CN106732650B - A kind of and doping and load dual modified perovskite type photocatalyst and preparation method thereof - Google Patents
A kind of and doping and load dual modified perovskite type photocatalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000009977 dual effect Effects 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000011068 loading method Methods 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000001879 gelation Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 17
- 239000000975 dye Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 7
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- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
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- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
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- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
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- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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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- 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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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/308—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of and doping and dual modified perovskite type photocatalyst is loaded, which combines the two-fold advantage of synchronous doping load and collaboration load, therefore has high visible light-responded ability.The invention also discloses above-mentioned and doping and the preparation methods for loading dual modified perovskite type photocatalyst, realize Mg to LaCoO first with improved sol-gel method is synchronous3Modification is synchronized inside and outside lattice, further utilize photoreduction met hod by the reducing loaded surface to catalyst Ag, catalyst after Ag load, on the one hand due to the surface plasma resonance effect of Embedded A g nanoparticle, internal field's enhancing, conducive to electronics transfer phenomenon, to enhance catalyst to the responding ability of visible light；The collaboration loaded favourable of another aspect Ag and MgO are shifted in the transition of catalyst surface electronics, to collectively promote the degradation to dyestuff.
Description
Technical field
The present invention relates to a kind of LaCo0.9Mg0.1O3- MgO-Ag Ca-Ti ore type visible light catalyst, further relates to above-mentioned
LaCo0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalyst, belongs to photocatalyst technology field.
Background technique
Environmental pollution restricts the sustainable development of human society.Waste water from dyestuff is lead to water pollution in environment main
One of reason.Waste water from dyestuff is mainly derived from textile and paper industry, have coloration is high, acid-base property variation greatly, organic content height,
Toxic feature.Wherein 60% to 70% dyestuff belongs to azo dyes, will increase carcinogen toxic in water body, endangers people
The health of class.The common processing method of waste water from dyestuff mainly has flocculence, coagulation method, absorption method, membrane filter method, chemical oxygen
Change method and bioanalysis etc..Although these methods all have certain decoloring ability, there is such as sludge quantity in practical applications
Greatly, adsorbent amount is big and be difficult to regenerate, fouling membrane, it is at high cost the problems such as.
With the development of economic science, Photocatalitic Technique of Semiconductor degradation of dye waste water is paid more and more attention.Semiconductor light
Catalysis technique carries out at normal temperature, can use sunlight or ultraviolet light as light source, organic dye molecule is degraded to CO2、
H2O and other inorganic matters, do not generate secondary pollution.Also, many is difficult to biodegrade or difficult with other methods in waste water from dyestuff
With the substance of removing, the removing of conductor photocatalysis method can use.Wherein, TiO2It is the photochemical catalyst of current most study, but
It is that its forbidden bandwidth is larger (about 3.2eV), it is lower to the efficiency of solar energy utilization.
In recent years, perovskite semiconductor material due to its structure-controllable, thermal stability is good, cheap the advantages that, gradually
Hot spot as the research of semiconductor catalytic field.Perovskite forbidden bandwidth is smaller (about 2.6eV), but still has quantum yield lower
The technical problems such as (about 4%), solar energy utilization ratio be low, difficult load, hinder it and are industrially widely applied.Therefore, pass through
Method of modifying improves the quantum yield of perovskite material, increase its to the utilization rate of sunlight be very it is necessary to.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of and doping and loads dual modified Ca-Ti ore type light and urge
Agent.
The present invention also technical problems to be solved, which are to provide above-mentioned and doping and load dual modified Ca-Ti ore type light, urges
The preparation method of agent.
In order to solve the above technical problems, the technology used in the present invention means are as follows:
A kind of and doping and load dual modified perovskite type photocatalyst, the catalyst A bit element is La3+From
Son, B bit element are doped with Mg2+The Co of ion2+Ion, while load has MgO and Ag on the catalyst；Wherein, Mg2+From
The doping of son is the 10% of catalyst quality；The load capacity of Ag is the 1%~2% of catalyst quality；The load capacity of MgO is to urge
The 13%~19% of agent quality.
