CN106732650A - 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 23
- 230000009977 dual effect Effects 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 20
- 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
- 239000011259 mixed solution Substances 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 25
- 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
- 238000002156 mixing Methods 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000001035 drying Methods 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
- 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
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 11
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- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 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
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
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- 238000006862 quantum yield reaction Methods 0.000 description 2
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- 239000003463 adsorbent Substances 0.000 description 1
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- 230000004888 barrier function Effects 0.000 description 1
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- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 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
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- 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
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of and doping and load dual modified perovskite type photocatalyst, the catalyst combines the two-fold advantage of synchronous doping load and collaboration load, therefore with visible light-responded ability high.The invention also discloses the above-mentioned simultaneous preparation method adulterated and load dual modified perovskite type photocatalyst, synchronously realize Mg to LaCoO first with improved sol-gal process3Synchronization inside and outside lattice is modified, photoreduction met hod is further utilized by the reducing loaded surfaces to catalyst of Ag, catalyst after Ag loads, on the one hand due to the surface plasma resonance effect of Embedded A g nano-particles, internal field strengthens, beneficial to electro transfer phenomenon, so as to strengthen responding ability of the catalyst to visible ray；The collaboration loaded favourable of another aspect Ag and MgO is shifted in the transition of catalyst surface electronics, so as to collectively promote the degraded to dyestuff.
Description
Technical field
The present invention relates to a kind of LaCo0.9Mg0.1O3- MgO-Ag Ca-Ti ore type visible light catalysts, further relate to above-mentioned
LaCo0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalysts, belongs to photocatalyst technology field.
Background technology
Environmental pollution governs the sustainable development of human society.Waste water from dyestuff is cause water pollution in environment main
One of reason.Waste water from dyestuff is mainly derived from textile and paper industry, with colourity is high, acid-base property change greatly, organic content it is high,
Poisonous the characteristics of.Wherein 60% to 70% dyestuff belongs to azo dyes, can increase poisonous carcinogen in water body, endangers people
Class it is healthy.The conventional 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 actual applications
Greatly, adsorbent amount is big and be difficult to regenerate, fouling membrane, high cost the problems such as.
With the development of economic science, Photocatalitic Technique of Semiconductor degradation of dye waste water is increasingly subject to pay attention to.Semiconductor light
Catalysis technique is carried out at normal temperatures, it is possible to use organic dye molecule is degraded to CO by sunshine or ultraviolet light as light source2、
H2O and other inorganic matters, do not produce secondary pollution.Also, many is difficult to biodegradable or difficult with other method in waste water from dyestuff
With the material for removing, it is possible to use conductor photocatalysis method is removed.Wherein, TiO2It is the photochemical catalyst of current most study, but
It is larger (about 3.2eV) its energy gap, it is less efficient to Solar use.
In recent years, perovskite semi-conducting material due to its structure-controllable, heat endurance it is good, it is cheap the advantages of, gradually
Focus as the research of semiconductor catalytic field.Perovskite energy gap is smaller (about 2.6eV), but still has quantum yield relatively low
The technical barriers such as (about 4%), solar energy utilization ratio are low, difficult load, hinder it and are industrially widely applied.Therefore, pass through
Method of modifying improves the quantum yield of perovskite material, increases its utilization rate to sunshine and is extremely necessary.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of and doping and load dual modified Ca-Ti ore type light and urge
Agent.
The technical problem also to be solved of the invention is to provide above-mentioned and doping and loads dual modified Ca-Ti ore type light and urges
The preparation method of agent.
In order to solve the above technical problems, the technology used in the present invention means are：
A kind of and doping and load dual modified perovskite type photocatalyst, the catalyst A bits element is La3+From
Son, B bit elements are doped with Mg2+The Co of ion2+Ion, while being loaded with 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.
