CN106582722B - Compound photocatalytic system and its preparation method and application - Google Patents
Compound photocatalytic system and its preparation method and application Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 49
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims abstract description 60
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 23
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 23
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 29
- 238000006731 degradation reaction Methods 0.000 claims description 24
- 230000015556 catabolic process Effects 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 6
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000003426 co-catalyst Substances 0.000 abstract description 5
- 230000009977 dual effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- 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
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- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The present invention relates to compound photocatalytic systems and its preparation method and application.The compound photocatalytic system is Er3+:Y3Al5O12/(MoS2/NiGa2O4)‑(BiVO4/PdS).First, up-conversion luminescence agent Er is synthesized by sol-gel method3+:Y3Al5O12Nano particle;Secondly, NiGa is synthesized by hydro-thermal method2O4And BiVO4, and prepare Er3+:Y3Al5O12/NiGa2O4‑BiVO4;Finally, load conduction band co-catalyst MoS2With valence band co-catalyst PdS, target product is obtained.The novel photocatalysis system that the present invention designs has strong oxidation-reduction quality, and pollutant is considered as a kind of resource, generates Hydrogen Energy while pollutant removal using photocatalysis technology, has reached environmental improvement while having generated the dual purpose of clean energy resource.
Description
Technical field
The invention belongs to photocatalysis fields, and in particular to compound photocatalytic system Er3+:Y3Al5O12/(MoS2/
NiGa2O4)-(BiVO4/ PdS) preparation and its under visible light illumination light degradation organic pollution while hydrogen manufacturing in answer
With.
Background technology
Environmental pollution has developed into the Tough questions that the mankind must face in social development process.The meeting in dye industry
Some azo dyes are generated, due to their stable structure, high toxicity carries electron-withdrawing group, therefore is difficult degradation.This kind of difficulty
Degradation of contaminant can exist in the environment for a long time has prodigious harm to ecological environment and human health.However, individually to this kind of
Recalcitrant chemicals are degraded without utilizing a kind of waste for being also resource.So the method that should propose an economical rationality
To solve the problems, such as this.In fact, Recalcitrant chemicals can be used as an available resource, pass through a suitable method
Not only regenerative resource can be generated with degradation of contaminant but also simultaneously, the problem of energy crisis has become global concern after all.
So far, many methods are used for degradation of contaminant, such as biology, physics and chemistry, flocculation and absorption method, but bioanalysis
Due to needing culture microorganism for a long time, thus processing time is longer;Other methods only only reside within how pollution degradation
On nitride layer face, a kind of contaminant degradation system for being conducive to environment of green high-efficient is not formed.Under comparing, photocatalytic method
Possess high efficiency, to waste water non-selectivity the characteristics of, and semiconductor light-catalyst chemical property stablize, oxidation-reduction quality is strong,
Service life is long.Therefore, by photocatalytic method, redox reaction occurs using cheap abundant solar energy, realizes and hardly possible is dropped
It solves the degradation of pollutant and generates high fuel value, the Hydrogen Energy of the water of combustion product and non-environmental-pollution simultaneously.This method not only drops
It has solved pollutant and has additionally provided a kind of production hydrogen technology of simplicity, realize environmental improvement and produced the dual purpose of clean energy resource.
In order to realize above-mentioned dual purpose, the wide band gap semiconducter catalyst with Strong oxdiative reduction activation should be selected.
However alternative such semi-conducting material is considerably less, and since wide band gap needs very high energy to excite.Cause
How this obtains a photocatalytic system with Strong oxdiative reduction activation, is urgently to realize photocatalytic degradation hydrogen manufacturing simultaneously
It solves the problems, such as.
Invention content
In order to solve problem above, the purpose of the present invention is one catalyst with relatively negative conduction band of selection to have with one
The catalyst of calibration conduction band carries out compound, one compound photocatalytic system Er with Strong oxdiative reduction activation of preparation3+:
Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/ PdS), and realize under visible light illumination to organic pollutant degradation while system
Hydrogen.