Above-mentioned and doping and the preparation method for loading dual modified perovskite type photocatalyst, include the following steps:
Step 1, the La (NO of corresponding amount is weighed by La: Co: Mg molar ratio 1: 0.9: 1~23)3·6H2O、Co(NO3)2·
6H2O and Mg (NO3)2·6H2O, then the citric acid for weighing corresponding amount by the molar ratio of metal cation and citric acid for 1: 1, will
La(NO3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid is soluble in water together obtains mixed solution, side
Stir side toward mixed solution and dripping ammonium hydroxide until mixed solution pH be 8, be persistently stirred solution under water-bath and to mix
Solution solation is closed, the mixed solution of solation is become at a temperature of being respectively placed in 400 DEG C and 750 DEG C after gelation, air atmosphere
4h is respectively roasted in enclosing, and obtains LaCo0.9Mg0.1O3- MgO powder；
Step 2, by the LaCo of aequum step 10.9Mg0.1O3- MgO powder is scattered in methanol (methanol as solvent and dispersion
Agent, the also sacrifice agent as hole) in, obtain A mixed liquor；
Step 3, by the desired amount of AgNO3Particle is added in A mixed liquor, is uniformly mixing to obtain B mixed liquor；
Step 4, B mixed liquor is placed under 125W high-pressure sodium lamp, while stirring ultraviolet light deposition a period of time；It utilizes
Ultraviolet light deposition, causes the of short duration separation of the electron-hole of catalyst under ultraviolet excitation, in order to avoid it is multiple again
It closes, methanol is added as hole sacrifice agent, consumes hole, such Ag+More electronics can be obtained, to be reduced into Ag
Grain, achievees the purpose that area load Ag；
Step 5, the product of step 4 is filtered, washed and is dried.
Wherein, in step 1, the metal cation refers to La in mixed solution3+Ion, Co2+Ion and Mg2+Ion
Quality summation.
Wherein, in step 1, the mass percentage concentration of the ammonium hydroxide is 30%.
Wherein, in step 1, the bath temperature is 80 DEG C, and the mixing time that continues is 3h.
Wherein, in step 1, solation mixed solution is placed at 110 DEG C after standing 12h and becomes gelation mixed solution.
Wherein, in step 2, every addition 1g LaCo0.9Mg0.1O3- MgO powder, the volume of required methanol are 200mL.
Wherein, in step 3, the AgNO3The addition quality of particle is 0.015~0.035g.
Wherein, in step 4, the time that the UV Light is penetrated is 5~6h.
Wherein, in step 5, the drying temperature is 80 DEG C, and the drying time is for 24 hours.
LaCo of the present invention0.9Mg0.1O3The preparation principle of-MgO-Ag Ca-Ti ore type visible light catalyst: the present invention is by changing
Into sol-gel method prepare the modified LaCo of synchronous Mg0.9Mg0.1O3- MgO is further restored Ag using photoreduction met hod
It is loaded to perovskite catalyst surface, ultimately generates LaCo0.9Mg0.1O3-MgO-Ag.Under the collective effect for loading and adulterating,
The Ca-Ti ore type visible light catalyst has stronger visible light-responded ability.
Compared with the prior art, technical solution of the present invention has the beneficial effect that
LaCo of the present invention0.9Mg0.1O3The load of Ag in-MgO-Ag visible light catalyst, on the one hand causes Embedded A g to receive
The surface plasma resonance effect of rice corpuscles, internal field's enhancing, conducive to the electronics transfer of catalyst, to enhance catalyst pair
Visible light-responded ability；The collaboration loaded favourable of another aspect Ag and MgO are shifted in the transition of catalyst surface electronics, thus altogether
With the degradation promoted to dyestuff；Preparation method simple process of the present invention has promotional value.
