CN107983377A - Silver/iodate silver composite material of cadmium tungstate modification and its preparation method and application - Google Patents
Silver/iodate silver composite material of cadmium tungstate modification and its preparation method and application Download PDFInfo
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- CN107983377A CN107983377A CN201711114483.8A CN201711114483A CN107983377A CN 107983377 A CN107983377 A CN 107983377A CN 201711114483 A CN201711114483 A CN 201711114483A CN 107983377 A CN107983377 A CN 107983377A
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- silver
- iodate
- composite material
- cadmium tungstate
- cadmium
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 245
- 239000004332 silver Substances 0.000 title claims abstract description 244
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 241
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 149
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 128
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 title claims abstract description 118
- 238000012986 modification Methods 0.000 title claims abstract description 64
- 230000004048 modification Effects 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910021612 Silver iodide Inorganic materials 0.000 claims abstract description 99
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000002351 wastewater Substances 0.000 claims abstract description 42
- 229940045105 silver iodide Drugs 0.000 claims abstract description 37
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000975 dye Substances 0.000 claims abstract description 26
- 238000010521 absorption reaction Methods 0.000 claims abstract description 24
- 230000003115 biocidal effect Effects 0.000 claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 23
- 239000004098 Tetracycline Substances 0.000 claims description 20
- 229960002180 tetracycline Drugs 0.000 claims description 20
- 229930101283 tetracycline Natural products 0.000 claims description 20
- 235000019364 tetracycline Nutrition 0.000 claims description 20
- 150000003522 tetracyclines Chemical class 0.000 claims description 20
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 16
- 229940043267 rhodamine b Drugs 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000011017 operating method Methods 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000002023 wood Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 238000001784 detoxification Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- YSVXTGDPTJIEIX-UHFFFAOYSA-M silver iodate Chemical compound [Ag+].[O-]I(=O)=O YSVXTGDPTJIEIX-UHFFFAOYSA-M 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000003672 processing method Methods 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- -1 silver halide Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
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- 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
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- 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
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Abstract
Silver/iodate silver composite material the invention discloses a kind of modification of cadmium tungstate and its preparation method and application, the composite material includes cadmium tungstate and silver/iodate ag material, on cadmium tungstate, silver/iodate ag material is made of silver/silver iodide material load Ag nano particles and silver iodide.Its preparation method includes：The preparation of silver iodide/cadmium tungstate and photo-reduction in situ prepare Ag@AgI/CdWO4Composite material.The composite material of the present invention have the advantages that wide to visible absorption scope, absorption intensity is high, photogenerated charge conduction with separative efficiency height, photocatalysis performance is good, stability and anti-light corrosive power are strong, its preparation method has the advantages that easy control of reaction conditions, operating method are simple, any organic solvent, non-secondary pollution, environmental benefit are good without using, and has the advantages that removal rate is high, removal rate is fast, easy to operate, of low cost, non-secondary pollution when being used for by the composite material and handle waste water from dyestuff and antibiotic waste water.
Description
Technical field
The invention belongs to material preparation and field of environment protection, it is related to a kind of silver/iodate silver composite material and its preparation side
Method and application, and in particular to a kind of silver/iodate silver composite material of cadmium tungstate modification and its preparation method and application.
Background technology
With expanding economy, energy and environment problem becomes increasingly conspicuous, Photocatalitic Technique of Semiconductor due to can realize from
Solar energy is considered as one of method of solution environment and energy problem's most application prospect to chemical transformation of energy.Tradition
Photochemical catalyst TiO2Due to be considered as with higher ultraviolet catalytic activity, environment friendly and chemical stability with
The catalysis material of good production capacity and environment remediation application prospect.However, due to TiO2Energy gap be 3.2eV so that its
It can only be seriously limited in visible ray to accounting for the ultraviolet light response of solar energy 4%（λ > 400 nm）The lower degradation of contaminant of irradiation
In application.Therefore, photochemical catalyst of the structure with high visible light catalytic activity becomes the research focus of photocatalysis field.
In recent years, silver halide semiconductor AgX（X=Cl, Br and I）Extensive research interest is drawn, and has been used as polluting
The catalysis material of thing degraded, especially AgI, it has the eV of relatively narrow forbidden band ~ 2.8 compared with AgCl and AgBr, this causes it to have
There is good visible light-responded characteristic, and AgI can coexist to form Ag@in photocatalytic process with silver nano-grain stabilization
AgI.Nano silver grain has plasma resonance effect, can be remarkably reinforced visible light catalysis activity.However, photogenerated charge is fast
Reply immediately conjunction and AgI easily photoetch and seriously limit Ag@AgI photocatalysis efficiency and practical application under visible ray photograph.Thus
Ag@AgI base optic catalytic material of the exploitation with high visible light catalytic activity is the necessary way for realizing the efficient removal efficiency of pollutant
Footpath.As multi-component metal oxide, tungstates is due to the excellent performance in its optics, chemistry and structure, it is considered to be
Widely used functional material.Wherein, CdWO4Not only have and TiO2Suitable ultraviolet catalytic activity, also has higher
Refractive index, Low emissivity damage and excellent X-ray absorption.Thus, CdWO4It is considered as the new and effective photocatalysis composite wood of structure
The good carrier of material.Up to the present, although a variety of CdWO4The light of base urges material, such as CdS/CdWO4、g−C3N4/CdWO4、
CdWO4/Bi2O2CO3、C3N4/CdS/CdWO4、WO3/CdWO4Deng being produced, but the synthetic method of above-mentioned material is complicated, institute
Need that temperature is high, energy consumption is big, production cost is high, and the photogenerated charge separative efficiency of product is unsatisfactory, it is difficult to meet that industrialization should
Demand.Therefore acquisition one kind is wide to visible light-responded scope, absorption intensity is high, photogenerated charge conduction and separative efficiency are high,
The wolframic acid alkali silver system that photocatalysis performance is good, anti-light corrosive nature is strong（Ag@AgI/CdWO4）Composite material and offer are a kind of anti-
Condition is answered to be easy to control, operating method is simple, is imitated in preparation process without using any organic solvent, non-secondary pollution, environmental protection
The good Ag@AgI/CdWO of benefit4The preparation method of composite material is of great significance.