The above-mentioned simultaneous preparation method adulterated and load dual modified perovskite type photocatalyst, comprises the following steps：
Step 1, by La: Co: Mg mol ratio 1: 0.9: 1~2 weighs the La (NO of respective amount3)3·6H2O、Co(NO3)2·
6H2O and Mg (NO3)2·6H2O, then be 1: 1 citric acid for weighing respective amount by the mol ratio of metal cation and citric acid, will
La(NO3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid are soluble in water together to obtain mixed solution, side
Stirring side toward mixed solution and dripping ammoniacal liquor until the pH of mixed solution is 8, in persistently stirring mixed solution under water-bath so that mixing
Solution solation is closed, at a temperature of the mixed solution of solation is become to be respectively placed in 400 DEG C and 750 DEG C after gelation, air atmosphere
Each roasting 4h, obtains LaCo in enclosing0.9Mg0.1O3- MgO powder；
Step 2, by the LaCo of aequum step 10.9Mg0.1O3- MgO powder is scattered in methyl alcohol (methanol as solvent and dispersion
Agent, also as the sacrifice agent in hole) in, obtain A mixed liquors；
Step 3, by the desired amount of AgNO3Particle is added in A mixed liquors, is uniformly mixing to obtain B mixed liquors；
Step 4, B mixed liquors are placed under 125W high-pressure sodium lamps, while stirring ultraviolet light deposition a period of time；Utilize
Ultraviolet light is deposited, and the of short duration separation of the electron-hole of catalyst is caused under ultraviolet excitation, in order to avoid it is multiple again
Close, add methyl alcohol as hole sacrifice agent, consume hole, such Ag+More electronics can be just obtained, so as to be reduced into Ag
Grain, reaches the purpose of area load Ag；
Step 5, suction filtration, washing and dried process are carried out by the product of step 4.
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 ammoniacal liquor 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, gelation mixed solution is become after standing 12h at solation mixed solution is placed in into 110 DEG C.
Wherein, in step 2,1g LaCo are often added0.9Mg0.1O3- MgO powder, the volume of required methyl alcohol is 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 24h.
LaCo of the present invention0.9Mg0.1O3The preparation principle of-MgO-Ag Ca-Ti ore type visible light catalysts：The present invention is by changing
The sol-gel process entered prepares the modified LaCo of synchronization Mg0.9Mg0.1O3- MgO, is further reduced Ag using photoreduction met hod
Perovskite catalyst surface is loaded to, LaCo is ultimately generated0.9Mg0.1O3-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 to prior art, technical solution of the present invention have the advantage that for：
LaCo of the present invention0.9Mg0.1O3The load of Ag in-MgO-Ag visible light catalysts, on the one hand causes Embedded A g to receive
The surface plasma resonance effect of rice corpuscles, internal field's enhancing, beneficial to the electro transfer of catalyst, so as to strengthen catalyst pair
Visible light-responded ability；The collaboration loaded favourable of another aspect Ag and MgO is shifted in the transition of catalyst surface electronics, so that altogether
With the degraded promoted to dyestuff；Preparation method process is simple of the present invention, with promotional value.
Brief description of the drawings
Fig. 1 is LaCo of the present invention0.9Mg0.1O3The process chart of-MgO-Ag visible light catalyst preparation methods；
Fig. 2 is LaCo of the present invention0.9Mg0.1O3Degradation effect under-MgO-Ag visible light catalyst visible rays to MO is contrasted
Figure；
Fig. 3 is LaCo of the present invention0.9Mg0.1O3Apparent first order kinetics figure under-MgO-Ag visible light catalyst visible rays.
Specific embodiment
With reference to the accompanying drawings and examples, technical scheme is described in detail.