Detailed description of the invention
Fig. 1 is LaCo of the present invention0.9Mg0.1O3The process flow chart of-MgO-Ag visible light catalyst preparation method；
Fig. 2 is LaCo of the present invention0.9Mg0.1O3The degradation effect of MO is compared under-MgO-Ag visible light catalyst visible light
Figure；
Fig. 3 is LaCo of the present invention0.9Mg0.1O3Apparent first order kinetics figure under-MgO-Ag visible light catalyst visible light.
Specific embodiment
With reference to the accompanying drawings and examples, technical solution of the present invention is described in detail.
Embodiment 1
LaCo of the present invention0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalyst, includes the following steps:
Step 1, the La (NO of corresponding amount is weighed by La: Co: Mg molar ratio 1: 0.9: 13)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then the citric acid for weighing corresponding amount by the molar ratio of metal cation and citric acid for 1: 1, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid are dissolved in deionized water together to be filled
Mixed solution is obtained after dividing dissolution, in magnetic agitation toward mixed solution and dripping ammonium hydroxide (30wt%) until the pH of mixed solution
It is 8, continuing magnetic force is stirred solution 3h and makes mixed solution solation under 80 DEG C of water-baths, and the mixed solution of solation is set
Stood at 110 DEG C 12h become respectively to roast at a temperature of being respectively placed in 400 DEG C and 750 DEG C again after gelation, in air atmosphere 4h with
Organic matter and abundant crystallization are removed respectively, obtain LaCo0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methanol, obtains A mixed liquor；
Step 3, by 0.016g AgNO3Particle is added in A mixed liquor, is uniformly mixing to obtain B mixed liquor；
Step 4, B mixed liquor is placed under 125W high-pressure sodium lamp, the ultraviolet light 5h in magnetic agitation；
Step 5, the product of step 4 filtered, washed, and dried for 24 hours at 80 DEG C.
Obtained LaCo0.9Mg0.1O3In-MgO-Ag catalyst, the load capacity of Ag is the 1% of catalyst quality；MgO's is negative
Carrying capacity is the 13% of catalyst quality.
Embodiment 2
LaCo of the present invention0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalyst, includes the following steps:
Step 1, the La (NO of corresponding amount is weighed by La: Co: Mg molar ratio 1: 0.9: 23)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then the citric acid for weighing corresponding amount by the molar ratio of metal cation and citric acid for 1: 1, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid are dissolved in deionized water together to be filled
Mixed solution is obtained after dividing dissolution, in magnetic agitation toward mixed solution and dripping ammonium hydroxide (30wt%) until the pH of mixed solution
It is 8, continuing magnetic force is stirred solution 3h and makes the abundant solation of mixed solution under 80 DEG C of water-baths, and the mixing of solation is molten
Liquid, which is placed at 110 DEG C, to be stood 12h and becomes respectively to roast at a temperature of being respectively placed in 400 DEG C and 750 DEG C again after gelation, in air atmosphere
4h obtains LaCo to remove organic matter and abundant crystallization respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methanol, obtains A mixed liquor；
Step 3, by 0.021g AgNO3Particle is added in A mixed liquor, is uniformly mixing to obtain B mixed liquor；
Step 4, B mixed liquor is placed under 125W high-pressure sodium lamp, the ultraviolet light 5h in magnetic agitation；
Step 5, the product of step 4 filtered, washed, and dried for 24 hours at 80 DEG C.
Obtained LaCo0.9Mg0.1O3In-MgO-Ag catalyst, the load capacity of Ag is the 1.3% of catalyst quality；MgO's
Load capacity is the 19% of catalyst quality.