The content of the invention
It is a kind of to visible absorption scope the technical problem to be solved in the present invention is overcoming the deficiencies of the prior art and provide
Extensively, absorption intensity height, photogenerated charge conduct and separative efficiency is high, photocatalysis performance is good, stability and anti-light corrosive power are strong, follows
Silver/iodate silver composite material of the good cadmium tungstate modification of ring usability, additionally provides a kind of easy control of reaction conditions, operation side
Method is simple, do not have in preparation process the silver modified using the good cadmium tungstate of any organic solvent, non-secondary pollution, environmental benefit/
The preparation method of iodate silver composite material, and the cadmium tungstate modification silver/iodate silver composite material processing waste water from dyestuff and
The application of antibiotic waste water, the application process have removal rate is high, removal rate is fast, it is easy to operate, of low cost, without secondary dirt
The advantages that dye.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of silver/iodate silver composite material of cadmium tungstate modification, including cadmium tungstate and silver/iodate ag material, the silver/silver iodide
Material load is on cadmium tungstate；The silver/iodate ag material is made of Ag nano particles and silver iodide.
It is further improved in silver/iodate silver composite material of above-mentioned cadmium tungstate modification, the cadmium tungstate modification
In silver/iodate silver composite material, the mass percentage of the Ag nano particles is 0.3%~1.5%, the quality of the silver iodide
Percentage composition is 21.3%~90.3%, and the mass percentage of the cadmium tungstate is 8.2%~78.3%.
It is further improved in silver/iodate silver composite material of above-mentioned cadmium tungstate modification, the cadmium tungstate modification
The specific surface area of silver/iodate silver composite material is 0.075 m2The m of/g~5.452/ g, average pore size are 2.30 nm~14.62
Nm, pore volume are 0.0005 cm3The cm of/g~0.01923/g；The silver/iodate ag material is graininess, a diameter of 200 nm~
800 nm；The cadmium tungstate is nano bar-shape, and length is the nm of 200 nm~400, the nm of a diameter of 50 nm~100.
The technical concept total as one, present invention also offers a kind of silver/silver iodide of above-mentioned cadmium tungstate modification are multiple
The preparation method of condensation material, comprises the following steps：
S1, mix KI, cadmium tungstate in water, and ultrasound, is added dropwise AgNO3Solution carries out in-situ precipitate reaction, is contained
The mixed liquor of silver iodide/cadmium tungstate；
The mixed liquor containing silver iodide/cadmium tungstate in step S1, is placed in progress photoreduction in situ by S2, is centrifuged, washing,
Vacuum drying, obtains silver/iodate silver composite material of cadmium tungstate modification.
Further improved in above-mentioned preparation method, in step S1, the preparation method of the cadmium tungstate includes following step
Suddenly：By Na2WO4·2H2O solution adds to Cd (NO dropwise3)2·4H2In O solution, the pH for adjusting gained mixed solution carries out hydro-thermal
Reaction, is filtered, and is washed, dry, obtains cadmium tungstate.
It is further improved in above-mentioned preparation method, the Na2WO4·2H2Na in O solution2WO4·2H2O and institute
State Cd (NO3)2·4H2Cd (NO in O solution3)2·4H2The mass ratio of O is 1.069~1.070: 1；
And/or the pH of the mixed solution is adjusted using ammonium hydroxide；The pH of the mixed solution is 9.2~9.4；The ammonium hydroxide
Mass concentration is 25%~28%；
And/or the temperature of the hydro-thermal reaction is 130 DEG C~150 DEG C；The time of the hydro-thermal reaction is 12h~16h；It is described
Washing uses absolute ethyl alcohol and water successively；The temperature of the drying is 50 DEG C~70 DEG C；The time of the drying is 10h~14
h。
It is further improved in above-mentioned preparation method, in step S1, the KI, the AgNO3AgNO in solution3With
The mass ratio of the cadmium tungstate is 0.19~7.73: 0.20~8.21: 1；The ultrasonic time is 30min~60min；It is described
In-situ precipitate reaction carries out under agitation；The rotating speed of the stirring is 300rpm~450rpm；The in-situ precipitate reaction
Time be 30min~60min；
And/or in step S2, the original position photoreduction carries out under ultraviolet light conditions；The original position photoreduction
Time is 25min~35min；The washing uses water and absolute ethyl alcohol successively；The vacuum drying temperature is 50 DEG C~70
℃；The vacuum drying time is 4 h~6h.
The technical concept total as one, the present invention provides a kind of silver/silver iodide of above-mentioned cadmium tungstate modification are compound
Application of the material in antibiotic waste water is handled.
It is further improved in above-mentioned application, comprise the following steps：Silver/silver iodide composite wood that cadmium tungstate is modified
Material is mixed with antibiotic waste water, and absorption is vibrated under dark condition, after reaching adsorption equilibrium, carries out photocatalysis drop under light illumination
Solution, completes the processing to antibiotic waste water；The additive amount of silver/iodate silver composite material of the cadmium tungstate modification is described in every liter
The mg of silver/iodate silver composite material 100mg of cadmium tungstate modification~300 is added in antibiotic waste water.