Embodiment 1
LaCo of the present invention0.9Mg0.1O3The preparation method of-MgO-Ag Ca-Ti ore type visible light catalysts, comprises the following steps：
Step 1, by La: Co: Mg mol ratio 1: 0.9: 1 weighs the La (NO of respective amount3)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then be 1: 1 citric acid for weighing respective amount by the mol ratio of metal cation and citric acid, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid fill in being dissolved in deionized water together
Mixed solution is obtained after dividing dissolving, in magnetic agitation toward mixed solution and dripping ammoniacal liquor (30wt%) until the pH of mixed solution
It is 8, mixed solution solation is caused in continuing magnetic force stirring mixed solution 3h under 80 DEG C of water-baths, the mixed solution of solation is put
In at 110 DEG C stand 12h become gelation after be respectively placed in 400 DEG C and 750 DEG C again at a temperature of, in air atmosphere respectively be calcined 4h with
Organics removal and abundant crystallization, obtain LaCo respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methyl alcohol, obtains A mixed liquors；
Step 3, by 0.016g AgNO3Particle is added in A mixed liquors, is uniformly mixing to obtain B mixed liquors；
Step 4, B mixed liquors are placed under 125W high-pressure sodium lamps, the ultraviolet light 5h in magnetic agitation；
Step 5, suction filtration, washing are carried out by the product of step 4, and in drying 24h at 80 DEG C.
The LaCo for obtaining0.9Mg0.1O3In-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 catalysts, comprises the following steps：
Step 1, by La: Co: Mg mol ratio 1: 0.9: 2 weighs the La (NO of respective amount3)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then be 1: 1 citric acid for weighing respective amount by the mol ratio of metal cation and citric acid, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid fill in being dissolved in deionized water together
Mixed solution is obtained after dividing dissolving, in magnetic agitation toward mixed solution and dripping ammoniacal liquor (30wt%) until the pH of mixed solution
It is 8, the abundant solation of mixed solution is caused in continuing magnetic force stirring mixed solution 3h under 80 DEG C of water-baths, the mixing of solation is molten
Liquid stood at being placed in 110 DEG C 12h become to be respectively placed in 400 DEG C and 750 DEG C again after gelation at a temperature of, be respectively calcined in air atmosphere
4h obtains LaCo with organics removal and abundant crystallization respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methyl alcohol, obtains A mixed liquors；
Step 3, by 0.021g AgNO3Particle is added in A mixed liquors, is uniformly mixing to obtain B mixed liquors；
Step 4, B mixed liquors are placed under 125W high-pressure sodium lamps, the ultraviolet light 5h in magnetic agitation；
Step 5, suction filtration, washing are carried out by the product of step 4, and in drying 24h at 80 DEG C.
The LaCo for obtaining0.9Mg0.1O3In-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 catalysts, comprises the following steps：
Step 1, by La: Co: Mg mol ratio 1: 0.9: 1 weighs the La (NO of respective amount3)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then be 1: 1 citric acid for weighing respective amount by the mol ratio of metal cation and citric acid, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid fill in being dissolved in deionized water together
Mixed solution is obtained after dividing dissolving, in magnetic agitation toward mixed solution and dripping ammoniacal liquor (30wt%) until the pH of mixed solution
It is 8, the abundant solation of mixed solution is caused in continuing magnetic force stirring mixed solution 3h under 80 DEG C of water-baths, the mixing of solation is molten
Liquid stood at being placed in 110 DEG C 12h become to be respectively placed in 400 DEG C and 750 DEG C again after gelation at a temperature of, be respectively calcined in air atmosphere
4h obtains LaCo with organics removal and abundant crystallization respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methyl alcohol, obtains A mixed liquors；
Step 3, by 0.026gAgNO3Particle is added in A mixed liquors, is uniformly mixing to obtain B mixed liquors；
Step 4, B mixed liquors are placed under 125W high-pressure sodium lamps, the ultraviolet light 6h in magnetic agitation；
Step 5, suction filtration, washing are carried out by the product of step 4, and in drying 24h at 80 DEG C.
