CN108187703B - Preparation method of silver/silver chloride/titanium dioxide composite photocatalyst - Google Patents
Preparation method of silver/silver chloride/titanium dioxide composite photocatalyst Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 74
- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 64
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 title claims abstract description 63
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 62
- 239000004332 silver Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 150000003608 titanium Chemical class 0.000 claims abstract description 58
- 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 abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims description 75
- 238000000889 atomisation Methods 0.000 claims description 19
- -1 titanium salt Chemical class 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 7
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 46
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 55
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 23
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 17
- 229940012189 methyl orange Drugs 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 238000005507 spraying Methods 0.000 description 12
- 239000007921 spray Substances 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- HUVAFPHSQFFCID-UHFFFAOYSA-N 5-chlorocyclopenta-1,3-diene titanium(2+) Chemical group [Ti++].Cl[c-]1cccc1.Cl[c-]1cccc1 HUVAFPHSQFFCID-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- SVXJKCNGKMBSJM-UHFFFAOYSA-N Cl[C-]1C=CC=C1.[C-]1(C=CC=C1)Cl.[Ti+2].[Ti] Chemical compound Cl[C-]1C=CC=C1.[C-]1(C=CC=C1)Cl.[Ti+2].[Ti] SVXJKCNGKMBSJM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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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
- 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
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- 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
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Abstract
The invention relates to a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst, belonging to the technical field of photocatalysis and composite material preparation. The method comprises the steps of respectively atomizing a titanium salt alcohol solution and a silver salt aqueous solution into liquid drops in an atomizing mode, introducing the liquid drops into a tubular furnace with temperature gradient distribution from different angles, and carrying out spray pyrolysis reaction to obtain the silver/silver chloride/titanium dioxide composite photocatalyst. The composite photocatalyst prepared by the invention has excellent photocatalytic performance and can effectively catalyze and degrade organic pollutants; the method has the advantages of simple process, short preparation period, excellent and stable photocatalytic performance and the like.
Description
Technical Field
The invention relates to a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst, belonging to the technical field of photocatalysis and composite material preparation.
Background
With the rapid development of industry, global environmental pollution and energy crisis problems have seriously affected human survival and development. Therefore, the environmental purification and energy conversion are carried out on the basis of high-efficiency photocatalyst and solar energy, and the great attention of people is drawn.
TiO because of its long-term stable photochemical reactivity and nontoxicity2The titanium dioxide is widely used for photocatalysts, but the large band gap (anatase 3.2 eV) of the titanium dioxide means that only ultraviolet rays in the solar spectrum can be used for photocatalysis, so that the utilization rate of the titanium dioxide to sunlight is low, the yield of photon is low, and the recombination of carriers is serious, and the problems restrict the application of the titanium dioxide in practical life.
Thus, how to enlarge TiO2Has been of great interest, including doping of TiO with metallic or non-metallic elements2And coupled with a material sensitive to visible light. However, doping leads to instability of the material, susceptibility to corrosion and difficulty in controlling the degree of doping. The silver/silver chloride photocatalytic material based on the silver nanoparticle plasma resonance effect is prepared by using hydrogen chloride to replace silver molybdate through a yellow-prime label and the like in a dye-sensitized reduction method, and the degradation of organic matters by visible light can be effectively improved; awzau et al, and titanium dioxide deposited on the silica coating of nano-silver ions, a novel photocatalytic film based on silver nano-ion plasmon resonance was preparedThe speed of the film material for degrading methylene blue under near ultraviolet light is improved by 5 times compared with that of the single titanium dioxide. However, the method has the defects that the preparation period is long and complicated, and the prepared photocatalytic material has no regular appearance. Twining 26101The silver chloride is deposited on the titanium dioxide nanotube by deposition reaction, and the silver/silver chloride/modified titanium dioxide nanotube is obtained by photoreduction, thus improving the dispersibility and stability of the silver chloride, but the silver chloride is still exposed outside when the silver chloride is deposited on the composite semiconductor by a deposition method, and the problems of photo-corrosion, coarsening of crystal grains and the like are inevitable.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst, which comprises the steps of atomizing a titanium salt alcohol solution and a silver salt aqueous solution into liquid drops, controlling the atomization amount, introducing the liquid drops into a tubular furnace at the same time, carrying out collision, evaporation and drying on the liquid drops in a low-temperature region to obtain silver chloride/titanium dioxide composite powder, then decomposing redundant silver salt covered on the surface into nano silver particles at high temperature, and finally obtaining the silver/silver chloride/titanium dioxide composite photocatalyst.
A preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst comprises the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt in the silver salt solution A is 1-500 mmol/L;
(2) preparing a titanium salt solution: dissolving a titanium salt in alcohol to prepare a titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare a titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt in the titanium salt solution C is 10-1000 mmol/L;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through an atomizing pipe A and an atomizing pipe B of the atomizer respectively at the temperature of 400-750 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 0.01-50L/h, the atomization amount of the titanium salt solution C of the atomizer B is 0.1-100L/h, and the atomization amount of the silver salt solution A is not higher than that of the titanium salt solution C;
the silver salt in the step (1) is one or more of silver nitrate, silver carbonate and silver acetate in any ratio;
in the step (2), the alcohol is one or more of methanol, ethanol, n-propanol and ethylene glycol in any ratio, and the titanium salt is one or more of titanium tetrachloride, titanium trichloride and titanocene dichloride in any ratio;
the included angle between the spraying pipe A and the spraying pipe B in the step (3) is 90-180 degrees;
the invention has the beneficial effects that:
(1) according to the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the method, the hydrochloric acid generated by dissolving titanium salt in deionized water is fully utilized, so that chloride ions in the hydrochloric acid are combined with silver ions to generate silver chloride in the catalyst;
(2) according to the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the method, two atomizers are used for atomizing a silver carbonate solution and a titanium salt solution into liquid drops at the same time, the liquid drops collide and react, and spherical particles with regular shapes are generated after pyrolysis evaporation, drying and pyrolysis reaction, wherein the particle size is 200-500 nm, and nano silver chloride and silver are uniformly distributed on the surface;
(3) the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the method has the advantages of short preparation period, simple process and excellent and stable catalytic performance.
Drawings
FIG. 1 is an SEM image at 300000 magnification of silver/silver chloride/titanium dioxide prepared in example 1;
FIG. 2 is an EDS plot at 300000 magnification of silver/silver chloride/titanium dioxide prepared in example 1;
FIG. 3 is an SEM image of the silver/silver chloride/titanium dioxide prepared in example 1 at magnification of 200000;
FIG. 4 is an XRD pattern of silver/silver chloride/titanium dioxide prepared in example 1;
fig. 5 is a graph comparing the photocatalytic results of the silver/silver chloride/titanium dioxide catalyst prepared in example 1 against methyl orange and the photocatalytic results of the comparative titanium dioxide against methyl orange.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Comparative example: preparing titanium tetrachloride solution with titanium salt concentration of 60 mmol/L as precursor solution, stirring at room temperature, and pouring into an atomizer; slowly raising the temperature of the tubular furnace to 500 ℃, starting an atomization mode, wherein the atomization amount is 0.5L/h, evaporating and drying generated precursor liquid fog drops to generate titanium dioxide, and collecting the titanium dioxide to obtain a titanium dioxide photocatalyst;
the titanium dioxide photocatalyst is used for catalytically decomposing methyl orange solution, and the method comprises the following specific steps: 0.1g of titanium dioxide photocatalytic material is weighed and placed in a 250mL photocatalytic reactor, 200mL of methyl orange solution with the concentration of 10mg/L is added into the photocatalytic reactor, and the methyl orange concentration under the condition is recorded as C0Standing in dark for 30min to reach adsorption equilibrium, irradiating with 300W xenon lamp light, taking 5mL samples every 5min, and recording the concentration of methyl orange after centrifugation as C1、C2、C3… …, finally, measuring the ultraviolet-visible light absorption spectrum of the sample respectively;
by calculation, C is obtained after the methyl orange solution is subjected to photocatalysis for 30min6/C0=0.93, and then the value no longer changes significantly; therefore, the titanium dioxide photocatalyst prepared under the experimental conditions has no photocatalytic degradation effect on 10mg/L methyl orange basically.
