CN105597765B - A kind of In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material and preparation method thereof - Google Patents
A kind of In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material and preparation method thereof Download PDFInfo
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 53
- 239000002077 nanosphere Substances 0.000 claims abstract description 46
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 18
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910009112 xH2O Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 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 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- 238000002474 experimental method Methods 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 6
- 235000011083 sodium citrates Nutrition 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- -1 oxygen hydro carbons Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J23/76—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
- B01J23/825—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 gallium, indium or thallium
-
- B01J35/23—
-
- B01J35/50—
-
- B01J35/51—
-
- 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
Abstract
The invention discloses a kind of In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material and preparation method thereof, belongs to catalysis material and technical field of environment pollution control.The monodispersed In of hydro-thermal legal system is used first2O3Nanosphere；Then it takes ferric acetyl acetonade, zinc nitrate and terephthalic acid (TPA) to be added to absolute ethyl alcohol and N, in the mixed solution of N dimethylformamides after being sufficiently stirred, then In is added thereto2O3Nanosphere finally passes through solvent thermal reaction, centrifugation, drying and calcination, finally obtains nano heterojunction composite photocatalyst material.Obtained In2O3/ZnFe2O4Nano heterojunction not only extends In2O3Spectral response range, and improve the separative efficiency of photogenerated charge, there is good application value and foreground in photocatalysis degradation organic contaminant field.The raw materials used in the present invention is cheap and easy to get, and reaction condition is easily controllable, and operation is simple, low for equipment requirements and environmentally friendly.
Description
Technical field
The invention belongs to field of environment pollution control, are related to a kind of ferromagnetic semiconductor modification In2O3The preparation side of nanosphere
Method concretely relates to a kind of In2O3/ZnFe2O4The preparation and application of nano heterojunction composite photocatalyst material.
Background technology
Volatile organic compounds (abbreviation VOCs) is the general name of volatile organic compound.Currently, in environment
In the VOCs pollutants that detect more than more than 300 kinds.VOCs include mainly aliphatic hydrocarbon, fragrant hydrocarbon system, oxygen hydro carbons,
The a series of organic compounds such as halogenated hydrocarbon, nitrogen hydro carbons, sulphur hydro carbons and low-boiling polycyclic aromatic hydrocarbon.For in outdoor air
VOCs pollutants, main source are the burning of the fuel such as coal, oil and natural gas, the production of the industrial chemicals such as coating and pesticide
Processing and the discharge etc. of vehicle exhaust.And indoor VOCs pollutants mostly come from the solvent of organic coating and paint etc.,
Representative compound has benzene, toluene and dimethylbenzene.It, can be to the liver, brain and god of human body when VOCs reaches a certain concentration
Serious harm is generated through system, causes the extensive concern of researcher in recent years.
Photocatalysis technology based on semiconductor is high with degradation efficiency, reaction condition is mild, non-secondary pollution, can utilize
Solar energy and to the low advantage of the selectivity of pollutant has become a kind of removing division ring with applications well foreground in recent years
The method of organic pollution in border.Hou et al. (Hou Y.D., Wang X.C., Wu L., et
Al.Environ.Sci.Technol.2006,40,5799-5803) synthesize porosity β-Ga2O3, under ultraviolet light,
Commercially available TiO is better than to the catalytic activity of gas-phase benzene2And Pt/TiO2.There are two critical issues in photocatalysis technology, first, pair can
Light-exposed utilization rate is low, second is that the recombination probability of the photogenerated charge generated after light excitation is larger.In recent years, numerous research is concentrated
There is visible light-responded photochemical catalyst in exploitation.
