CN109433273A - A kind of novel photocatalyst NiGa2O4/AQ/MoO3And its preparation method and application - Google Patents
A kind of novel photocatalyst NiGa2O4/AQ/MoO3And its preparation method and application Download PDFInfo
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- CN109433273A CN109433273A CN201811545602.XA CN201811545602A CN109433273A CN 109433273 A CN109433273 A CN 109433273A CN 201811545602 A CN201811545602 A CN 201811545602A CN 109433273 A CN109433273 A CN 109433273A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 177
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 230000001699 photocatalysis Effects 0.000 claims abstract description 35
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 4
- 229920006362 Teflon® Polymers 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 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
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 95
- 150000004056 anthraquinones Chemical class 0.000 description 95
- 238000007146 photocatalysis Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 by volume Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
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- 230000001629 suppression Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8874—Gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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Abstract
The present invention relates to a kind of novel photochemical catalyst NiGa2O4/AQ/MoO3And its preparation method and application, belong to photocatalyst technology field.The present invention prepares NiGa using hydro-thermal method2O4/AQ/MoO3, by Ni nanoparticle Ga2O4/ AQ and nanometer MoO3It is added in dehydrated alcohol, after ultrasonic disperse, simultaneously constant temperature 30min is boiled into the heating of gained suspension, it is by the dry 8.0h of gained much filtrate after filtering, powder is finely ground, obtain NiGa2O4/AQ/MoO3.NiGa prepared by the present invention2O4/AQ/MoO3Composite material shows the photocatalytic activity of efficient stable in nitrite and sulphite conversion process, has broad application prospects in nitrite and sulphite wastewater treatment.
Description
Technical field
The invention belongs to photocatalyst technology fields, and in particular to a kind of novel photocatalyst NiGa2O4/AQ/MoO3And its
Preparation method and application.
Background technique
Nitrite and sulphite are widely used in each neck of food processing by people as food additives
Domain.But nitrite has certain toxic, and the discharge of wastewater containing excessive nitrite salt can make aquatile into water body
Organism metabolism functional disturbance, immunity degradation, so that it is even dead to bring it about lesion.Waste water row containing excessive sulphite
Being put into water body can make the nervous system of aquatic animal and respiratory system severely damaged.Therefore, the nitrous in industrial wastewater
The removal of hydrochlorate and sulphite is extremely important for the aquatic ecosystem for maintaining a balance and stability.With semiconductor material
Material is that the photocatalysis technology of core is that we provide a kind of new approaches of more satisfactory pollution control.Using photocatalysis technology
It handles nitrite and sulphite is a kind of green, clean, effective processing mode.The core that photocatalysis technology is faced
Heart problem is to find the photochemical catalyst of function admirable, so the screening of high efficiency photocatalyst and preparation are the cores of photocatalysis research
Project.
The key for improving Z-type photochemical catalyst photocatalysis efficiency is to enhance the separative efficiency of photo-generate electron-hole pairs.Traditional
Method is to increase conductive channel such as noble metal, graphene, carbon nanotubes etc., so that the photoproduction electricity on one of semiconductor conduction band
Son can be compound by conductive channel and the photohole in another semiconductor valence band, to improve light induced electron and hole pair
Separative efficiency.During electronics is transmitted using conductive channel, since electronics has a quality, there are resistance in transmittance process,
The speed of electron-transport can be slack-off, to influence photocatalysis efficiency.Therefore it provides a kind of not by electron mass and transmission range
The photochemical catalyst of limitation becomes urgent problem.
Summary of the invention
In view of the above-mentioned problems, the present invention design synthesize it is a kind of by AQ (anthraquinone) as conductive channel effectively accelerate electronics turn
Move the NEW TYPE OF COMPOSITE photochemical catalyst NiGa of rate2O4/AQ/MoO3.Compound involved in the present invention belongs to novel Z-type semiconductor light
Catalyst is applied to while converting nitrite and sulphite and generates in ammonium sulfate fertilizer, easy to operate, without dirt
Dye, catalyst stability is good, is easily isolated.