The technical solution adopted by the present invention is:Compound photocatalytic system, the compound photocatalytic system is Er3+:
Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS)。
The present invention synthesizes up-conversion luminescence agent Er by sol-gel method first3+:Y3Al5O12Nano particle;Secondly,
NiGa is synthesized by hydro-thermal method2O4And BiVO4, and prepare Er3+:Y3Al5O12/NiGa2O4-BiVO4;Finally, load conduction band, which helps, urges
Agent MoS2With valence band co-catalyst PdS, Er is obtained3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS).Specific steps
For:
1) Er is prepared3+:Y3Al5O12Nano particle:By a certain amount of Er2O3And Y2O3Powder, magnetic agitation simultaneously heat holding
It is dissolved at 60 DEG C in concentrated nitric acid until water white transparency, obtains mixed rare-earth oxide solution.Then by a certain amount of Al (NO3)3·
9H2(molar ratio of citric acid and rare earth ion is 3 for O and solid citric acid:1) it is dissolved in redistilled water, and is slowly added to
In mixed rare-earth oxide solution made of above-mentioned, stirring is until solution is in sticky foaming colloidal solution at 50-60 DEG C.Then
It is placed into baking oven and maintains 36h at 80 DEG C, obtain gel.Obtained gel is first to heat to 500 DEG C in Muffle furnace and is maintained
50min is continued thereafter with and is heated to 1100 DEG C and continues 2.0h.Finally the residue after high-temperature heating is taken out, cools down and grinds
Er is obtained after mill3+:Y3Al5O12Nano particle.
2) NiGa is prepared2O4:Metal Ga, which is dissolved in nitric acid, obtains Ga (NO3)3, the Ga (NO that will be evaporated3)3It is placed on Muffle furnace
In, in 550 DEG C of calcination 5.0-5.5h, is taken out after cooling, obtain Ga2O3;Ga2O3Solid is added in nickel nitrate solution, stirring
After 30min, pH to 12 is adjusted, then proceedes to stirring 30min, obtained aaerosol solution is transferred in reaction kettle, is maintained at 180 DEG C
48.0-49.0h, obtained sediment are cleaned with deionized water, dry, obtain NiGa2O4。
3) BiVO is prepared4:Bi(NO3)3·5H2O is dissolved completely in nitric acid, and NH is then added dropwise4VO3Sodium hydroxide
Solution after being sufficiently stirred, adjusts pH=8, is followed by stirring for 30min, is then transferred into reaction kettle, 180 DEG C of maintenance 24.0-
25.0h obtains solid, cleans, dry, obtains BiVO4。
4) Er is prepared3+:Y3Al5O12/NiGa2O4:By Er3+:Y3Al5O12And NiGa2O4It is added to the water, ultrasonic disperse, shape
At suspension, after boiling 15-20min at 95-105 DEG C, 2.0-2.5h is calcined at 300 DEG C, obtains Er3+:Y3Al5O12/
NiGa2O4.Preferably, in mass ratio, Er3+:Y3Al5O12:NiGa2O4=3:7.
5) Er is prepared3+:Y3Al5O12/NiGa2O4-BiVO4:By Er3+:Y3Al5O12/NiGa2O4And BiVO4It is added to the water,
Ultrasonic disperse forms suspension, after boiling 15-20min at 95-105 DEG C, calcines 2.0-2.5h at 500 DEG C, obtain Er3+:
Y3Al5O12/NiGa2O4-BiVO4.Preferably, in molar ratio, NiGa2O4:BiVO4=1:0.5-1.0.