The LaCo for obtaining0.9Mg0.1O3In-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 catalysts, comprises the following steps：
Step 1, by La: Co: Mg mol ratio 1: 0.9: 2 weighs the La (NO of respective amount3)3·6H2O、Co(NO3)2·6H2O
With Mg (NO3)2·6H2O, then be 1: 1 citric acid for weighing respective amount by the mol ratio of metal cation and citric acid, will be above-mentioned
La (the NO of corresponding amount3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid fill in being dissolved in deionized water together
Mixed solution is obtained after dividing dissolving, in magnetic agitation toward mixed solution and dripping ammoniacal liquor (30wt%) until the pH of mixed solution
It is 8, the abundant solation of mixed solution is caused in continuing magnetic force stirring mixed solution 3h under 80 DEG C of water-baths, the mixing of solation is molten
Liquid stood at being placed in 110 DEG C 12h become to be respectively placed in 400 DEG C and 750 DEG C again after gelation at a temperature of, be respectively calcined in air atmosphere
4h obtains LaCo with organics removal and abundant crystallization respectively0.9Mg0.1O3- MgO powder；
Step 2, by 1g LaCo0.9Mg0.1O3- MgO powder is scattered in 200mL methyl alcohol, obtains A mixed liquors；
Step 3, by 0.032gAgNO3Particle is added in A mixed liquors, is uniformly mixing to obtain B mixed liquors；
Step 4, B mixed liquors are placed under 125W high-pressure sodium lamps, the ultraviolet light 6h in magnetic agitation；
Step 5, suction filtration, washing are carried out by the product of step 4, and in drying 24h at 80 DEG C.
The LaCo for obtaining0.9Mg0.1O3In-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 the preparation of embodiment 1~4 is respectively adopted0.9Mg0.1O3- MgO-Ag catalyst is carried out to methyl orange in solution can
See the experiment of light absorption-photocatalysis removal ability：
Take the MO solution 100mL that initial concentration is 20mg/L, the LaCo for adding 0.05g embodiments 1 to prepare0.9Mg0.1O3-
MgO-Ag photochemical catalysts, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, it is light source, 2mol/L to open 500W xenon lamps
NaNO23h is filtered and irradiated, photocatalysis experiment is carried out.Treat that experiment terminates, take out solution, and with supercentrifuge be centrifuged after, survey
Go out MO concentration in solution, according to formula (1)Clearance is obtained, in formula (1)：R is clearance (%), C0It is solution
The initial concentration (mg/L) of middle MO, CtIt is the concentration (mg/L) of MO in solution after absorption-light-catalyzed reaction；
Take the MO solution 100mL that initial concentration is 20mg/L, the LaCo for adding 0.05g embodiments 2 to prepare0.9Mg0.1O3-
MgO-Ag photochemical catalysts, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, it is light source, 2mol/L to open 500W xenon lamps
NaNO2Filter and irradiate 3h, carry out photocatalysis experiment, treat that experiment terminates, take out solution, and with supercentrifuge be centrifuged after, survey
Go out MO concentration in solution, obtain clearance；
Take the MO solution 100mL that initial concentration is 20mg/L, the LaCo for adding 0.05g embodiments 3 to prepare0.9Mg0.1O3-
MgO-Ag photochemical catalysts, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, it is light source, 2mol/L to open 500W xenon lamps
NaNO2Filter and irradiate 3h, carry out photocatalysis experiment, treat that experiment terminates, take out solution, and with supercentrifuge be centrifuged after, survey
Go out MO concentration in solution, obtain clearance；
Take the MO solution 100mL that initial concentration is 20mg/L, the LaCo for adding 0.05g embodiments 4 to prepare0.9Mg0.1O3-
MgO-Ag photochemical catalysts, temperature constant magnetic stirring 1h, it is to be adsorbed reach balance after, it is light source, 2mol/L to open 500W xenon lamps
NaNO2Filter and irradiate 3h, carry out photocatalysis experiment, treat that experiment terminates, take out solution, and with supercentrifuge be centrifuged after, survey
Go out MO concentration in solution, obtain clearance；
LaCo prepared by embodiment 1~40.9Mg0.1O3Absorption-visible ray light of-MgO-Ag the photochemical catalysts 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 is 13%, Ag load capacity in catalyst, the visible ray of catalyst
Catalytic effect is best.