The technical solution adopted by the present invention is that: a kind of novel photocatalyst NiGa2O4/AQ/MoO3, preparation method includes such as
Lower step: by Ni nanoparticle Ga2O4/ AQ and nanometer MoO3It is added in dehydrated alcohol, after ultrasonic disperse, gained suspension is heated,
10~20min of constant temperature at 100 DEG C, after filtering that gained much filtrate is dry, grinding obtains NiGa2O4/AQ/MoO3。
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3, the NiGa2O4/ AQ preparation method
Are as follows: by Ni nanoparticle Ga2O4It is put into beaker and dehydrated alcohol is added, 20~40min of ultrasonic disperse, magnetic agitation adds after mixing
Nanometer AQ is added to boiling in heat after 10~30min of constant temperature at 100 DEG C, be centrifuged after being cleaned with dehydrated alcohol and distilled water, be dry,
Grinding, obtains Ni nanoparticle Ga2O4/AQ。
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3, the temperature of magnetic agitation is 40~60 DEG C.
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3Preparation method, the nanometer
NiGa2O4The preparation method comprises the following steps: by Ga2O3Solid is added in nickel nitrate solution, the mixed liquor sodium hydroxide solution tune of generation
PH to 12 is saved, 30~40min is stirred when adjusting, obtained aaerosol solution is transferred in reaction kettle and is reacted, cooling sample is extremely
Room temperature obtains drying at 80 DEG C, then at 500 DEG C, roasting 2~3h, grinding obtains after sediment cleans with deionized water
To Ni nanoparticle Ga2O4。
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3, aaerosol solution is in a kettle at 180 DEG C
React 48h.
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3, the nanometer MoO3Preparation method
Are as follows: by (NH4)6Mo7O24·4H2O is dissolved in 65%HNO3Solution in, be added deionized water, after being completely dissolved, by reaction solution
It is transferred in teflon lining stainless steel autoclave and is reacted, after cooling, obtained solid is washed with deionized for centrifugation,
It is dried at 80 DEG C, obtains a nanometer MoO3。
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3, reaction solution is stainless in Teflon lining
It is reacted 24 hours for 180 DEG C in steel autoclave.
Preferably, above-mentioned a kind of novel photocatalyst NiGa2O4/AQ/MoO3, by volume, (NH4)6Mo7O24·4H2O
With HNO3Mixed solution: deionized water=1:5.
A kind of above-mentioned novel photocatalyst NiGa2O4/AQ/MoO3In photocatalytic conversion nitrite and/or sulphite
In application.Method is as follows: by Ni nanoparticle Ga2O4/AQ/MoO3It is added to the waste water containing nitrite and/or sulphite
In, it is irradiated with 500W xenon lamp, light application time 4.0h.
The beneficial effects of the present invention are:
1. Ni nanoparticle Ga prepared by the present invention2O4/AQ/MoO3Photochemical catalyst property is stablized, and high temperature resistant is and simple
NiGa2O4And MoO3It compares, this catalyst converts nitrite and the efficiency of sulphite under the irradiation of sunlight to be had substantially
Degree improves.
2. the photochemical catalyst NiGa prepared in the present invention2O4/AQ/MoO3Not only have the advantages that traditional photochemical catalyst, but also
It is most it is worth noting that be directed to NiGa2O4And MoO3Bandwidth feature has conduction band and valence band location unique, this method solve
The efficiency of photocatalytic conversion nitrite and sulphite is greatly improved in the problem of light induced electron and hole-recombination.
3. electric charge transfer, it is not by the limit of electron mass and transmission range the invention proposes a kind of new electrically conducting manner
System, increases substantially electron transfer efficiency in this way, to enhance photocatalytic activity.
4. the bridge of anthraquinone (AQ) as charge transfer is selected in the present invention, it can be rapidly using the redox reaction of AQ
By electric charge transfer, electronics is made not need to be moved in conductive channel.It obtains electronics by AQ to be reduced, then again by hole
It is oxidized to AQ, forms the redox complex centre centered on AQ.Since the oxidation-reduction potential of AQ is located at MoO3Conduction band
Position and NiGa2O4Between valence band location, therefore AQ can be by MoO3The negative electrical charge of conduction band positions restores, then by NiGa2O4Valence band position
The Hole oxidation set realizes the transmitting of charge.