6) Er is prepared3+:Y3Al5O12/MoS2-(NiGa2O4-BiVO4):By Er3+:Y3Al5O12/NiGa2O4-BiVO4And MoS2
In ethanol, ultrasonic disperse boils 15-20min at 75-80 DEG C for dissolving, filters, and washs, dry, obtains Er3+:Y3Al5O12/
MoS2-(NiGa2O4-BiVO4)。
7) Er is prepared3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS):By Er3+:Y3Al5O12/MoS2-
(NiGa2O4-BiVO4) it is dissolved in Na2In S aqueous solutions, under magnetic stirring, PdCl is added dropwise2Solution reacts 5.0-
6.0min is centrifuged, and is washed, dry, obtains Er3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS)。
The application in light degradation organic pollution under visible light of above-mentioned compound photocatalytic system.Method is as follows:In
In solution containing organic pollution, above-mentioned compound photocatalytic system is added, irradiates 1.0-8.0h under visible light.
Above-mentioned compound photocatalysis body ties up to the application in the hydrogen manufacturing simultaneously of light degradation organic pollution under visible illumination.Side
Method is as follows:Solution containing organic pollution is placed in Photocatalyzed Hydrogen Production reactor, in addition the compound photocatalytic system stated,
1.0~8.0h is irradiated under visible light.
The beneficial effects of the invention are as follows:NiGa2O4Hydrolyzing production hydrogen material as light, there are two defects:First, wider band gap
(Ebg=3.54eV), energy gap is larger, makes NiGa2O4The visible light part in sunlight, light utilization efficiency cannot be efficiently used
It is low.Utilize up-conversion luminescent material Er3+:Y3Al5O12It can will be seen that light is converted into ultraviolet light this feature, can solve
NiGa2O4Visible light this drawback in sunlight cannot be efficiently used.The other is NiGa2O4The relatively low discomfort of oxidability
It shares in contaminant degradation.It needs to carry out compound, BiVO with a semi-conducting material with Strong oxdiative ability thus4Have relatively strong
Oxidability be useful in light degradation pollutant field.After carrying out level analysis to the two, NiGa is found2O4Conduction band (-
2.29eV) and BiVO4Energy difference (2.59eV) between conduction band (+0.3eV) will be significantly greater than NiGa2O4Valence band (+1.25eV)
With BiVO4Energy difference (0.95eV) between conduction band (- 2.29eV).Based on this feature, the present invention is compound by the two, NiGa2O4Valence
It the hole taken can quickly and BiVO4Electronics progress on conduction band is compound, to retain NiGa2O4Strong reducing property on conduction band
Electronics and BiVO4The hole of strong oxidizing property in valence band.NiGa2O4The electronics of strong reducing property on conduction band, by conduction band co-catalyst MoS2
Capture and H+Reaction generates H2, BiVO4The hole of strong oxidizing property in valence band captures deoxidation orange G by valence band co-catalyst PdS,
Hydrogen manufacturing while to realize efficient photocatalytic degradation.The novel photocatalysis system that the present invention designs has strong redox
Property, and pollutant is considered as a kind of resource, Hydrogen Energy is generated while pollutant removal using photocatalysis technology, has reached ring
Border is administered while generating the dual purpose of clean energy resource.
Description of the drawings
Fig. 1 is the X-ray diffractogram of compound photocatalytic system;
Wherein, a:NiGa2O4With BiVO4Molar ratio be 1.0:0.0;
b:NiGa2O4With BiVO4Molar ratio be 1.0:0.5;
c:NiGa2O4With BiVO4Molar ratio be 1.0:1.0.
Specific implementation mode
1 compound photocatalytic system Er of embodiment3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS)
Preparation method is as follows:
1) Er is prepared3+:Y3Al5O12Nano particle:By the Er of 2.2715g2O3With 0.0128g Y2O3Powder, magnetic agitation
And it heats and is dissolved in concentrated nitric acid at 60 DEG C of holding until water white transparency, obtains mixed rare-earth oxide solution.Then will
12.6208gAl(NO3)3·9H2(molar ratio of citric acid and rare earth ion is 3 for O and solid citric acid:1) it is dissolved in secondary steaming
It in distilled water, and is slowly added in above-mentioned manufactured mixed rare-earth oxide solution, stirring is until solution is in sticky at 50-60 DEG C
Foam colloidal solution.It is then placed into baking oven and maintains 36h at 80 DEG C, obtain gel.In Muffle furnace first by obtained gel
It is heated to 500 DEG C and maintains 50min, continue thereafter with and be heated to 1100 DEG C and continue 2.0h.Finally by the residue after high-temperature heating
Object takes out, obtains Er after cooling and grinding3+:Y3Al5O12Nano particle.
