible light of catalyst is as blank group.
Fig. 5 is a series of degradation effect of silver orthophosphates/hydro-thermal charcoal composite photo-catalyst prepared by the present invention to SMX
Figure.As shown in Figure 5, in the case where no catalysis material and only hydro-thermal charcoal, it is seen that light is unknown to the removal effect of SMX
It is aobvious.Under visible light illumination, 90min reaches 48% to the degradation rate of SMX to pure phosphoric acid silver, and silver orthophosphate/hydro-thermal charcoal is compound
Photochemical catalyst under visible light illumination significantly improves the degradation effect of SMX, and effect is best for 0.1C/Ag3PO4, 90min's
Degradation removal rate has reached 98%, and degradation rate and degradation rate significantly improve.
By the result in above-mentioned Fig. 1~5 it is found that the present invention is by the way that hydro-thermal charcoal and silver orthophosphate to be combined with each other preparation
The composite photo-catalyst of formation has strong absorbing ability, the separation of photoproduction quantum and high, the photocatalysis performance enhancing of transfer efficiency etc. excellent
Point.
Embodiment 4
Investigate pure phosphoric acid silver and 0.1C/Ag3PO4Photochemical catalyst goes the stability of sulfamethoxazole (SMX) in water removal, including
Following steps:
Take silver orthophosphate/hydro-thermal charcoal composite photo-catalyst (0.1C/Ag3PO4) and silver orthophosphate (Ag3PO4) each 50mg, point
It is not added to 200mL, in sulfamethoxazole (SMX) solution that concentration is 5mg/L, is mixed under conditions of 25 DEG C, 400rpm equal
It is even, it is placed under xenon lamp (λ > 420nm, optical power 50W), light-catalyzed reaction is carried out under conditions of 25 DEG C, 400rpm
90min completes the processing to SMX.And after the completion of reaction, it is filtered with 0.22 μm of film, cleaning rejoins the sulfanilamide (SN) of 5mg/L
The use that first oxazole (SMX) solution is recycled next time, is repeated 3 times altogether.After per treatment, two kinds of photochemical catalysts are measured
To the degradation efficiency of SMX, as a result as shown in Figure 6.
Fig. 6 is pure phosphoric acid silver and 0.1C/Ag in the embodiment of the present invention 43PO4Photochemical catalyst reprocesses corresponding when SMX solution
Degradation effect figure.It will be appreciated from fig. 6 that after 3 cyclic tests, 0.1C/Ag of the present invention3PO4Drop of the photochemical catalyst to SMX
Solution efficiency drops to 83.2% from the 93.2% of first time, and pure phosphoric acid silver to the degradation efficiency of SMX from first time application
68.2% drops to 31.1%.This illustrates that silver orthophosphate of the invention/hydro-thermal charcoal composite photo-catalyst has excellent stabilization
Property, it is reusable.
Embodiment 5
Investigate silver orthophosphate/hydro-thermal charcoal composite photo-catalyst (0.1C/Ag3PO4) sulfalene is disliked in photocatalytic degradation water
The production of free radical during azoles SMX, comprising the following steps:
(1) 3 parts of 0.1C/Ag are taken3PO4Composite photo-catalyst respectively takes 20mg, is respectively added to 200mL, concentration is 1mg/L's
In sulfamethoxazole (SMX) solution, it is uniformly mixed under conditions of 25 DEG C, 400rpm；
(2) isopropanol of 10mM, 0.5 μM of 1,4-benzoquinone and 5mM are separately added into the resulting 3 portions of mixed liquors of step (1)
EDTA-Na2；
(3) it is placed under xenon lamp (λ > 420nm, optical power 50W), it is anti-that photocatalysis is carried out under conditions of 25 DEG C, 400rpm
90min is answered, the processing to SMX is completed.