Detailed description of the invention
Fig. 1 is NiGa2O4, AQ, MoO3And NiGa2O4/AQ/MoO3Scanning electron microscope (SEM) figure.
Fig. 2 is MoO3,NiGa2O4,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Photoluminescence spectra (PL) figure.
Fig. 3 is NiGa2O4/AQ/MoO3Transmission electron microscope (TEM) figure.
Fig. 4 is NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Density of photocurrent (IT) figure.
Fig. 5 a-1 is using NiGa2O4/MoO3When catalyst, light application time is to nitrite and sulphite conversion ratio
It influences.
Fig. 5 a-2 is using NiGa2O4/AQ/MoO3When catalyst, light application time is to nitrite and sulphite conversion ratio
Influence.
Fig. 5 b-1 is using NiGa2O4/MoO3When catalyst, influence of the light application time to nitrate and sulfate generation rate.
Fig. 5 b-2 is using NiGa2O4/AQ/MoO3When catalyst, shadow of the light application time to nitrate and sulfate generation rate
It rings.
Fig. 6 is NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3To the light of nitrite and sulphite
The influence diagram of catalytic conversion.
Fig. 7 is NiGa2O4/AQ/MoO3Influence of the access times to the photocatalytic conversion rate of nitrite and sulphite
Figure.
Fig. 8 is novel photocatalyst NiGa2O4/AQ/MoO3Photocatalytic conversion nitrite and sulphite mechanism figure.
Specific embodiment
1 novel photocatalyst NiGa of embodiment2O4/AQ/MoO3
(1) preparation method is as follows
1. preparing Ni nanoparticle Ga2O4
By 0.37g nanometers of Ga2O3It is added to 50mL to contain in the solution of 0.45g nickel nitrate, the mixture 1mol/L of generation
Sodium hydroxide adjust pH to 12, while adjust while stir 30min, obtained aaerosol solution is transferred in reaction kettle at 180 DEG C instead
48h is answered, cooling sample obtains light blue sediment, cleaned several times with deionized water to room temperature.Obtained sediment is at 80 DEG C
Drying 8h obtains NiGa2O4Powder.Powder is finely ground, in 500 DEG C of Muffle furnace, 2h is roasted, grinding obtains nanometer after taking-up
NiGa2O4。
2. preparing nanometer MoO3
By 1g (NH4)6Mo7O24·4H2O is dissolved in 36mL 65%HNO3In, by volume, (NH4)6Mo7O24·4H2O with
HNO3Mixed liquor: deionized water=1:5, be added deionized water, after being completely dissolved, by the mixed solution be transferred to teflon lining
In reacted 24 hours in stainless steel autoclave (50mL capacity) and at 180 DEG C.After cooling, white product is obtained, is used after centrifugation
Deionized water is sufficiently washed, and obtained sediment is dried to 8h at 80 DEG C and obtains a nanometer MoO3。
3. preparing Ni nanoparticle Ga2O4/AQ
By 0.5g Ni nanoparticle Ga2O4It is put into beaker and 50mL dehydrated alcohol is added, after ultrasonic disperse 30min, at 40~60 DEG C
Lower magnetic agitation is uniformly mixed, and is heated to boiling, and at 100 DEG C after constant temperature 30min, 0.05g nanometers of AQ is added, then with anhydrous second
It after pure and mild distilled water cleaning for several times, is centrifuged, dry, grinding obtains Ni nanoparticle Ga2O4/AQ.4. preparing Ni nanoparticle Ga2O4/AQ/
MoO3
By 1.0g NiGa2O4/ AQ and 1.0g nanometers of MoO3It is added in 100mL dehydrated alcohol, ultrasonic disperse 1min will hang
Supernatant liquid heating is boiled, the constant temperature 30min at 100 DEG C, much filtrate is put into baking oven at 60 DEG C dry 8.0h after filtering, by powder
It is finely ground, obtain Ni nanoparticle Ga2O4/AQ/MoO3。
(2) it detects
1.NiGa2O4,AQ,MoO3And NiGa2O4/AQ/MoO3Scanning electron microscope (SEM) picture analyzing.