2) NiGa is prepared2O4:Metal Ga, which is dissolved in nitric acid, obtains Ga (NO3)3, the Ga (NO that will be evaporated3)3It is placed on Muffle furnace
In, in 550 DEG C of calcination 5.0h, is taken out after cooling, obtain Ga2O3;2mmol Ga2O3Solid is added to a concentration of 2mmol/L of 75ml
Nickel nitrate solution in, after stirring 30min, adjust pH to 12, then proceed to stirring 30min, obtained aaerosol solution is transferred to
In reaction kettle, 48.0h is maintained at 180 DEG C, obtained sediment is cleaned with deionized water, dry, obtains NiGa2O4。
3) BiVO is prepared4:5mmol Bi(NO3)3·5H2O is dissolved completely in 20ml nitric acid, and 10ml is then added dropwise
The NH of a concentration of 5mmol/L4VO3Sodium hydroxide solution, after being sufficiently stirred, adjust pH=8, be followed by stirring for 30min, then turn
It moves on in reaction kettle, 180 DEG C of maintenance 24.0h obtain solid, clean, dry, obtain BiVO4。
4) Er is prepared3+:Y3Al5O12/NiGa2O4:In mass ratio, Er3+:Y3Al5O12:NiGa2O4=3:7, by Er3+:
Y3Al5O12And NiGa2O4It is added to the water, ultrasonic disperse forms aaerosol solution, after boiling 15-20min at 100 DEG C, in 300
2.0-2.5h is calcined at DEG C, obtains Er3+:Y3Al5O12/NiGa2O4。
5) Er is prepared3+:Y3Al5O12/NiGa2O4-BiVO4:In molar ratio, NiGa2O4:BiVO4It is 1.0:0.0,1.0:0.5
With 1.0:1.0, BiVO is weighed respectively4.Respectively by Er3+:Y3Al5O12/NiGa2O4And BiVO4It is added to the water, ultrasonic disperse, shape
At aaerosol solution, after boiling 15min at 100 DEG C, 2.0h is calcined at 500 DEG C, respectively obtains different NiGa2O4And BiVO4It rubs
The Er of your ratio3+:Y3Al5O12/NiGa2O4-BiVO4。
6) Er is prepared3+:Y3Al5O12/MoS2-(NiGa2O4-BiVO4):By 2.0g Er3+:Y3Al5O12/NiGa2O4-BiVO4
With 0.006g MoS2In ethanol, ultrasonic disperse boils 15min at 78 DEG C for dissolving, filters, and washs, dry, obtains Er3+:
Y3Al5O12/MoS2-(NiGa2O4-BiVO4)。
7) Er is prepared3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS):The Er that will be obtained3+:Y3Al5O12/MoS2-
(NiGa2O4-BiVO4) it is dissolved in a concentration of 0.05molL of 10ml-1Na2In S aqueous solutions, under magnetic stirring, it is added dropwise
A concentration of 1.10mmolL of 10ml-1PdCl2Solution reacts 5.0min, centrifuges, and washs, dry, obtains Er3+:Y3Al5O12/
(MoS2/NiGa2O4)-(BiVO4/PdS)。
The photocatalytic system prepared as can be seen from Figure 1 contains Er3+:Y3Al5O12, NiGa2O4And BiVO4.And with
BiVO4The increase of content, BiVO4Main diffraction peak intensity increase, NiGa2O4Main diffraction peak remitted its fury.