Further improved in above-mentioned application, the antibiotic in the antibiotic waste water is tetracycline；The antibiotic
The concentration of antibiotic is the mg/L of 15 mg/L~25 in waste water；
And/or the time of the vibration absorption is the min of 60 min~120；
And/or the photocatalytic degradation carries out under the visible ray of 400 nm of wavelength ＞；
And/or the time of the photocatalytic degradation is the min of 2 min~24.
The technical concept total as one, the present invention provides a kind of silver/silver iodide of above-mentioned cadmium tungstate modification are compound
Application of the material in waste water from dyestuff is handled.
It is further improved in above-mentioned application, comprise the following steps：Silver/silver iodide composite wood that cadmium tungstate is modified
Material is mixed with waste water from dyestuff, and absorption is vibrated under dark condition, after reaching adsorption equilibrium, carries out photocatalysis drop under light illumination
Solution, completes the processing to waste water from dyestuff；The additive amount of silver/iodate silver composite material of the cadmium tungstate modification is every liter of dye
The mg of silver/iodate silver composite material 100mg of cadmium tungstate modification~300 is added in material waste water.
Further improved in above-mentioned application, the dyestuff in the waste water from dyestuff is rhodamine B；The waste water from dyestuff
The concentration of middle dyestuff is the mg/L of 15 mg/L~25；
And/or the time of the vibration absorption is the min of 60 min~120；
And/or the photocatalytic degradation carries out under the visible ray of 400 nm of wavelength ＞；
And/or the time of the photocatalytic degradation is the min of 2 min~24.
Compared with prior art, the advantage of the invention is that：
1st, the present invention provides a kind of silver/iodate silver composite material of cadmium tungstate modification, including cadmium tungstate and silver/silver iodide material
Material, silver/iodate ag material are made of Ag nano particles and silver iodide, are supported on cadmium tungstate, and wherein AgI has visible light-responded
Characteristic, Ag nano particles have plasma resonance effect, the two is combined into silver/iodate ag material can be by long wave excited by visible light
Photogenerated charge is produced, lifts the utilization rate of solar energy；CdWO4With big specific surface area, be conducive to pollutant on its surface
Mass transfer spreads and is contacted with free radical.On this basis, by the silver/silver iodide material load being made of Ag, AgI in CdWO4On,
Make Ag, AgI and CdWO4It is compound and be closely linked, conduction and the separative efficiency of photogenerated charge can not only be improved, moreover it is possible to open up
AgI is opened up to the absorption region of visible ray, enhancing to the absorption intensity of visible ray, lifting photocatalysis performance, stability and anti-light corruption
Erosion ability.Silver/iodate silver composite material of cadmium tungstate of the present invention modification have wide to visible absorption scope, absorption intensity is high,
Photogenerated charge conduct with separative efficiency is high, photocatalysis performance is good, stability and anti-light corrosive power by force, recycling property it is good etc. excellent
Point.
2nd, the preparation method for the silver/iodate silver composite material modified present invention also offers a kind of cadmium tungstate, utilizes CdWO4
With I-Between electrostatic attraction effect, first by I-It is adsorbed to CdWO4Surface, passes through in-situ precipitate Ag+With I-In CdWO4Surface into
Nucleus growth crystallizes, and forms AgI/CdWO4Hetero-junctions, and then under ultraviolet lighting, AgI/CdWO4It is stimulated and produces light induced electron, will
Ag (I) in the AgI of part is reduced into Ag0, obtain Ag@AgI/CdWO4Composite material.The obtained Ag@AgI/CdWO of the present invention4
Middle Ag@AgI are supported on CdWO4On, it is closely linked, wherein Ag@AgI are random graininess, the size of Ag@AgI
For 200 nm~800 nm, CdWO4For the nano bar-shape of rule, CdWO4The length of rod is the nm of 200 nm~400, a diameter of 50
The nm of nm~100, and gained Ag@AgI/CdWO4The specific surface area of composite material is 0.075 m2The m of/g~5.452/ g, average hole
Footpath is the nm of 2.30 nm~14.62, and pore volume is 0.0005 cm3The cm of/g~0.01923/g。
3rd, in preparation method of the invention, composite material is prepared using in-situ precipitate-photoreduction met hod, there is reaction condition to hold
Easy to control, operating method is simple, in preparation process without good etc. excellent using any organic solvent, non-secondary pollution, environmental benefit
Point.
4th, present invention also offers a kind of method for handling waste water from dyestuff, Ag@AgI/CdWO using the present invention4Composite wood
Material processing waste water from dyestuff, have removal rate is high, removal rate is fast, processing time is short, it is easy to operate, of low cost, without secondary dirt
The advantages that dye.By taking rhdamine B waste water as an example, by Ag@AgI/CdWO4Composite material is used to handle the rhodamine B in water body,
High visible light catalytic performance is shown, wherein 99.3% is respectively reached to the most degradation rate of rhodamine B, and at five times
Degradation rate after recycling remains to reach 90.2 %, with good stability and reusing.As it can be seen that Ag@of the present invention
AgI/CdWO4The detoxification of Wastewater Dyes and harmless processing are can be widely applied to, to the silver-colored system of exploitation, halide, tungstates
Sill and applied to environmental area tool be of great significance.