NiGa is observed by scanning electron microscope (SEM)2O4,AQ,MoO3And NiGa2O4/AQ/MoO3Form, as a result
As shown in Figure 1.In (the NiGa of Fig. 12O4) in, there are many size ranges in the blocky-shaped particle of 100-200nm, this belongs to
NiGa2O4Particle.(AQ) of Fig. 1 is the SEM picture of the pure AQ particle of purchase, and as can be seen from the figure pure AQ is irregularly to assemble
Body.From (the MoO of Fig. 13) in it can be seen that uniform and smooth nanometer rods, are MoO3Particle.(NiGa in Fig. 12O4/AQ/
MoO3) in, it can be seen that the little particle of AQ is uniformly dispersed in nanometer rods (MoO3) and blocky-shaped particle (NiGa2O4) between, this card
It is bright to be successfully prepared NiGa2O4/AQ/MoO3Sample.
2.NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Photoluminescence spectra (PL) picture analyzing.
By PL analysis it can be seen that the rate of departure of the electrons and holes of semiconductor light-catalyst.In general, low Poison is strong
The separating effect for spending the electron hole pair shown, this imply that excellent photocatalysis performance.High fluorescent show compared with
The separation effect of the electron hole pair of difference, this imply that photocatalysis performance is lower.It has been presented in Fig. 2 respectively in 260nm,
NiGa under the excitation of 325nm, 325nm and 325nm wavelength light2O4, MoO3, NiGa2O4/MoO3And NiGa2O4/AQ/MoO3PL light
Spectrum.It was found that pure NiGa2O4And MoO3It all shows relatively high PL intensity, reflects the recombination rate of their high electrons and holes.
Work as NiGa2O4And MoO3In conjunction with when, the Z-type NiGa of formation2O4/MoO3With pure NiGa2O4And MoO3Sample is compared and shows significant drop
Low PL intensity, shows Z-type NiGa2O4/MoO3Configuration be conducive to the separation of electrons and holes.In particular, when addition AQ and shape
At Z-type NiGa2O4/AQ/MoO3When, PL intensity is minimum, shows the optimal separation rate of electrons and holes.
3.NiGa2O4/AQ/MoO3Transmission electron microscope (TEM) picture analyzing.
Pass through tem observation NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Microstructure and form.?
(a) in Fig. 3, it can be seen that the fritter particle with opposite large scale (200-300nm) is NiGa2O4, uniform and smooth receives
Rice stick is MoO3.According to preparation method, it can be seen that NiGa2O4And MoO3Between there are much smaller particle, primarily determine these
Small particles are AQ.Their the Nomenclature Composition and Structure of Complexes can further be verified in Fig. 3.In (b) in Fig. 3, it can be found that existing brilliant
Interplanar distance is the crystal face of 0.280nm, determines that it is NiGa2O4D220Crystal face.In addition, crystal face has the interplanar distance of 0.209nm,
Belong to MoO3The d of particle040Crystal face.In NiGa2O4And MoO3Between, there is the crystal face with 0.253nm interplanar distance, according to cloth
Glug formula: 2dsin θ=n λ (d: interplanar distance, θ: diffraction half-angle, n: diffraction series and λ: the wavelength of target) calculates 2 θ and (spreads out
Penetrate half-angle), it is about 34.5 °, the d corresponding to AQ312Crystal face.These are the result shows that be prepared for NiGa2O4/AQ/MoO3Sample
Product.4.NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Density of photocurrent (IT) picture analyzing.
In order to further estimate influence of the rate of departure to photocatalytic activity of electrons and holes, the sample of preparation is measured
Density of photocurrent, as a result as shown in Figure 4.In general, high density of photocurrent shows the high separating efficiency of electrons and holes pair.
As can be seen that the sample NiGa of preparation2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3All have the day of fast and stable
Light irradiates transient photocurrents.Z-type NiGa2O4/MoO3Photo-current intensity be higher than NiGa2O4And MoO3, show Z-type photocatalytic system
Electrons and holes can be significantly improved to the rate of departure.In addition, Z-type NiGa2O4/AQ/MoO3It is shown in all samples highest
Photo-current intensity, it means that AQ with fast transfer electronics and can inhibit the weight in light induced electron and hole as electron transfer pathways
Group.Z-type NiGa2O4/AQ/MoO3Photochemical catalyst would indicate that highest photocatalytic activity.