In2O3It is a kind of important areas p metal oxide, energy gap 2.8eV has centainly visible light-responded.So
And the separative efficiency of the photogenerated charge generated after light excitation is relatively low, in order to solve this critical issue, numerous document reports
Choose other narrow-band semiconductors and In2O3It is coupled, builds In2O3Base heterojunction type composite photo-catalyst, has reached promotion light
Raw charge efficiently separates and further widens the purpose of spectral response range.Chen et al. (Chen Y.C., Pu Y.C., Hsu
Y.J., J.Phys.Chem.C, 2012,116,2967-2975) it is prepared for Pt-In2O3/TiO2Three-element composite photocatalyst is led to
It crosses transient state fluorescence spectroscopy technique and analyzes transmission path of the light induced electron between three kinds of components, to build efficient nano hetero-junctions
Photochemical catalyst provides good reference.ZnFe2O4It is a kind of multi-functional semi-conducting material, serves not only as important magnetism
Material, but also be a kind of good catalysis material.Its chemistry and photochemistry property is stablized, to sunlight spectral response range
Width has higher photocatalytic activity.Due to the relatively narrow (E of its energy gapg=1.9eV), it is widely used as other broad-band gaps
The visible light-sensitive agent of semiconductor.Wang et al. (Wang M.Y., Sun L., Cai J.H., et al.J.Mater.Chem.A,
2013,1,12082-12087) a kind of ZnFe is reported2O4Nano-particle modified TiO2Nano-tube array combination electrode, can
Under light-exposed irradiation, which shows higher catalytic activity to Acid Orange II.
Currently, using ZnFe2O4Modify In2O3It has no and has been reported that, especially with ZnFe2O4Nano-particle modified monodisperse
In2O3Nanometer spherical is at hetero-junctions composite photocatalyst material and for vapor phase toluene of degrading, and also there is not been reported both at home and abroad.This hair
It is bright to construct In for the first time2O3/ZnFe2O4Nano heterojunction composite photocatalyst material, has not only widened In2O3Spectral response model
It encloses, and improves the separative efficiency of photogenerated charge, there is higher Photocatalytic activity to vapor phase toluene.
Invention content
In is prepared the technical problem to be solved in the present invention is to provide a kind of2O3/ZnFe2O4Nano heterojunction composite photocatalyst
The method of material.Using hydro-thermal method combination solvent-thermal method, it is made by ZnFe2O4Nano-particle modified In2O3Nanosphere is heterogeneous
Composite photocatalyst material is tied, reaches and widens In2O3Spectral response range and improve photogenerated charge separative efficiency purpose.This hair
Bright raw materials used cheap and easy to get, reaction condition is easily controllable, and operation is simple, low for equipment requirements and environmentally friendly.Made from this method
Catalysis material shows good catalytic effect to photocatalytic degradation vapor phase toluene.
Technical scheme of the present invention：
A kind of In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material includes monodisperse In2O3Nanosphere and ZnFe2O4
Nano particle；Monodisperse In2O3A diameter of 150-300nm of nanosphere, by the primary nanoparticle group that grain size is 15-30nm
At；ZnFe2O4The grain size of nano particle is 10-30nm；ZnFe2O4Nano particle is supported on monodisperse In2O3The surface of nanosphere,
Form In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
A kind of In2O3/ZnFe2O4The preparation method of nano heterojunction composite photocatalyst material, steps are as follows：
(1) hydro-thermal method prepares monodisperse In2O3Nanosphere：By InCl3·xH2O and sodium citrate are with molar ratio for 1:3.5–
1:1.5 are dissolved into deionized water, and stirring is until obtain mixed solution A, wherein InCl3·xH2A concentration of the 0.02-of O solution
0.06mol/L；Urea is added with the isometric deionized water of mixed solution A, stirring obtains clear solution B until dissolving,
The wherein a concentration of 0.1-0.2mol/L of urea liquid；Clear solution B is slowly added drop-wise in mixed solution A, continues to stir
20-60min, are then transferred in ptfe autoclave, the 16-22h of hydro-thermal reaction under the conditions of 120-180 DEG C；It is cooled to room
Wen Hou repeatedly washs the purifying removal complete reactant of unreacted with ethyl alcohol and deionized water, centrifuges and dry, obtain white
Color sediment (In (OH)3), by white depositions In (OH)32h is calcined in 450-550 DEG C, monodisperse In is made2O3Nanosphere.