5th, present invention also offers a kind of method for handling antibiotic waste water, Ag@AgI/CdWO using the present invention4It is compound
Material process antibiotic waste water, has fast removal rate height, removal rate, processing time is short, easy to operate, of low cost, nothing two
The advantages that secondary pollution.By taking tetracycline wastewater as an example, by Ag@AgI/CdWO4Composite material is used to handle the tetracycline in water body, table
Reveal high visible light catalytic performance, wherein 77.0% is respectively reached to the most degradation rate of tetracycline, and in five circulations
Degradation rate after utilization remains to reach 67.6%, with good stability and reusing.As it can be seen that Ag@AgI/ of the present invention
CdWO4The detoxification of antibiotic and harmless processing in waste water are can be widely applied to, to the silver-colored system of exploitation, halide, wolframic acid alkali
Material and applied to environmental area tool be of great significance.
Brief description of the drawings
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, clear, complete description is carried out to the technical solution in the embodiment of the present invention.
Fig. 1 is the scanning electron microscope (SEM) photograph for silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified.
Fig. 2 is the transmission electron microscope picture for silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified.
Fig. 3 is silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified（AICW-3）And cadmium tungstate
Material（CW）, silver/iodate silver composite material made from comparative example 1（AI）Ultraviolet-visible light diffusing reflection abosrption spectrogram.
Fig. 4 is silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified（AICW-3）And cadmium tungstate
Material（CW）, silver/iodate silver composite material made from comparative example 1（AI）Photoproduction surface photoelectricity flow graph.
Fig. 5 is the N for silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified2Adsorption-desorption is bent
Line chart.
Fig. 6 is silver/iodate silver composite material that cadmium tungstate made from 1-4 of the embodiment of the present invention is modified（AICW-1、AICW-
2、AICW-3、AICW-4）, wolframic acid cadmium material（CW）With comparative example 1 made from silver/iodate silver composite material（AI）XRD diagram.
Fig. 7 is silver/iodate silver composite material that cadmium tungstate made from 1-4 of the embodiment of the present invention is modified（AICW-1、AICW-
2、AICW-3、AICW-4）, wolframic acid cadmium material（CW）With comparative example 1 made from silver/iodate silver composite material（AI）In visible ray（λ
> 400 nm）To the degradation effect figure of rhodamine B under irradiation.
Fig. 8 is silver/iodate silver composite material that cadmium tungstate made from 1-4 of the embodiment of the present invention is modified（AICW-1、AICW-
2、AICW-3、AICW-4）, wolframic acid cadmium material（CW）With comparative example 1 made from silver/iodate silver composite material（AI）In visible ray（λ
> 400 nm）To the degradation effect figure of tetracycline under irradiation.
Fig. 9 is silver/iodate silver composite material that cadmium tungstate is modified in the embodiment of the present invention 7（AICW-3）Circulation degraded Luo Dan
The degradation effect figure of bright B and tetracycline.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Raw material and instrument employed in following embodiments are commercially available.In following embodiments, unless otherwise noted, gained
Data are to repeat the average value of experiment above three times.
Embodiment 1
A kind of silver/iodate silver composite material of cadmium tungstate modification, including cadmium tungstate and silver/iodate ag material, silver/iodate ag material
It is supported on cadmium tungstate, silver/iodate ag material is made of Ag nano particles and silver iodide.
In the present embodiment, in silver/iodate silver composite material of cadmium tungstate modification, the mass percentage of Ag nano particles is
1.2%, the mass percentage of silver iodide is 72.4%, and the mass percentage of cadmium tungstate is 26.4%.
In the present embodiment, the specific surface area of silver/iodate silver composite material of cadmium tungstate modification is 3.42 m2/ g, average hole
Footpath is 6.44 nm, and pore volume is 0.0096 cm3/g。
In the present embodiment, silver/iodate ag material is random graininess, and size is the nm of 200nm~800；Cadmium tungstate is
The nano bar-shape of rule, length are the nm of 200 nm~400, the nm of a diameter of 50 nm~100.
A kind of preparation method of silver/iodate silver composite material of cadmium tungstate modification in above-mentioned the present embodiment, including it is following
Step：
（1）CdWO 4Preparation：By 20 ml, the Na that concentration is 0.1M2WO4·2H2O solution adds to 20 ml dropwise, concentration is
Cd (the NO of 0.1 M3)2·4H2In O solution, with mass concentration be 25%~28% ammonium hydroxide adjust gained mixed solution pH to
9.3,30 min are stirred, solution is transferred in 100 ml reaction kettles, in 140 DEG C of 12 h of hydro-thermal reaction, filtering, by filtering
Obtain solid product and use absolute ethyl alcohol and water washing successively, dry 12 h, obtain cadmium tungstate at 60 DEG C（CdWO 4）, it is denoted as CW.
（2）AgI/CdWO4Preparation：By 386.4 mg KI, 200 mg above-mentioned steps（1）In obtained CdWO4Add to 50
In ml water, 30 min of ultrasound, are added dropwise 6 ml and are dissolved with 410.1 mg AgNO3AgNO3Solution and rotating speed be 400
30 min are vigorously stirred under rpm, are reacted by in-situ precipitate in CdWO4Surface nucleation growth crystallization, forms AgI/CdWO4It is heterogeneous
Knot, obtains containing silver iodide/cadmium tungstate（AgI/CdWO4）Mixed liquor.
（3）Ag@AgI/CdWO4Preparation：By above-mentioned steps（2）In contain silver iodide/cadmium tungstate（AgI/CdWO4）'s
Mixed liquor is placed in 30 min of illumination under the ultraviolet xenon lamp of 300 W, by photoreduction in situ by the silver iodide of part silver from
Son is reduced into Ag0；Photoreduction products therefrom in situ is centrifuged, centrifugation obtained solid material is washed with water and ethanol successively
Wash, 6h is dried in vacuo at 60 DEG C, obtain silver/iodate silver composite material of cadmium tungstate modification（Ag@AgI/CdWO4）, it is denoted as
AICW-3。
Comparative example 1
A kind of preparation method of silver/iodate silver composite material, comprises the following steps：
（1）The preparation of AgI：386.4 mg KI are added in 50 ml water, 30 min of ultrasound, 6 ml dissolvings are then added dropwise
There are 410.1 mg AgNO3Solution and be vigorously stirred 30 min, obtain the mixed liquor containing AgI.