2 compound photocatalytic system of embodiment is to dyestuff-orange G photocatalytic degradation
Method:The orange G solution of 25mL10mg/L is measured in 100mL conical flasks, 25mg embodiments 1 are added and prepare not
Same NiGa2O4And BiVO4The compound photocatalytic system Er of molar ratio3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/ PdS),
8.0h is irradiated under visible light (300W).Filtering, its ultraviolet spectra is measured in 200-800nm.The absorbance at 475nm is taken to calculate
The degradation rate of orange G, the results are shown in Table 1.
Degradation rate (%)=(C0–C)/C0× 100%
Wherein, C0:The concentration of stoste;C:The concentration of sample
1 different composite type photocatalytic system Photocatalytic Activity for Degradation orange G of table
As shown in table 1, as 3 kinds of catalyst of the extension of light application time gradually increase the degradation rate of orange G, and with
BiVO4Increase of the amount in catalyst system and catalyzing, increased trend is also presented in the degradation rate of orange G.In NiGa2O4With BiVO4Mole
Than being 1.0:1.0, when light application time is 8.0h, reach highest degradation rate 71.9%.
3 compound photocatalytic system of embodiment is using dyestuff-orange G as sacrifice agent Photocatalyzed Hydrogen Production
Method:The orange G solution of 500mL 50mg/L is measured in Photocatalyzed Hydrogen Production reactor, 200mg embodiments 1 are added
The different NiGa of preparation2O4And BiVO4The compound photocatalytic system Er of molar ratio3+:Y3Al5O12/(MoS2/NiGa2O4)-
(BiVO4/ PdS), irradiate 8.0h under visible light (300W).The amount of generated hydrogen in reaction is measured with gas-chromatography.
It the results are shown in Table 2.
2 different composite type photocatalysis body series visible-light photocatalysis of table produces hydrogen
As shown in table 2, with the hydrogen output of 3 kinds of catalyst of the extension of light application time and with BiVO4Amount be catalyzed
Increased trend is also presented in increase in system, hydrogen output.In NiGa2O4With BiVO4Molar ratio is 1.0:1.0, light application time is
When 8.0h, reach 120.6 μm of ol of highest hydrogen output.
Embodiment 4 changes the access times of compound photocatalytic system to the photodegradative influence of orange G
Photocatalytic system preparation method is with embodiment 2, and degradation process is the same as embodiment 2.NiGa2O4With BiVO4Molar ratio be
1.0:1.0, other change the access times of catalyst, the results are shown in Table 3.
Table 3 changes influence of the access times to degradable smooth orange G
From table 3 it is observed that the degradation rate of orange G keeps stabilization not significantly decrease.This is indicated continuous three times
Cyclic test in, Er in photocatalytic system3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS)(NiGa2O4With BiVO4
Molar ratio is 1.0:1.0) good light degradation activity is presented.Therefore when removing water pollutant, which has
Preferable stability.
Embodiment 5 changes influence of the access times of compound photocatalytic system to Photocatalyzed Hydrogen Production, and (orange G is as sacrificial
Domestic animal agent)
Photocatalytic system preparation method is with embodiment 3, and Photocatalyzed Hydrogen Production process is the same as embodiment 3.NiGa2O4With BiVO4Rub
You are than being 1.0:1.0, other change the access times of catalyst, the results are shown in Table 4.
Table 4 changes influence of the access times to visible light hydrogen manufacturing
As can be seen from Table 4, Photocatalyzed Hydrogen Production amount keeps stablizing, and does not significantly decrease.This is indicated continuous three
In secondary cyclic test, photocatalytic system Er3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS)(NiGa2O4With BiVO4It rubs
You are than being 1.0:1.0) good photocatalytic activity is presented.Therefore photocatalysis hydrolyze production hydrogen when, the catalyst system and catalyzing have compared with
Good stability.