Embodiment 3
LaCo of the present invention0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalyst, includes the following steps:
Step 1, the La (NO of corresponding amount is weighed by La: Co: Mg molar ratio 1: 0.9: 13)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then the citric acid for weighing corresponding amount by the molar ratio of metal cation and citric acid for 1: 1, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid are dissolved in deionized water together to be filled
Mixed solution is obtained after dividing dissolution, in magnetic agitation toward mixed solution and dripping ammonium hydroxide (30wt%) until the pH of mixed solution
It is 8, continuing magnetic force is stirred solution 3h and makes the abundant solation of mixed solution under 80 DEG C of water-baths, and the mixing of solation is molten
Liquid, which is placed at 110 DEG C, to be stood 12h and becomes respectively to roast at a temperature of being respectively placed in 400 DEG C and 750 DEG C again after gelation, in air atmosphere
4h obtains LaCo to remove organic matter and abundant crystallization respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methanol, obtains A mixed liquor；
Step 3, by 0.026gAgNO3Particle is added in A mixed liquor, is uniformly mixing to obtain B mixed liquor；
Step 4, B mixed liquor is placed under 125W high-pressure sodium lamp, the ultraviolet light 6h in magnetic agitation；
Step 5, the product of step 4 filtered, washed, and dried for 24 hours at 80 DEG C.
Obtained LaCo0.9Mg0.1O3In-MgO-Ag catalyst, the load capacity of Ag is the 1.6% of catalyst quality；MgO's
Load capacity is the 13% of catalyst quality.
Embodiment 4
LaCo of the present invention0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalyst, includes the following steps:
Step 1, the La (NO of corresponding amount is weighed by La: Co: Mg molar ratio 1: 0.9: 23)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then the citric acid for weighing corresponding amount by the molar ratio of metal cation and citric acid for 1: 1, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid are dissolved in deionized water together to be filled
Mixed solution is obtained after dividing dissolution, in magnetic agitation toward mixed solution and dripping ammonium hydroxide (30wt%) until the pH of mixed solution
It is 8, continuing magnetic force is stirred solution 3h and makes the abundant solation of mixed solution under 80 DEG C of water-baths, and the mixing of solation is molten
Liquid, which is placed at 110 DEG C, to be stood 12h and becomes respectively to roast at a temperature of being respectively placed in 400 DEG C and 750 DEG C again after gelation, in air atmosphere
4h obtains LaCo to remove organic matter and abundant crystallization respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methanol, obtains A mixed liquor；
Step 3, by 0.032gAgNO3Particle is added in A mixed liquor, is uniformly mixing to obtain B mixed liquor；
Step 4, B mixed liquor is placed under 125W high-pressure sodium lamp, the ultraviolet light 6h in magnetic agitation；
Step 5, the product of step 4 filtered, washed, and dried for 24 hours at 80 DEG C.
Obtained LaCo0.9Mg0.1O3In-MgO-Ag catalyst, the load capacity of Ag is the 2% of catalyst quality；MgO's is negative
Carrying capacity is the 19% of catalyst quality.