（2）The preparation of Ag@AgI：By above-mentioned steps（1）In the mixed liquor containing AgI be placed under the ultraviolet xenon lamp of 300 W
30 min of illumination, by photoreduction in situ by the silver ion reduction in the silver iodide of part into Ag0；By photoreduction in situ
Products therefrom is centrifuged, and centrifugation obtained solid material is washed with water and ethanol successively, and 6 h are dried in vacuo at 60 DEG C, are obtained
Silver/iodate silver composite material（Ag@AgI）, it is denoted as AI.
Silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified is scanned Electronic Speculum, transmission electricity
Mirror is analyzed, as a result as depicted in figs. 1 and 2.Fig. 1 is silver/silver iodide composite wood that cadmium tungstate made from the embodiment of the present invention 1 is modified
The scanning electron microscope (SEM) photograph of material.Fig. 2 is the transmission electricity for silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified
Mirror figure.From Fig. 1 and Fig. 2, in silver/iodate silver composite material of cadmium tungstate modification of the present invention, Ag AgI are supported on CdWO4
On, the two is closely combined together, and wherein Ag@AgI are random graininess, and the size of Ag@AgI is 200nm~800
Nm, CdWO4For the nano bar-shape of rule, CdWO4The length of rod is the nm of 200 nm~400, the nm of a diameter of 50 nm~100.
By silver/iodate silver composite material of cadmium tungstate modification, wolframic acid cadmium material, comparative example 1 made from the embodiment of the present invention 1
Obtained silver/iodate silver composite material carries out ultraviolet-visible light diffusing reflection absorption spectroanalysis, and the results are shown in Figure 3.Fig. 3 is
Silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified（AICW-3）With wolframic acid cadmium material（CW）, contrast
Silver made from example 1/iodate silver composite material（AI）Ultraviolet-visible light diffusing reflection abosrption spectrogram.From the figure 3, it may be seen that cadmium tungstate
The silver of modification/iodate silver composite material has very strong absorbent properties to visible ray, compared with Ag AgI materials and monomer CdWO4And
Speech, its absorption to visible ray are remarkably reinforced, this is conducive to the generation of photogenerated charge, meanwhile, silver/silver iodide of cadmium tungstate modification
Red shift to visible absorption, its energy gap are reduced to 2.78 composite material by 2.80 eV compared with Ag@AgI materials shows
EV, has expanded its visible absorption edge.
By silver/iodate silver composite material of cadmium tungstate modification, wolframic acid cadmium material, comparative example 1 made from the embodiment of the present invention 1
Obtained silver/iodate silver composite material carries out the photoelectric current analysis of photoproduction surface, and the results are shown in Figure 4.Fig. 4 is the embodiment of the present invention
Silver/iodate silver composite material that cadmium tungstate made from 1 is modified（AICW-3）With wolframic acid cadmium material（CW）, silver made from comparative example 1/
Iodate silver composite material（AI）Photoproduction surface photoelectricity flow graph.As shown in Figure 4, silver/iodate silver composite material of cadmium tungstate modification
（Ag@AgI/CdWO4）The photoelectric current produced under visible light illumination is apparently higher than Ag@AgI and monomer CdWO4, this illustrates Ag@
AgI and CdWO4After compound, the light absorptive of material is not only improved, and causes photogenerated charge transfer and the component efficiency of material
It is improved, and then increases photocatalysis performance.
The silver that cadmium tungstate made from the embodiment of the present invention 1 is modified/iodate silver composite material carries out N2Adsorption-desorption is real
Test, the results are shown in Figure 5.Fig. 5 is the N for silver/iodate silver composite material that cadmium tungstate made from the embodiment of the present invention 1 is modified2Inhale
Attached-desorption curve figure.As shown in Figure 5, silver/iodate silver composite material of cadmium tungstate modification（Ag@AgI/CdWO4）Specific surface area
For 3.42 m2/ g, average pore size are 6.44 nm, and pore volume is 0.0096 cm3/g。
Embodiment 2
A kind of silver/iodate silver composite material of cadmium tungstate modification, the silver/silver iodide composite wood modified with the cadmium tungstate of embodiment 1
Expect essentially identical, difference is：In silver/iodate silver composite material of the cadmium tungstate modification of embodiment 2, the matter of Ag nano particles
It is 1.5% to measure percentage composition, and the mass percentage of silver iodide is 90.3%, and the mass percentage of cadmium tungstate is 8.2%.
The preparation method of silver/iodate silver composite material of the cadmium tungstate modification of a kind of above-mentioned the present embodiment, with 1 tungsten of embodiment
The preparation method of silver/iodate silver composite material of sour cadmium modification is essentially identical, and difference is：The step of embodiment 2（2）In
CdWO4Dosage be 50 mg.
Silver/iodate silver composite material of obtained cadmium tungstate modification in embodiment 2（Ag@AgI/CdWO4）, it is denoted as AICW-
1。
Embodiment 3
A kind of silver/iodate silver composite material of cadmium tungstate modification, the silver/silver iodide composite wood modified with the cadmium tungstate of embodiment 1
Expect essentially identical, difference is：In silver/iodate silver composite material of the cadmium tungstate modification of embodiment 3, the matter of Ag nano particles
It is 1.3% to measure percentage composition, and the mass percentage of silver iodide is 83.4%, and the mass percentage of cadmium tungstate is 15.3%.