2 novel photocatalyst NiGa of embodiment2O4/AQ/MoO3Answering in photocatalytic conversion nitrite and sulphite
With by 0.05g Ni nanoparticle Ga2O4/AQ/MoO3It is added to 50mL to contain in the waste water of nitrite and sulphite, wherein nitrous
The concentration of hydrochlorate is 10ppm, and the concentration of sulphite is 18.2ppm.It is irradiated with 500W xenon lamp, light application time 4.0h.Respectively
In the conversion ratio of illumination 0.00h, 1.00h, 2.00h, 3.00h, 4.00h measurement nitrite and sulphite.
Comparative example
By 0.05g NiGa2O4, 0.05g MoO3With 0.05g NiGa2O4/MoO3It is added separately to 50mL and contains nitrous acid
In the waste water of salt and sulphite, wherein the concentration of nitrite is 10ppm, and the concentration of sulphite is 18.2ppm.Use 500W
Xenon lamp irradiation, light application time 4.0h.Respectively illumination 0.00h, 1.00h, 2.00h, 3.00h, 4.00h measure nitrite and
The conversion ratio of sulphite.
(1) photocatalysis of simulated solar irradiation irradiation time and corresponding kinetics to nitrite and sulphite
The influence of conversion ratio
In Z-type NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Light application time is had studied in photocatalytic system respectively to nitrous
The influence of hydrochlorate and sulphite conversion.Reach absorption and desorption balance after half an hour in the dark, it can be found that NO2 -And SO3 2-
Conversion ratio slightly decline.This shows Z-type NiGa2O4/MoO3And NiGa2O4/AQ/MoO3A small amount of NO can only be absorbed2 -And SO3 2-。
In Fig. 5 a-1 and Fig. 5 a-2, with the increase of solar radiation time, NO2 -And SO3 2-Conversion ratio gradually rise.At first
In hour, with the increase of light application time, NO2 -And SO3 2-Photocatalytic conversion rate and NH4 +, NO3 -, N2And SO4 2-Generation
Rate increases sharply, then slowly enhancing.This may be the NO in solution due to the increase with the reaction time2 -And SO3 2-It is dense
Degree reduces, then photocatalytic conversion rate relative reduction.Wherein, NH4 +Generating rate be much higher than NO3 -And N2, this shows in weak acid
NO under the conditions of property2 -Converted product be mainly NH4 +.In addition, in Fig. 5 a-2, under irradiation in 4 hours, NO2 -And SO3 2-Conversion
Rate is respectively up to 89.81% and 94.47%, NH4 +, NO3 -, N2And SO4 2-Generating rate can respectively reach 73.38%,
15.19%, 1.24% and 93.25%.Obviously, in NiGa2O4/AQ/MoO3Under the action of, NO2 -And SO3 2-Conversion ratio and NH4 +, NO3 -, N2And SO4 2-Generating rate be all higher than NiGa2O4/MoO3.This shows the AQ as electron transfer pathways in Z-type
NiGa2O4/AQ/MoO3Middle conversion NO2 -And SO3 2-It plays an important role.