Example 1: a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst comprises the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt (silver nitrate) in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt (silver nitrate) in the silver salt solution A is 1 mmol/L;
(2) preparing a titanium salt solution: dissolving a titanium salt (titanium tetrachloride) in alcohol (alcohol is ethanol) to prepare a titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare a titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt (titanium tetrachloride) in the titanium salt solution C is 100 mmol/L; the volume ratio of the titanium tetrachloride to the ethanol is 1: 5;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through a spray pipe A and a spray pipe B of the atomizer respectively at the temperature of 500 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 0.01L/h, and the atomization amount of the titanium salt solution C of the atomizer B is 0.1L/h; the included angle between the spraying pipe A and the spraying pipe B is 90 degrees;
the SEM image of the silver/silver chloride/titanium dioxide prepared in this example at 300000 times magnification is shown in fig. 1, the EDS image of the silver/silver chloride/titanium dioxide prepared in this example at 300000 times magnification is shown in fig. 2, and as is known from fig. 1 and 2, the spherical titanium dioxide with regular morphology is rough in surface, and by performing point scanning on any position on the surface of the titanium dioxide, it is found that a small amount of Ag and Cl elements are present in addition to the main Ti and O elements, indicating that the surface of the titanium dioxide is uniformly distributed with elemental silver and silver chloride, wherein C, Al comes from the sample stage;
an SEM image of the silver/silver chloride/titanium dioxide prepared in this example under the magnification of 200000 is shown in fig. 3, as is known from fig. 3, the titanium dioxide is regular spherical, the size is 200-500 nm, and the surface is distributed with elemental silver and silver chloride particles;
the XRD pattern of the silver/silver chloride/titanium dioxide prepared in this example is shown in fig. 4, and as known from fig. 4, the prepared composite catalyst is mainly composed of elemental silver, silver chloride and anatase, and a small amount of rutile, and no other impurities exist;
the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the embodiment is used for catalytically decomposing methyl orange solution, and the method comprises the following specific steps: 0.1g of silver/silver chloride/titanium dioxide composite photocatalytic material is weighed and placed in a 250mL photocatalytic reactor, and200mL of methyl orange solution with the concentration of 10mg/L is added into the photocatalytic reactor, and the concentration of the methyl orange under the condition is recorded as C0Standing in dark for 30min to reach adsorption equilibrium, irradiating with 300W xenon lamp light, taking 5mL samples every 5min, and recording the concentration of the centrifuged methyl orange solution as C1、C2、C3… …, finally, measuring the ultraviolet-visible light absorption spectrum of the sample respectively;
in a photocatalysis experiment, after carrying out photocatalysis on a methyl orange solution for 10min by calculation, C is carried out on the composite photocatalyst prepared by the invention2/C0=0, and then the value is not changed significantly any more, so that the photocatalytic degradation rate of the composite photocatalyst prepared under the experimental condition on 10mg/L methyl orange can reach 100%;
a comparison graph of the photocatalytic result of the silver/silver chloride/titanium dioxide catalyst prepared in the embodiment on methyl orange and the photocatalytic result of the titanium dioxide prepared in the comparative example on methyl orange is shown in fig. 5, and it is known from fig. 5 that the silver/silver chloride/titanium dioxide composite photocatalyst can basically degrade MO within 10min, which is much higher than that of elemental titanium dioxide, which shows that after elemental silver and silver chloride are compounded on the surface of titanium dioxide, the compounding of carriers is effectively inhibited, and the photocatalytic efficiency is improved.