The preparation method of silver/iodate silver composite material of the cadmium tungstate modification of a kind of above-mentioned the present embodiment, with embodiment 1
The preparation method of silver/iodate silver composite material of cadmium tungstate modification is essentially identical, and difference is：The step of embodiment 3（2）In
CdWO4Dosage be 100 mg.
Silver/iodate silver composite material of obtained cadmium tungstate modification in embodiment 3（Ag@AgI/CdWO4）, it is denoted as AICW-
2。
Embodiment 4
A kind of silver/iodate silver composite material of cadmium tungstate modification, the silver/silver iodide composite wood modified with the cadmium tungstate of embodiment 1
Expect essentially identical, difference is：In silver/iodate silver composite material of the cadmium tungstate modification of embodiment 4, the matter of Ag nano particles
It is 0.3% to measure percentage composition, and the mass percentage of silver iodide is 21.4%, and the mass percentage of cadmium tungstate is 78.3%.
The preparation method of silver/iodate silver composite material of the cadmium tungstate modification of a kind of above-mentioned the present embodiment, with 1 tungsten of embodiment
The preparation method of silver/iodate silver composite material of sour cadmium modification is essentially identical, and difference is：The step of embodiment 4（2）In
CdWO4Dosage be 2000 mg.
Silver/iodate silver composite material of obtained cadmium tungstate modification in embodiment 4（Ag@AgI/CdWO4）, it is denoted as AICW-
4。
Silver/iodate silver composite material, wolframic acid cadmium material and the contrast that cadmium tungstate made from 1-4 of the embodiment of the present invention is modified
Obtained silver/iodate silver composite material carries out X-ray diffractogram spectrum analysis in example 1, and the results are shown in Figure 6.Fig. 6 is real for the present invention
Apply silver/iodate silver composite material that cadmium tungstate made from a 1-4 is modified（AICW-1、AICW-2、AICW-3、AICW-4）, wolframic acid
Cadmium material（CW）With comparative example 1 made from silver/iodate silver composite material（AI）XRD diagram.It will be appreciated from fig. 6 that CdWO4Diffraction maximum
Meet monoclinic crystal CdWO4Classical diffraction maximum（JCPDS No.14−0676）.Ag@AgI 2 θ=23.7 °, 39.1 °,
46.3 °, 56.7 °, 62.3 °, 71.0 ° and 76.1 ° correspond to cubic crystal γ AgI respectively（JCPDS No.09−0399）In
(111), (220), (311), (400), (331), (422) and (511) crystal face, and then belong to six sides at the peak of 2 θ=22.3 °
Crystal β AgI（JCPDS No. 09−0374）(100) crystal face, show there are multiphase in AgI, but due to Ag0Low contain
Amount, small size and good dispersiveness so that there is no obvious Ag in these peaks0Diffraction maximum.See at the same time, Ag@AgI/CdWO4
Contain Ag@AgI and CdWO4Diffraction maximum, and with Ag@AgI amount increase, Ag@AgI/CdWO4AgI in composite material
Diffraction peak intensity strengthens, and shows Ag@AgI/CdWO4The successful preparation of composite material.
Embodiment 5
A kind of application of silver/iodate silver composite material of cadmium tungstate modification in waste water from dyestuff is handled, comprises the following steps：
Silver/iodate silver composite material that cadmium tungstate made from 20 mg embodiments 1-4 is modified is weighed respectively（AICW-1、AICW-2、
AICW-3、AICW-4）, wolframic acid cadmium material（CW）With comparative example 1 made from silver/iodate silver composite material（AI）, it is added separately to
100 mL concentration are 1 h of vibration absorption under dark condition in the rhodamine B aqueous solution of 20 mg/L, after reaching adsorption equilibrium,
In visible ray（λ > 400 nm）Irradiation is lower to carry out 24 min of photocatalytic degradation, completes the processing to rhodamine B aqueous solution.
In the present embodiment, sky is used as to be not added with rhodamine B aqueous solution of the 100 mL concentration of any material as 20 mg/L
In vain, for contrasting.
After the completion for the treatment of photocatalytic degradation, residual reaction liquid is centrifuged, using UV absorptiometry in wavelength 554
The content of the rhodamine B in filtrate is measured at nm, and calculates different materials in visible ray（λ > 400 nm）To sieve under irradiation
The residual rate of red bright B（Degradation rate=1- residual rates）, the results are shown in Figure 7.Fig. 7 is cadmium tungstate made from 1-4 of the embodiment of the present invention
The silver of modification/iodate silver composite material（AICW-1、AICW-2、AICW-3、AICW-4）, wolframic acid cadmium material（CW）With comparative example 1
Obtained silver/iodate silver composite material（AI）In visible ray（λ > 400 nm）To the degradation effect figure of rhodamine B under irradiation.By
Fig. 7 is understood, using CW, AI, AICW-1, AICW-2, AICW-3, AICW-4 24 min of photocatalytic degradation under visible light illumination
Afterwards, the residual rate of rhodamine B is respectively 98.6%, 15.7%, 8.3%, 2.2%, 0.7% and 13.0 % in waste water, corresponding degraded
Rate is respectively 1.4%, 84.3%, 91.7%, 97.8%, 99.3% and 87%.