Kinetics can intuitively compare NO2 -And SO3 2-Conversion ratio, and calculate data-ln (Ct/C0)
It is provided in Fig. 5 b-1 and Fig. 5 b-2.Wherein, CtAnd C0Respectively represent instantaneous concentration and initial concentration.-ln(Ct/C0) calculated value
There are linear approximate relationships between sunlight irradiation time (t).Therefore, NO2 -And SO3 2-Conversion in both Z-type photocatalysis
System NiGa2O4/MoO3And NiGa2O4/AQ/MoO3In follow first order reaction rule.In NiGa2O4/MoO3In photocatalytic system
NO2 -And SO3 2-Kinetics equation be-ln (C respectivelyt/C0)=0.2475t+0.4539 (R2=0.9583) and-ln (Ct/C0)
=0.3347t+0.5232 (R2=0.9780).Rate constant is respectively 0.2475min-1 and 0.3347min-1.In Z-type
NiGa2O4/AQ/MoO3NO in photocatalytic system2 -And SO3 2-Kinetics equation be-ln (C respectivelyt/C0)=0.4266t+
0.5845(R2=0.9878) and-ln (Ct/C0)=0.5535t+0.6523 (R2=0.9938).Rate constant is
0.4266min-1 and 0.5535min-1.In contrast, in NiGa2O4/MoO3NO in photocatalytic system2 -And SO3 2-Rate is normal
Number is lower than Z-type NiGa2O4/AQ/MoO3In photocatalytic system.It was therefore concluded that with NiGa2O4/MoO3It compares, Z-type
NiGa2O4/AQ/MoO3Show relatively high NO2 -And SO3 2-Photocatalytic conversion rate.
(2) compare the photocatalytic activity for preparing sample and access times to turn the photocatalysis of nitrite and sulphite
The influence of rate
Photochemical catalyst that four kinds prepare is had studied to NO under simulated solar irradiation irradiation2 -And SO3 2-The influence of conversion, as a result
As shown in Figure 6.In the case where no any catalyst, NO2 -And SO3 2-Conversion ratio it is very low.The light prepared for four kinds is urged
Agent, NO2 -And SO3 2-With different degrees of conversion, show the use of photochemical catalyst to NO2 -And SO3 2-Conversion it is very heavy
It wants.Obviously, it can be seen that due to Z-type photocatalytic system NiGa2O4/MoO3Formation, e-And h+The available effective suppression of recombination
System, with NiGa2O4And MoO3It compares, in NO2 -And SO3 2-Photocatalytic activity in conversion further enhances.In addition, in Z-type
NiGa2O4/AQ/MoO3It is middle to find that highest conversion ratio and generating rate, the photocatalytic activity of enhancing are attributed to as electronics transfer
The AQ in channel with fast transfer electronics and can inhibit photoproduction e-And h+Recombination.
An important factor for stability of photochemical catalyst is evaluation practical application performance.Therefore, pass through photocatalytic conversion NO2 -With
SO3 2-, have studied and reuse the time to the Z-type NiGa of preparation2O4/AQ/MoO3The influence of the photocatalytic activity of photochemical catalyst.From
As can be seen that NO in Fig. 72 -And SO3 2-Photocatalytic conversion rate be declined slightly with the increase of access times, the 5th recycle
When still respectively reach 85.51% and 89.24%.This shows Z-type NiGa2O4/AQ/MoO3With high stability.In brief, Z-type
NiGa2O4/AQ/MoO3It can repeatedly use, and still maintain high photocatalysis performance.
(3) novel photocatalyst NiGa2O4/AQ/MoO3Photocatalytic conversion nitrite and sulphite mechanism
In order to effectively inhibit the electronics (e on conduction band (CB)-) and valence band (VB) on hole (h+) compound, NiGa2O4
And MoO3Combination forms Z-type photocatalytic system and is necessary.Due to NiGa2O4Valence band and MoO3Conduction band current potential is close, MoO3Conduction band
Electronics is easily transferred to NiGa2O4On hole.But in order to further increase their transfer rate.Anthraquinone is selected in this research
(AQ) as the bridge of charge transfer, electronics can be made not need rapidly by electric charge transfer using the redox reaction of AQ
It is moved in conductive channel.Electronics is obtained by AQ to be reduced, and is then and by Hole oxidation AQ, is formd centered on AQ
Redox complex centre.As shown in figure 8, the oxidation-reduction potential due to AQ is located at MoO3Conduction band positions and NiGa2O4Valence band
Between position, therefore AQ can be by MoO3The negative electrical charge of conduction band positions restores, then by NiGa2O4The Hole oxidation of valence band location is realized
The transmitting of charge, this conduction pattern are significantly faster than transfer of the electronics in conductive channel.This is for improving photocatalytic activity tool
It is significant, a kind of new method is provided for the research of subsequent photochemical catalyst.NiGa2O4Electronics in valence band has very strong
Reducing power, it can make the NO with certain oxidisability2 -Reduction, generates NH respectively4 +And N2.Specific product depends on
The acid condition of pH, pH less than 7 is easy to generate NH4 +Ion, alkaline condition of the pH value greater than 7 are easy to generate N2.Simultaneously in MoO3
Valence band on SO3 2-It is SO by the Hole oxidation in valence band4 2-, can be with the NH of generation4 +In conjunction with generation ammonium sulfate ((NH4)2SO4)。
Actually in NO2 -And SO3 2-In treatment process, ultimately generate containing ammonium sulfate ((NH4)2SO4) aqueous solution, by proper treatment
It can be used as chemical fertilizer directly to use.