Example 2: a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst comprises the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt (silver carbonate) in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt (silver carbonate) in the silver salt solution A is 100 mmol/L;
(2) preparing a titanium salt solution: dissolving titanium salt (titanium trichloride is titanium trichloride) in alcohol (methanol) to prepare a titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare a titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt (titanium trichloride) in the titanium salt solution C is 10.0 mmol/L; the volume ratio of the titanium trichloride to the methanol is 1: 20;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through a spray pipe A and a spray pipe B of the atomizer respectively at the temperature of 400 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 1.0L/h, and the atomization amount of the titanium salt solution C of the atomizer B is 1.0L/h; the included angle between the spraying pipe A and the spraying pipe B is 120 degrees;
the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the embodiment is used for catalytically decomposing methyl orange solution, and the method comprises the following specific steps: weighing 0.1g of silver/silver chloride/titanium dioxide composite photocatalytic material, placing the silver/silver chloride/titanium dioxide composite photocatalytic material in a 250mL photocatalytic reactor, adding 200mL of methyl orange solution with the concentration of 10mg/L into the photocatalytic reactor, and recording the methyl orange concentration under the condition as C0Standing in dark for 30min to reach adsorption equilibrium, irradiating with 300W xenon lamp light, taking 5mL samples every 5min, and recording the concentration of the centrifuged methyl orange solution as C1、C2、C3… …, finally, measuring the ultraviolet-visible light absorption spectrum of the sample respectively;
in a photocatalysis experiment, after carrying out photocatalysis on a methyl orange solution for 30min by calculation, the composite photocatalyst prepared by the invention is C6/C0=0.12, and then the value is not changed significantly any more, so that the photocatalytic degradation rate of the composite photocatalyst prepared under the experimental condition on 10mg/L methyl orange is 88%.
Example 3: a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst comprises the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt (silver acetate) in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt (silver acetate) in the silver salt solution A is 300 mmol/L;
(2) preparing a titanium salt solution: dissolving titanium salt (titanium salt is dichlorotitanocene) in alcohol (alcohol is n-propanol) to prepare titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt (dichlorotitanocene) in the titanium salt solution C is 500 mmol/L; the volume ratio of the titanocene dichloride to the n-propanol is 1: 5;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through a spray pipe A and a spray pipe B of the atomizer respectively at the temperature of 550 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 10.0L/h, and the atomization amount of the titanium salt solution C of the atomizer B is 10.0L/h; the included angle between the spraying pipe A and the spraying pipe B is 180 degrees;
the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the embodiment is used for catalytically decomposing methyl orange solution, and the method comprises the following specific steps: weighing 0.1g of silver/silver chloride/titanium dioxide composite photocatalytic material, placing the silver/silver chloride/titanium dioxide composite photocatalytic material in a 250mL photocatalytic reactor, adding 200mL of methyl orange solution with the concentration of 10mg/L into the photocatalytic reactor, and recording the methyl orange concentration under the condition as C0Standing in dark for 30min to reach adsorption equilibrium, irradiating with 300W xenon lamp light, taking 5mL samples every 5min, and recording the concentration of the centrifuged methyl orange solution as C1、C2、C3… …, finally, measuring the ultraviolet-visible light absorption spectrum of the sample respectively;
in a photocatalysis experiment, after carrying out photocatalysis on a methyl orange solution for 60min by calculation, the composite photocatalyst prepared by the invention is C12/C0=0.23, and then the value is not changed significantly any more, so that the photocatalytic degradation rate of the composite photocatalyst prepared under the experimental condition on 10mg/L methyl orange is 77%.
Example 4: a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst comprises the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt (silver nitrate) in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt (silver nitrate) in the silver salt solution A is 400 mmol/L;
(2) preparing a titanium salt solution: dissolving a titanium salt (titanium tetrachloride) in alcohol (alcohol is ethylene glycol) to prepare a titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare a titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt (titanium tetrachloride) in the titanium salt solution C is 800 mmol/L; the volume ratio of titanium tetrachloride to ethylene glycol is 1: 10;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through a spray pipe A and a spray pipe B of the atomizer respectively at the temperature of 750 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 30.0L/h, and the atomization amount of the titanium salt solution C of the atomizer B is 50.0L/h; the included angle between the spraying pipe A and the spraying pipe B is 160 degrees;
the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the embodiment is used for catalytically decomposing methyl orange solution, and the method comprises the following specific steps: weighing 0.1g of silver/silver chloride/titanium dioxide composite photocatalytic material, placing the silver/silver chloride/titanium dioxide composite photocatalytic material in a 250mL photocatalytic reactor, adding 200mL of methyl orange solution with the concentration of 10mg/L into the photocatalytic reactor, and recording the methyl orange concentration under the condition as C0Standing in dark for 30min to reach adsorption equilibrium, irradiating with 300W xenon lamp light, taking 5mL samples every 5min, and recording the concentration of the centrifuged methyl orange solution as C1、C2、C3… …, finally, measuring the ultraviolet-visible light absorption spectrum of the sample respectively;
in a photocatalysis experiment, after carrying out photocatalysis on a methyl orange solution for 25min by calculation, the composite photocatalyst prepared by the invention is C5/C0=0, and then the value is not changed significantly any more, so that the photocatalytic degradation rate of the composite photocatalyst prepared under the experimental condition on 10mg/L methyl orange is 100%.