Embodiment 6
A kind of application of silver/iodate silver composite material of cadmium tungstate modification in antibiotic waste water is handled, comprises the following steps：
Silver/iodate silver composite material that cadmium tungstate made from 20 mg embodiments 1-4 is modified is weighed respectively（AICW-1、AICW-2、
AICW-3、AICW-4）, wolframic acid cadmium material（CW）With comparative example 1 made from silver/iodate silver composite material（AI）, it is added separately to
100 mL concentration are in the tetracycline aqueous solution of 20 mg/L, and 1 h of vibration absorption, reaches adsorption equilibrium, can under dark condition
See light（λ > 400 nm）Irradiation is lower to carry out 20 min of photocatalytic degradation, completes the processing to tetracycline aqueous solution.
It is the tetracycline aqueous solution of 20 mg/L as blank to be not added with 100 mL concentration of any material in the present embodiment,
For contrasting.
After the completion for the treatment of photocatalytic degradation, residual reaction liquid is centrifuged, using UV absorptiometry in wavelength 357
The content of the tetracycline in filtrate is measured at nm, and calculates different materials in visible ray（λ > 400 nm）To Fourth Ring under irradiation
The residual rate of element（Degradation rate=1- residual rates）, the results are shown in Figure 8.Fig. 8 repaiies for cadmium tungstate made from 1-4 of the embodiment of the present invention
The silver of decorations/iodate silver composite material（AICW-1、AICW-2、AICW-3、AICW-4）, wolframic acid cadmium material（CW）Made with comparative example 1
Silver/iodate the silver composite material obtained（AI）In visible ray（λ > 400 nm）To the degradation effect figure of tetracycline under irradiation.By Fig. 8
Understand, after CW, AI, AICW-1, AICW-2, AICW-3, AICW-4 under visible light illumination 20 min of photocatalytic degradation, give up
The residual rate of tetracycline is respectively 99.7%, 43.7%, 29.1%, 23.1%, 23.0% and 27.8% in water, corresponding degradation rate difference
For 0.3%, 56.3%, 70.9%, 76.9%, 77.0% and 72.2%.
Embodiment 7
The stability of silver/iodate silver composite material of cadmium tungstate modification of the present invention is investigated, is comprised the following steps：
（1）Weigh silver/iodate silver composite material of the cadmium tungstate modification in two parts of 20mg embodiments 1（AICW-3）, it is separately added into
Into the rhodamine B aqueous solution that 100mL concentration is 20 mg/L and tetracycline aqueous solution that 100mL concentration is 20 mg/L, black
Vibration absorption 1h, reaches adsorption equilibrium, respectively in wavelength under dark condition>Photocatalytic degradation is carried out under the radiation of visible light of 400nm
24 min and 20 min, complete the processing to rhodamine B aqueous solution and tetracycline aqueous solution.
（2）Step（1）In processing after the completion of, collect silver/iodate silver composite material of cadmium tungstate modification, and use ultra-pure water
Clean, be dried in vacuo at 80 DEG C.
（3）Using with step（1）Identical processing method, reuses step（2）The cadmium tungstate obtained after middle drying is repaiied
The silver of decorations/iodate silver composite material handles rhodamine B aqueous solution and tetracycline aqueous solution, carries out 4 repetitions and tests.
By the reaction solution obtained after each photocatalytic degradation centrifuge, using UV absorptiometry respectively at
The content of the rhodamine B and tetracycline in filtrate is measured at wavelength 554nm and 357nm, and calculates AICW-3 circular treatment sieve
Photocatalytic degradation residual rate when red bright B and tetracycline, the results are shown in Figure 9.
Fig. 9 is silver/iodate silver composite material that cadmium tungstate is modified in the embodiment of the present invention 7（AICW-3）Circulation degraded Luo Dan
The degradation effect figure of bright B and tetracycline.As shown in Figure 9, AICW-3 of the present invention through absorption-it is light-catalysed recycle 5 times after, it is right
The visible light photocatalytic degradation efficiency of rhodamine B and tetracycline is still respectively 90.2% and 67.6%, this illustrates that cadmium tungstate of the present invention is repaiied
The silver of decorations/iodate silver composite material is with good stability, and light induced electron is by fast transfer, it is suppressed that the photoetch of material.
In summary, silver/iodate silver composite material of cadmium tungstate modification of the present invention has, suction wide to visible absorption scope
Receive high intensity, photogenerated charge conduction and separative efficiency height, photocatalysis performance are good, stability and anti-light corrosive power are strong, circulation profit
With property it is good the advantages that, its preparation method have easy control of reaction conditions, operating method be simple, in preparation process without using appointing
The advantages of what organic solvent, non-secondary pollution, good environmental benefit.Silver/silver iodide composite wood that the cadmium tungstate of the present invention is modified
Material（Ag@AgI/CdWO4）Waste water from dyestuff and antibiotic waste water are handled, there is removal rate height, speed is fast, easy to operate, cost is low
The advantages that honest and clean, non-secondary pollution, can be widely applied to the detoxification of Wastewater Dyes and antibiotic and harmless processing, to exploitation
Silver material, haloid material and tungstate material and applied to environmental area tool be of great significance.
Above example is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
- A kind of 1. silver/iodate silver composite material of cadmium tungstate modification, it is characterised in that including cadmium tungstate and silver/iodate ag material, The silver/silver iodide material load is on cadmium tungstate；The silver/iodate ag material is made of Ag nano particles and silver iodide.
- 2. silver/iodate the silver composite material modified according to the cadmium tungstate described in claim 1, it is characterised in that the wolframic acid In silver/iodate silver composite material of cadmium modification, the mass percentage of the Ag nano particles is 0.3%~1.5%, the iodate The mass percentage of silver is 21.3%~90.3%, and the mass percentage of the cadmium tungstate is 8.2%~78.3%.