Control group: any capturing agent is not added, specially takes 20mg0.1C/Ag3PO4Composite photo-catalyst is added to
In 200mL, sulfamethoxazole (SMX) solution that concentration is 1mg/L, it is uniformly mixed, is placed under conditions of 25 DEG C, 400rpm
Under xenon lamp (λ > 420nm, optical power 50W), light-catalyzed reaction 90min, completion pair are carried out under conditions of 25 DEG C, 400rpm
The processing of SMX.
Fig. 7 is silver orthophosphate/hydro-thermal charcoal (0.1C/Ag in the embodiment of the present invention 53PO4) composite photo-catalyst is in photocatalysis
In the process to the degradation effect figure of SMX in water after addition capturing agent.As shown in Figure 7, it is imitated compared to the degradation for being not added with capturing agent
Simultaneously degradation effect is not significantly changed in the addition of fruit, isopropanol and 1,4-benzoquinone, but EDTA-Na2Addition greatly reduce light and urge
Agent reacts after 90min degradation rate from be not added with capturing agent 98.2% and is reduced to 23.7% to the degradation effect of SMX.As a result
Illustrate that hole is the main oxidation group during this light-catalyzed reaction.
As seen from the above embodiment, silver orthophosphate provided by the invention/hydro-thermal charcoal composite photo-catalyst has extinction energy
The advantages that power is strong, the separation of photoproduction quantum and transfer efficiency are high, photocatalysis performance enhancing；And there is good cyclical stability, energy
The antibiotic being enough recycled and reused in photocatalysis removal water body.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of silver orthophosphate/hydro-thermal charcoal composite photo-catalyst, which is characterized in that including hydro-thermal charcoal and be scattered in described
The silver orthophosphate of hydro-thermal biology carbon surface.
2. silver orthophosphate according to claim 1/hydro-thermal charcoal composite photo-catalyst, which is characterized in that the silver orthophosphate
Mass percentage be 45.6~83.4%, the mass percentage of hydro-thermal charcoal is 16.6~54.4%.
3. silver orthophosphate as claimed in claim 1 or 2/hydro-thermal charcoal composite photo-catalyst preparation method, which is characterized in that including
Following steps:
Hydro-thermal reaction is carried out after branch powder is distributed in water, obtains hydro-thermal charcoal；
After the dispersion liquid of the hydro-thermal charcoal is mixed with soluble silver salt, phosphorus-containing acid ion is added into mixed system
Solution carries out precipitation reaction, obtains silver orthophosphate/hydro-thermal charcoal composite photo-catalyst.
4. preparation method according to claim 3, which is characterized in that the temperature of the hydro-thermal reaction is 180~200 DEG C,
Soaking time is 5~8h.
5. preparation method according to claim 3 or 4, which is characterized in that when carrying out the hydro-thermal reaction, branch powder with
The solid-to-liquid ratio of water is (4~6) g:(60~80) mL.
6. preparation method according to claim 3, which is characterized in that the soluble silver salt is mentioned in the form of silver salt solution
For the concentration of silver ion is 0.02~0.03mol/L in silver salt solution；Phosphate anion is dense in the solution of phosphorus-containing acid ion
Degree is 0.1~0.15mol/L；Phosphate anion rubs in the solution of silver ion and phosphorus-containing acid ion in the soluble silver salt
You are than being 3:1.
7. preparation method according to claim 3, which is characterized in that the hydro-thermal charcoal and the theoretical of silver orthophosphate generate
Mass ratio is (0.05~0.3): 0.25.
8. preparation method according to claim 3, which is characterized in that the time of the precipitation reaction is 1~2h.
9. any one of any one of the claim 1~2 silver orthophosphate/hydro-thermal charcoal composite photo-catalyst or claim 3~8
The silver orthophosphate that the preparation method is prepared/hydro-thermal charcoal composite photo-catalyst is in visible light catalytic removal antibiotic
Using.
10. application according to claim 9, which is characterized in that it is described application the following steps are included:
By silver orthophosphate/hydro-thermal charcoal composite photo-catalyst and antibiotic water mixing, light is carried out under visible light conditions
Catalysis reaction.
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