Example 5: a preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst comprises the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt (silver carbonate) in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt (silver carbonate) in the silver salt solution A is 500 mmol/L;
(2) preparing a titanium salt solution: dissolving a titanium salt (titanium tetrachloride) in alcohol (alcohol is a mixed solution of methanol and ethanol) to prepare a titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare a titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt (titanium tetrachloride) in the titanium salt solution C is 1000 mmol/L; the volume ratio of titanium tetrachloride to alcohol is 1: 8;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through a spray pipe A and a spray pipe B of the atomizer respectively at the temperature of 600 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 50.0L/h, and the atomization amount of the titanium salt solution C of the atomizer B is 100.0L/h; the included angle between the spraying pipe A and the spraying pipe B is 90 degrees;
the silver/silver chloride/titanium dioxide composite photocatalyst prepared by the embodiment is used for catalytically decomposing methyl orange solution, and the method comprises the following specific steps: weighing 0.1g of silver/silver chloride/titanium dioxide composite photocatalytic material, placing the silver/silver chloride/titanium dioxide composite photocatalytic material in a 250mL photocatalytic reactor, adding 200mL of methyl orange solution with the concentration of 10mg/L into the photocatalytic reactor, and recording the methyl orange concentration under the condition as C0Standing in dark for 30min to reach adsorption equilibrium, irradiating with 300W xenon lamp light, taking 5mL samples every 5min, and recording the concentration of the centrifuged methyl orange solution as C1、C2、C3… …, finally, measuring the ultraviolet-visible light absorption spectrum of the sample respectively;
in a photocatalysis experiment, after carrying out photocatalysis on a methyl orange solution for 15min by calculation, C is carried out on the composite photocatalyst prepared by the invention5/C0=0, and then the value is not changed significantly any more, so that the photocatalytic degradation rate of the composite photocatalyst prepared under the experimental condition on 10mg/L methyl orange is 100%.
Claims (3)
1. A preparation method of a silver/silver chloride/titanium dioxide composite photocatalyst is characterized by comprising the following specific steps:
(1) preparation of silver salt solution: under the condition of stirring, dissolving silver salt in deionized water to prepare silver salt solution A, wherein the concentration of the silver salt in the silver salt solution A is 1-500 mmol/L;
(2) preparing a titanium salt solution: dissolving a titanium salt in alcohol to prepare a titanium salt/alcohol solution B, and dissolving the titanium salt/alcohol solution B in deionized water to prepare a titanium salt solution C under the stirring condition, wherein the concentration of the titanium salt in the titanium salt solution C is 10-1000 mmol/L, and the titanium salt is one or more of titanium tetrachloride, titanium trichloride and titanocene dichloride in any ratio;
(3) spray pyrolysis reaction: placing the silver salt solution A obtained in the step (1) into an atomizer A, placing the titanium salt solution C obtained in the step (2) into an atomizer B, and performing spray pyrolysis reaction through an atomizing pipe A and an atomizing pipe B of the atomizer respectively at the temperature of 400-750 ℃ to obtain the silver/silver chloride/titanium dioxide composite photocatalyst, wherein the atomization amount of the silver salt solution A of the atomizer A is 0.01-50L/h, the atomization amount of the titanium salt solution C of the atomizer B is 0.1-100L/h, the atomization amount of the silver salt solution A is not higher than that of the titanium salt solution C, and the included angle between the atomizing pipe A and the atomizing pipe B is 90-180 degrees.
2. The method for preparing the silver/silver chloride/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: in the step (1), the silver salt is one or more of silver nitrate, silver carbonate and silver acetate.
3. The method for preparing the silver/silver chloride/titanium dioxide composite photocatalyst as claimed in claim 1, wherein: in the step (2), the alcohol is one or more of methanol, ethanol, n-propanol and glycol in any ratio.
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