Claims (9)
1. compound photocatalytic system, which is characterized in that the compound photocatalytic system is Er3+:Y3Al5O12/(MoS2/
NiGa2O4)-(BiVO4/PdS);Preparation method includes the following steps:
1) Er is prepared3+:Y3Al5O12/NiGa2O4:By Er3+:Y3Al5O12And NiGa2O4It is added to the water, ultrasonic disperse is formed outstanding
Supernatant liquid after boiling 15-20min at 95-105 DEG C, calcines 2.0-2.5h at 300 DEG C, obtains Er3+:Y3Al5O12/NiGa2O4;
2) Er is prepared3+:Y3Al5O12/NiGa2O4-BiVO4:By Er3+:Y3Al5O12/NiGa2O4And BiVO4It is added to the water, ultrasound
Dispersion forms suspension and calcines 2.0-2.5h after 95-105 DEG C is boiled 15-20min at 500 DEG C, obtain Er3+:Y3Al5O12/
NiGa2O4-BiVO4;
3) Er is prepared3+:Y3Al5O12/MoS2-(NiGa2O4-BiVO4):By Er3+:Y3Al5O12/NiGa2O4-BiVO4And MoS2Dissolving
In ethanol, ultrasonic disperse boils 15-20min at 75-80 DEG C, filters, and washs, dry, obtains Er3+:Y3Al5O12/MoS2-
(NiGa2O4-BiVO4);
4) Er is prepared3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS):By Er3+:Y3Al5O12/MoS2-(NiGa2O4-
BiVO4) it is dissolved in Na2In S aqueous solutions, under magnetic stirring, PdCl is added dropwise2Solution, reacts 5.0-6.0min, and centrifugation is washed
It washs, it is dry, obtain Er3+:Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS)。
2. compound photocatalytic system according to claim 1, which is characterized in that the NiGa2O4Preparation method is such as
Under:Metal Ga, which is dissolved in nitric acid, obtains Ga (NO3)3, the Ga (NO that will be evaporated3)3It is placed in Muffle furnace, in 550 DEG C of calcination 5.0-
5.5h takes out after cooling, obtains Ga2O3;Ga2O3Solid is added in nickel nitrate solution, after stirring 30min, adjusts pH to 12,
Stirring 30min is then proceeded to, obtained aaerosol solution is transferred in reaction kettle, and 48.0-49.0h is maintained at 180 DEG C, and what is obtained is heavy
Starch is cleaned with deionized water, dry, obtains NiGa2O4。
3. compound photocatalytic system according to claim 1, which is characterized in that in mass ratio, Er3+:Y3Al5O12:
NiGa2O4=3:7.
4. compound photocatalytic system according to claim 1, which is characterized in that the BiVO4Preparation method such as
Under:Bi(NO3)3·5H2O is dissolved completely in nitric acid, and NH is then added dropwise4VO3Sodium hydroxide solution, after being sufficiently stirred,
PH=8 is adjusted, 30min is followed by stirring for, is then transferred into reaction kettle, 180 DEG C of maintenance 24.0-25.0h obtain solid, clean,
It is dry, obtain BiVO4。
5. compound photocatalytic system according to claim 1, which is characterized in that in molar ratio, NiGa2O4:BiVO4=
1.0:0.5-1.0。
6. compound photocatalytic system described in claim 1 application in light degradation organic pollution under visible light.
7. application according to claim 6, which is characterized in that method is as follows:In the solution containing organic pollution, add
Enter compound photocatalytic system described in claim 1, irradiates 1.0-8.0h under visible light.
8. compound photocatalytic system described in claim 1 is under visible light illumination in the hydrogen manufacturing simultaneously of light degradation organic pollution
Application.
9. application according to claim 8, it is characterised in that method is as follows:Solution containing organic pollution is placed in light
In catalysis production hydrogen reactor, compound photocatalytic system described in claim 1 is added, irradiates 1.0-8.0h under visible light.
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