Comparative example
LaCo prepared by embodiment 30.9Mg0.1O3- MgO-Ag photochemical catalysts and LaCo0.9Mg0.1O3- MgO photochemical catalysts enter
The absorption of row MO-photocatalysis experiment：
LaCo prepared by 0.05g embodiments 30.9Mg0.1O3- MgO-Ag photochemical catalysts and 0.05g LaCo0.9Mg0.1O3-
MgO photochemical catalysts, are separately added into the MO solution that two parts of 100mL initial concentrations are 20mg/L, and two parts of solution constant temperature magnetic force are stirred
Mix 1h, it is to be adsorbed reach balance after, with 500W xenon lamps as light source, 2mol/LNaNO23h is filtered and irradiated, photocatalysis reality is carried out
Test.Interval 30min samplings, after being centrifuged with supercentrifuge, it are surveyed with V-5100 types visible spectrophotometer under 460nm wavelength
Absorbance, is converted by standard curve and obtains solution dye concentration.According to formula k=C0/CtThe concentration for calculating MO in solution becomes
Change, wherein C0It is the initial concentration (mg/L) of MO in solution, CtIt is the concentration (mg/L) of MO in solution after absorption-light-catalyzed reaction,
Result is as shown in Figure 3.Catalyst after loaded Ag has more preferable absorption degradation effect under visible light, because on the one hand
Produce the surface plasma resonance effect of Embedded A g nano-particles, internal field's enhancing, beneficial to the electro transfer of catalyst, from
And strengthen catalyst to visible light-responded ability；The collaboration loaded favourable of another aspect Ag and MgO is in catalyst surface electronics
Transition is shifted, so as to collectively promote the degraded 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 has more preferable ultraviolet light response ability, and can also represent 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, and it is first with improved molten
Glue-gel method synchronously realizes Mg to LaCoO3Synchronization inside and outside lattice is modified, further using photoreduction met hod that Ag reduction is negative
It is loaded onto the surface of catalyst, the catalyst after Ag loads, on the one hand due to the surface plasma resonance of Embedded A g nano-particles
Effect, internal field's enhancing, beneficial to electro transfer phenomenon, so as to strengthen responding ability of the catalyst to visible ray；On the other hand
The collaboration loaded favourable of Ag and MgO is shifted in the transition of catalyst surface electronics, so as to collectively promote the degraded to dyestuff.
Above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to embodiment party of the invention
The restriction of formula.For those of ordinary skill in the field, it is different that other can also be made on the basis of the above description
The change or variation of form.There is no need and unable to be exhaustive to all of implementation method.And these belong to essence of the invention
Among the refreshing obvious change extended out or variation are still in protection scope of the present invention.
Claims (10)
1. a kind of and doping and dual modified perovskite type photocatalyst loaded, it is characterised in that：The catalyst A bits element
It is La3+Ion, B bit elements are doped with Mg2+The C of ionO 2+Ion, while being loaded with MgO and Ag on the catalyst；Its
In, Mg2+The doping of ion is the 10% of catalyst quality；The load capacity of Ag is the 1%~2% of catalyst quality；MgO's is negative
Carrying capacity is the 13%~19% of catalyst quality.