The LaCo of Examples 1 to 4 preparation is respectively adopted0.9Mg0.1O3- MgO-Ag catalyst can to methyl orange progress in solution
The experiment of light-exposed absorption-photocatalysis removal ability:
Taking initial concentration is the MO solution 100mL of 20mg/L, and LaCo prepared by 0.05g embodiment 1 is added0.9Mg0.1O3-
MgO-Ag photochemical catalyst, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, unlatching 500W xenon lamp is light source, 2mol/L
NaNO2It filters and irradiates 3h, carry out photocatalysis experiment.To the end of testing, solution is taken out, and after being centrifuged with supercentrifuge, surveyed
MO concentration in solution out, according to formula (1)Find out removal rate, in formula (1): R is removal rate (%), C0For solution
The initial concentration (mg/L) of middle MO, CtFor the concentration (mg/L) of MO in solution after absorption-light-catalyzed reaction；
Taking initial concentration is the MO solution 100mL of 20mg/L, and LaCo prepared by 0.05g embodiment 2 is added0.9Mg0.1O3-
MgO-Ag photochemical catalyst, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, unlatching 500W xenon lamp is light source, 2mol/L
NaNO2It filters and irradiates 3h, carry out photocatalysis experiment, to the end of testing, take out solution, and after being centrifuged with supercentrifuge, survey
MO concentration in solution out, finds out removal rate；
Taking initial concentration is the MO solution 100mL of 20mg/L, and LaCo prepared by 0.05g embodiment 3 is added0.9Mg0.1O3-
MgO-Ag photochemical catalyst, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, unlatching 500W xenon lamp is light source, 2mol/L
NaNO2It filters and irradiates 3h, carry out photocatalysis experiment, to the end of testing, take out solution, and after being centrifuged with supercentrifuge, survey
MO concentration in solution out, finds out removal rate；
Taking initial concentration is the MO solution 100mL of 20mg/L, and LaCo prepared by 0.05g embodiment 4 is added0.9Mg0.1O3-
MgO-Ag photochemical catalyst, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, unlatching 500W xenon lamp is light source, 2mol/L
NaNO2It filters and irradiates 3h, carry out photocatalysis experiment, to the end of testing, take out solution, and after being centrifuged with supercentrifuge, survey
MO concentration in solution out, finds out removal rate；
The LaCo of Examples 1 to 4 preparation0.9Mg0.1O3Absorption-visible light light of-MgO-Ag the photochemical catalyst to MO in solution
Catalytic result is as shown in table 1:
Table 1
As shown in Table 1, when it is 1.6% that MgO load capacity, which is 13%, Ag load capacity, in catalyst, the visible light of catalyst
Catalytic effect is best.
Comparative example
LaCo prepared by embodiment 30.9Mg0.1O3- MgO-Ag photochemical catalyst and LaCo0.9Mg0.1O3- MgO photochemical catalyst into
The absorption of row MO-photocatalysis experiment:
LaCo prepared by 0.05g embodiment 30.9Mg0.1O3- MgO-Ag photochemical catalyst and 0.05g LaCo0.9Mg0.1O3-
MgO photochemical catalyst is separately added into the MO solution that two parts of 100mL initial concentrations are 20mg/L, two parts of solution constant temperature magnetic force is stirred
Mix 1h, it is to be adsorbed reach balance after, using 500W xenon lamp as light source, 2mol/LNaNO2It filters and irradiates 3h, it is real to carry out photocatalysis
It tests.It is spaced 30min sampling, after being centrifuged with supercentrifuge, surveys it under 460nm wavelength with V-5100 type visible spectrophotometer
Absorbance converts to obtain solution dye concentration by standard curve.According to formula k=C0/CtThe concentration for calculating MO in solution becomes
Change, wherein C0For the initial concentration (mg/L) of MO in solution, CtFor the concentration (mg/L) of MO in solution after absorption-light-catalyzed reaction,
As a result as shown in Figure 3.Catalyst after loaded Ag has better absorption degradation effect under visible light, this is because on the one hand
Generate the surface plasma resonance effect of Embedded A g nanoparticle, internal field's enhancing, conducive to the electronics transfer of catalyst, from
And enhance catalyst to visible light-responded ability；The collaboration loaded favourable of another aspect Ag and MgO are in catalyst surface electronics
Transition transfer, to collectively promote the degradation to dyestuff.
From figure 3, it can be seen that the photocatalytic degradation apparent constant of loaded Ag rear catalyst is the 3.7 of unsupported Ag catalyst
Times, i.e., under the same terms, photocatalytic speed is increased dramatically the catalyst after loaded Ag under visible light, relative to
LaCo0.9Mg0.1O3- MgO, catalyst of the present invention have better ultraviolet light response ability, and can also show under visible light compared with
Good photocatalysis effect.