Claims (10)
1. a kind of novel photocatalyst NiGa2O4/AQ/MoO3, which is characterized in that preparation method includes the following steps: nanometer
NiGa2O4/ AQ and nanometer MoO3It is added in dehydrated alcohol, after ultrasonic disperse, gained suspension is heated, the constant temperature at 100 DEG C
10~30min, after filtering that gained much filtrate is dry, grinding obtains NiGa2O4/AQ/MoO3。
2. a kind of novel photocatalyst NiGa as described in claim 12O4/AQ/MoO3, which is characterized in that the nanometer
NiGa2O4/ AQ's the preparation method comprises the following steps: by Ni nanoparticle Ga2O4It is put into beaker and dehydrated alcohol is added, 20~40min of ultrasonic disperse,
Magnetic agitation is heated to boiling after mixing, nanometer AQ is added at 100 DEG C after 10~30min of constant temperature, with dehydrated alcohol and steaming
Centrifugation, dry, grinding, obtain Ni nanoparticle Ga after distilled water cleaning2O4/AQ。
3. a kind of novel photocatalyst NiGa as claimed in claim 22O4/AQ/MoO3, it is characterised in that: the temperature of magnetic agitation
Degree is 40~60 DEG C.
4. a kind of novel photocatalyst NiGa as claimed in claim 22O4/AQ/MoO3, which is characterized in that the nanometer
NiGa2O4The preparation method comprises the following steps: by Ga2O3Solid is added in nickel nitrate solution, the mixed liquor sodium hydroxide solution tune of generation
PH to 12 is saved, 30~40min is stirred when adjusting, obtained aaerosol solution is transferred in reaction kettle and is reacted, cooling sample is extremely
Room temperature obtains drying at 80 DEG C, then at 500 DEG C, roasting 2~3h, grinding obtains after sediment cleans with deionized water
To Ni nanoparticle Ga2O4。
5. a kind of novel photocatalyst NiGa as claimed in claim 42O4/AQ/MoO3, it is characterised in that: aaerosol solution is anti-
It answers in kettle and reacts 48h at 180 DEG C.
6. a kind of novel photocatalyst NiGa as described in claim 12O4/AQ/MoO3, it is characterised in that: the nanometer
MoO3The preparation method comprises the following steps: by (NH4)6Mo7O24·4H2O is dissolved in 65%HNO3Solution in, be added deionized water, be completely dissolved
Afterwards, reaction solution is transferred in teflon lining stainless steel autoclave and is reacted, after cooling, obtained solid is used in centrifugation
Deionized water washing, dries at 80 DEG C, obtains a nanometer MoO3。
7. a kind of novel photocatalyst NiGa as claimed in claim 62O4/AQ/MoO3, it is characterised in that: reaction solution is in spy
It is reacted 24 hours for 180 DEG C in fluorine dragon lining stainless steel autoclave.
8. a kind of novel photocatalyst NiGa as claimed in claim 62O4/AQ/MoO3, it is characterised in that: by volume,
(NH4)6Mo7O24·4H2O and HNO3Mixed solution: deionized water=1:5.
9. a kind of novel photocatalyst NiGa described in claim 12O4/AQ/MoO3In photocatalytic conversion nitrite and/or
Application in sulphite.
10. application as claimed in claim 9, which is characterized in that method is as follows: by Ni nanoparticle Ga2O4/AQ/MoO3It is added to and contains
In the waste water for having nitrite and/or sulphite, irradiated with 500W xenon lamp, light application time 4.0h.
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