- 3. silver/iodate the silver composite material modified according to the cadmium tungstate described in claim 1 or 2, it is characterised in that the tungsten The specific surface area of silver/iodate silver composite material of sour cadmium modification is 0.075 m2The m of/g~5.452/ g, average pore size are 2.30 nm ~14.62 nm, pore volume are 0.0005 cm3The cm of/g~0.01923/g；The silver/iodate ag material is graininess, a diameter of The nm of 200 nm~800；The cadmium tungstate is nano bar-shape, and length is the nm of 200 nm~400, the nm of a diameter of 50 nm~100.
- A kind of 4. preparation side for the silver/iodate silver composite material modified such as cadmium tungstate according to any one of claims 1 to 3 Method, it is characterised in that comprise the following steps：S1, mix KI, cadmium tungstate in water, and ultrasound, is added dropwise AgNO3Solution carries out in-situ precipitate reaction, obtains containing iodine Change the mixed liquor of silver/cadmium tungstate；The mixed liquor containing silver iodide/cadmium tungstate in step S1, is placed in progress photoreduction in situ by S2, is centrifuged, washing, Vacuum drying, obtains silver/iodate silver composite material of cadmium tungstate modification.
- 5. according to the preparation method described in claim 4, it is characterised in that in step S1, the preparation method of the cadmium tungstate Comprise the following steps：By Na2WO4·2H2O solution adds to Cd (NO dropwise3)2·4H2In O solution, gained mixed solution is adjusted PH carries out hydro-thermal reaction, filters, and washs, dry, obtains cadmium tungstate.
- 6. according to the preparation method described in claim 5, it is characterised in that the Na2WO4·2H2Na in O solution2WO4· 2H2The O and Cd (NO3)2·4H2Cd (NO in O solution3)2·4H2The mass ratio of O is 1.069~1.070: 1；And/or the pH of the mixed solution is adjusted using ammonium hydroxide；The pH of the mixed solution is 9.2~9.4；The ammonium hydroxide Mass concentration is 25%~28%；And/or the temperature of the hydro-thermal reaction is 130 DEG C~150 DEG C；The time of the hydro-thermal reaction is 12h~16h；It is described Washing uses absolute ethyl alcohol and water successively；The temperature of the drying is 50 DEG C~70 DEG C；The time of the drying is 10h~14 h。
- 7. the preparation method according to any one of claim 4~6, it is characterised in that the KI, described in step S1 AgNO3AgNO in solution3Mass ratio with the cadmium tungstate is 0.19~7.73: 0.20~8.21: 1；The ultrasonic time For 30min~60min；The in-situ precipitate reaction carries out under agitation；The rotating speed of the stirring for 300rpm~ 450rpm；The time of the in-situ precipitate reaction is 30min~60min；And/or in step S2, the original position photoreduction carries out under ultraviolet light conditions；The original position photoreduction Time is 25min~35min；The washing uses water and absolute ethyl alcohol successively；The vacuum drying temperature is 50 DEG C~70 ℃；The vacuum drying time is 4 h~6h.
- It is 8. a kind of if silver/iodate silver composite material of cadmium tungstate according to any one of claims 1 to 3 modification is in processing antibiosis Application in plain waste water or waste water from dyestuff.
- 9. according to the application described in claim 8, it is characterised in that comprise the following steps：Silver/iodate that cadmium tungstate is modified Silver composite material is mixed with antibiotic waste water or waste water from dyestuff, absorption is vibrated under dark condition, after reaching adsorption equilibrium, in light Irradiation is lower to carry out photocatalytic degradation, completes the processing to antibiotic waste water or waste water from dyestuff；Silver/iodate of the cadmium tungstate modification The additive amount of silver composite material is silver/iodate that the cadmium tungstate modification is added in every liter of antibiotic waste water or waste water from dyestuff The mg of silver composite material 100mg~300.
- 10. according to the application described in claim 9, it is characterised in that the antibiotic in the antibiotic waste water is tetracycline； The concentration of antibiotic is the mg/L of 15 mg/L~25 in the antibiotic waste water；Dyestuff in the waste water from dyestuff is rhodamine B； The concentration of dyestuff is the mg/L of 15 mg/L~25 in the waste water from dyestuff；And/or the time of the vibration absorption is the min of 60 min~120；And/or the photocatalytic degradation carries out under the visible ray of 400 nm of wavelength ＞；And/or the time of the photocatalytic degradation is the min of 2 min~24.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109225282A (en) * | 2018-10-24 | 2019-01-18 | 福建师范大学 | A kind of p-n junction CdWO4/ BiOCl heterojunction photocatalyst, preparation method and its usage |
| WO2021068570A1 (en) * | 2019-10-12 | 2021-04-15 | 湖南大学 | Composite photocatalyst for degrading tetracycline, preparation method therefor and use thereof |
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| CN106890655A (en) * | 2017-01-16 | 2017-06-27 | 南京工业大学 | A kind of Ag/AgCl/CdWO with high efficiency and visible light photocatalytic activity4Catalyst |
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| CN106890655A (en) * | 2017-01-16 | 2017-06-27 | 南京工业大学 | A kind of Ag/AgCl/CdWO with high efficiency and visible light photocatalytic activity4Catalyst |
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| XIAOJU WEN ET AL.: ""In-situ synthesis of visible-light-driven plasmonic Ag/AgCl-CdWO4 photocatalyst"", 《CERAMICS INTERNATIONAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225282A (en) * | 2018-10-24 | 2019-01-18 | 福建师范大学 | A kind of p-n junction CdWO4/ BiOCl heterojunction photocatalyst, preparation method and its usage |
| WO2021068570A1 (en) * | 2019-10-12 | 2021-04-15 | 湖南大学 | Composite photocatalyst for degrading tetracycline, preparation method therefor and use thereof |
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