Catalyst of the present invention combines the two-fold advantage of synchronous doping load and collaboration load, first with improved molten
Glue-gel method is synchronous to realize Mg to LaCoO3Modification is synchronized inside and outside lattice, is further restored Ag using photoreduction met hod negative
It is loaded onto the surface of catalyst, the catalyst after Ag load, on the one hand due to the surface plasma resonance of Embedded A g nanoparticle
Effect, internal field's enhancing, is conducive to electronics transfer phenomenon, to enhance catalyst to the responding ability of visible light；On the other hand
The collaboration loaded favourable of Ag and MgO is shifted in the transition of catalyst surface electronics, to collectively promote the degradation to dyestuff.
The above embodiment is merely an example for clearly illustrating the present invention, and is not to embodiment party of the invention
The restriction of formula.For those of ordinary skill in the art, other differences can also be made on the basis of the above description
The variation or variation of form.There is no necessity and possibility to exhaust all the enbodiments.And these belong to essence of the invention
The obvious changes or variations that mind is extended out are still in the protection scope of this invention.
Claims (9)
1. a kind of and doping and the preparation method for loading dual modified perovskite type photocatalyst, which is characterized in that including such as
Lower step:
Step 1, the La (NO of corresponding amount is weighed by La: Co: Mg molar ratio 1: 0.9: 1~23)3·6H2O、Co(NO3)2·6H2O and
Mg(NO3)2·6H2O, then the citric acid for weighing corresponding amount by the molar ratio of metal cation and citric acid for 1: 1, by La
(NO3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid is soluble in water together obtains mixed solution, while stirring
Mix side toward mixed solution and dripping ammonium hydroxide until mixed solution pH be 8, be persistently stirred solution under water-bath and to mix
Solution solation becomes the mixed solution of solation at a temperature of being respectively placed in 400 DEG C and 750 DEG C after gelation, air atmosphere
In respectively roast 4h, obtain LaCo0.9Mg0.1O3- MgO powder；
Step 2, by the LaCo of aequum step 10.9Mg0.1O3- MgO powder is scattered in methanol, obtains A mixed liquor；
Step 3, by the desired amount of AgNO3Particle is added in A mixed liquor, is uniformly mixing to obtain B mixed liquor；
Step 4, B mixed liquor is placed under 125w high-pressure sodium lamp, while stirring ultraviolet light deposition a period of time；
Step 5, the product of step 4 is filtered, washed and is dried；
Wherein, products therefrom A bit element is La3+Ion, B bit element are doped with Mg2+The Co of ion2+Ion, while described urging
Load has MgO and Ag in agent；Wherein, Mg2+The doping of ion is the 10% of catalyst quality；The load capacity of Ag is catalyst
The 1%~2% of quality；The load capacity of MgO is the 13%~19% of catalyst quality.
2. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 1, the metal cation refers to La in mixed solution3+Ion, Co2+Ion and Mg2+The quality of ion is total
With.
3. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 1, the mass percentage concentration of the ammonium hydroxide is 30%.
4. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 1, the bath temperature is 80 DEG C, and the mixing time that continues is 3h.
5. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 1, solation mixed solution being placed at 110 DEG C after standing 12h and becomes gelation mixed solution.
6. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 2, every addition 1gLaCo0.9Mg0.1O3- MgO powder, the volume of required methanol are 200mL.
7. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 3, the AgNO3The addition quality of particle is 0.015~0.035g.
8. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 4, the time that the UV Light is penetrated is 5~6h.
9. the simultaneous preparation method for adulterating and loading dual modified perovskite type photocatalyst according to claim 1, special
Sign is: in step 5, the drying temperature is 80 DEG C, and the drying time is for 24 hours.
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| Title |
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| "LaCoO3晶格结构内外Mg的同步改性及其光催化性能";孙慧华，等;《无机化学学报》;20161031;第32卷(第10期);摘要、第0、1节 * |
| "Pt沉积对LaCoO3 光催化还原二氧化碳活性的影响";唐勇，等;《硅酸盐通报》;20080831;第672-676、680页 * |
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