(2) solvent-thermal method prepares In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material：It will be obtained in step (1)
Monodisperse In2O3Nanosphere is added in the mixed solution of n,N-Dimethylformamide and absolute ethyl alcohol, then ultrasonic disperse
30-90min, ultrasonic power are 40-100W, obtain In2O3The mixing suspension of nanosphere；Wherein, n,N-Dimethylformamide with
The volume ratio of absolute ethyl alcohol is 3:1–5:3, monodisperse In is added in the mixed solution of unit volume2O3The amount of nanosphere is 0.5-
2.0g/L。
(3) zinc nitrate and ferric acetyl acetonade with molar ratio for 0.9:1 is added to the In of gained in step (2)2O3Mixing it is outstanding
In turbid, wherein a concentration of 6mmol/L of zinc nitrate solution stirs 30-90min, adds terephthalic acid (TPA) at room temperature, right
A concentration of 0.33-the 4.44g/L of phthalic acid, continues 30-60min of stirring, is then transferred in ptfe autoclave, carries out
Hydro-thermal reaction, reaction temperature are 100-160 DEG C, 5-9h of reaction time, after cooled to room temperature, use N, N- dimethyl successively
Formamide and ethyl alcohol wash the sediment of collection repeatedly, after being centrifuged, collect sediment, dry, and in 500-
600 DEG C of calcining 2h, heating rate is 1-2 DEG C/min, obtains In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
The beneficial effects of the invention are as follows：It is prepared for a kind of In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material,
ZnFe2O4Nano particle is dispersed in monodisperse In2O3The surface of nanosphere；Utilize ferromagnetic semiconductor ZnFe2O4Nano particle pair
Monodisperse In2O3Nanosphere is modified, and In has not only been widened2O3Spectral response range, and improve photogenerated charge point
From efficiency.In addition, the In of this method synthesis2O3/ZnFe2O4Nano heterojunction composite photocatalyst material is in catalytic degradation volatility
There is good application value and foreground in organic pollution field.
Description of the drawings
Fig. 1 (a) is the monodisperse In prepared2O3Nanosphere, ZnFe2O4Nano particle and In2O3/ZnFe2O4Nano heterojunction
The x-ray diffraction pattern of composite photocatalyst material.
Fig. 1 (b) is x-ray diffraction pattern of 2 times of angles of diffraction within the scope of 55-58 °.
Fig. 2 (a) is the monodisperse In prepared2O3The field emission scanning electron microscope figure of nanosphere.
Fig. 2 (b) is the In prepared2O3/ZnFe2O4The field emission scanning electron microscope figure of nano heterojunction composite photocatalyst material.
Fig. 3 (a) is the In prepared2O3/ZnFe2O4The transmission electron microscope picture of nano heterojunction composite photocatalyst material.
Fig. 3 (b) is the In prepared2O3/ZnFe2O4The high-resolution-ration transmission electric-lens figure of nano heterojunction composite photocatalyst material.
Fig. 4 (a) is the In prepared2O3/ZnFe2O4The full spectrograms of XPS of nano heterojunction composite photocatalyst material.
Fig. 4 (b) is the XPS spectrum figure of In 3d.
Fig. 4 (c) is the XPS spectrum figure of Fe 2p.
Fig. 4 (d) is the XPS spectrum figure of Zn 2p.
Fig. 4 (e) is the XPS spectrum figure of O 1s.
Fig. 5 (a) is the monodisperse In prepared2O3Nanosphere and In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
UV-visible absorption spectrum.
Fig. 5 (b) is (α h ν)2The relational graph of corresponding photon energy.
Fig. 6 (a) is the monodisperse In prepared2O3Nanosphere and In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
Fluorescence spectra.
Fig. 6 (b) is the monodisperse In prepared2O3Nanosphere and In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
Surface photovoltage spectrogram.
Fig. 7 is the monodisperse In prepared2O3Nanosphere and In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material is can
To the degradation efficiency of vapor phase toluene under light-exposed irradiation condition.
Specific implementation mode
Describe the specific implementation mode of the present invention in detail below in conjunction with attached drawing and technical solution.
Embodiment 1
Monodispersed In is prepared using hydro-thermal method2O3Nanosphere
By 0.2mmol InCl3·xH2O and 0.4mmol sodium citrates are dissolved into 10mL deionized waters, and stirring is until obtain
To clear solution A；1mmol urea is taken to be added in 10mL deionized waters, stirring is until dissolving obtains solution B；Solution B is slow
Ground is added drop-wise in solution A, is continued 20-60min of stirring, is then transferred in ptfe autoclave, hydro-thermal under the conditions of 150 DEG C
React 22h；After being cooled to room temperature, the purifying removal complete reactant of unreacted, centrifugation are repeatedly washed with ethyl alcohol and deionized water
It is separated and dried, obtains white depositions (In (OH)3), by In (OH)3White powder calcines 2h in 500 DEG C, is made monodispersed
In2O3Nanosphere.