2. described in a kind of claim 1 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be, comprise the following steps：
Step 1, by La: Co: Mg mol ratio 1: 0.9: 1~2 weighs the La (NO of respective amount3)3·6H2O、Co(NO3)2·6H2O and
Mg(NO3)2·6H2O, then be 1: 1 citric acid for weighing respective amount by the mol ratio of metal cation and citric acid, by La
(NO3)3·6H2O、Co(NO3)2·6H2O、Mg(NO3)2·6H2O and citric acid are soluble in water together to obtain mixed solution, while stirring
Side is mixed toward mixed solution and dripping ammoniacal liquor up to the pH of mixed solution is 8, mixing is caused in mixed solution is persistently stirred under water-bath
Solution solation, at a temperature of the mixed solution of solation is become to be respectively placed in 400 DEG C and 750 DEG C after gelation, air atmosphere
In each roasting 4h, obtain LaCo0.9Mg0.1O3- MgO powder；
Step 2, by the LaCo of aequum step 10.9Mg0.1O3- MgO powder is scattered in methyl alcohol, obtains A mixed liquors；
Step 3, by the desired amount of AgNO3Particle is added in A mixed liquors, is uniformly mixing to obtain B mixed liquors；
Step 4, B mixed liquors are placed under 125W high-pressure sodium lamps, while stirring ultraviolet light deposition a period of time；
Step 5, suction filtration, washing and dried process are carried out by the product of step 4.
3. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 1, the metal cation refers to La in mixed solution3+Ion, CO 2+Ion and Mg2+The quality of ion is total
With.
4. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 1, the mass percentage concentration of the ammoniacal liquor is 30%.
5. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 1, the bath temperature is 80 DEG C, and the mixing time that continues is 3h.
6. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 1, gelation mixed solution is become after standing 12h at solation mixed solution is placed in into 110 DEG C.
7. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 2,1g LaCo are often added0.9Mg0.1O3- MgO powder, the volume of required methyl alcohol is 200mL.
8. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 3, the AgNO3The addition quality of particle is 0.015~0.035g.
9. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 4, the time that the UV Light is penetrated is 5~6h.
10. according to claim 2 and doping and the preparation method of dual modified perovskite type photocatalyst is loaded, it is special
Levy and be：In step 5, the drying temperature is 80 DEG C, and the drying time is 24h.
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| CN109364915A (en) * | 2018-11-23 | 2019-02-22 | 江苏中创清源科技有限公司 | A kind of Ca-Ti ore type O composite metallic oxide catalyst and preparation method thereof |
| CN112439431A (en) * | 2020-11-30 | 2021-03-05 | 佛山科学技术学院 | Composite photocatalyst based on strontium doping and preparation method and application thereof |
| CN114014343A (en) * | 2021-10-22 | 2022-02-08 | 湖北大学 | High-activity defect-state magnesium oxide nanosheet and preparation method and application thereof |
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|---|---|---|---|---|
| CN103372447A (en) * | 2012-04-26 | 2013-10-30 | 北京化工大学 | High-specific-surface-area perovskite catalyst LaCo0.9Mg0.1O3 and preparation method thereof |
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| CN103372447A (en) * | 2012-04-26 | 2013-10-30 | 北京化工大学 | High-specific-surface-area perovskite catalyst LaCo0.9Mg0.1O3 and preparation method thereof |
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| 唐勇，等: ""Pt沉积对LaCoO3 光催化还原二氧化碳活性的影响"", 《硅酸盐通报》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364915A (en) * | 2018-11-23 | 2019-02-22 | 江苏中创清源科技有限公司 | A kind of Ca-Ti ore type O composite metallic oxide catalyst and preparation method thereof |
| CN112439431A (en) * | 2020-11-30 | 2021-03-05 | 佛山科学技术学院 | Composite photocatalyst based on strontium doping and preparation method and application thereof |
| CN114014343A (en) * | 2021-10-22 | 2022-02-08 | 湖北大学 | High-activity defect-state magnesium oxide nanosheet and preparation method and application thereof |
| CN114014343B (en) * | 2021-10-22 | 2023-08-29 | 湖北大学 | High-activity defect-state magnesium oxide nano-sheet and preparation method and application thereof |
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