Embodiment 2
According to the preparation method in embodiment 1, hydrothermal temperature is 120 DEG C, reacts 18h, and other parameters remain unchanged,
Monodispersed In is made2O3Nanosphere.
Embodiment 3
According to the preparation method in embodiment 1, the dosage of sodium citrate is increased into 0.7mmol, other raw material dosages and
Experimental procedure remains unchanged, and monodispersed In is made2O3Nanosphere.
Embodiment 4
According to the preparation method in embodiment 1, the dosage of sodium citrate is reduced to 0.3mmol, other raw material dosages and
Experimental procedure remains unchanged, and monodispersed In is made2O3Nanosphere.
Embodiment 5
According to the preparation method in embodiment 1, by 1.4mmol InCl3·xH2O and 2.8mmol sodium citrates are dissolved into
In 45mL deionized waters, stirring is until obtain clear solution A；7mmol urea is added in 45mL deionized waters, stirring is straight
Solution B is obtained to dissolving.Other raw material dosages and experimental procedure remain unchanged, and monodispersed In is made2O3Nanosphere.Gained
In2O3The X-ray diffracting spectrum of nanosphere is shown in that Fig. 1, field emission scanning electron microscope figure are shown in Fig. 2, UV-visible absorption spectrum and taboo
Bandwidth estimation result is shown in that Fig. 5, fluorescence spectrum and surface photovoltaic spectroscopy are shown in Fig. 6.
Embodiment 6
According to the preparation method in embodiment 5, InCl3·xH2O and sodium citrate addition are increased separately to 2.7mmol
And 5.4mmol, other raw material dosages and experimental procedure remain unchanged, and monodispersed In is made2O3Nanosphere.
Embodiment 7
According to the preparation method in embodiment 5, the dosage of urea is reduced to 4.5mmol, other raw material dosages and experiment walk
Suddenly it remains unchanged, monodispersed In is made2O3Nanosphere.
Embodiment 8
According to the preparation method in embodiment 5, the dosage of urea increases to 9.0mmol, other raw material dosages and experiment walk
Suddenly it remains unchanged, monodispersed In is made2O3Nanosphere.
Embodiment 9
In is prepared using solvent-thermal method2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
By 0.1g monodisperses In obtained in embodiment 52O3Nanosphere is added to N,N-dimethylformamide and anhydrous second
(volume ratio 2 in the mixed solution of alcohol:1, total volume 90mL), then ultrasonic disperse 40min, ultrasonic power 60W are obtained
In2O3Mixing suspension.0.21g ferric acetyl acetonades and 0.16g zinc nitrates are added to In2O3Mixing suspension in, room temperature
Lower stirring 60min, adds 0.18g terephthalic acid (TPA)s, continues to stir 40min, then be transferred in ptfe autoclave, into
Row hydro-thermal reaction, reaction temperature are 100 DEG C, reaction time 6h, after cooled to room temperature, after cooled to room temperature, successively
The sediment of collection is washed repeatedly with n,N-Dimethylformamide and ethyl alcohol, after being centrifuged, sediment is collected, dries
It is dry, and 2h is calcined in 550 DEG C, heating rate is 1 DEG C/min, obtains In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
Material.
Embodiment 10
According to the preparation method in embodiment 9, the dosage of terephthalic acid (TPA) is increased into 0.40g, other raw material dosages and
Experimental procedure remains unchanged, and In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.The X- of gained composite material is penetrated
Ray diffraction diagram spectrum is shown in that Fig. 1, field emission scanning electron microscope figure are shown in that Fig. 2, transmission electron microscope picture are shown in Fig. 3, fluorescence spectrum and surface photovoltaic spectroscopy
See Fig. 6.
Embodiment 11
According to the preparation method in embodiment 9, the dosage of terephthalic acid (TPA) is reduced to 0.03g, other raw material dosages and
Experimental procedure remains unchanged, and In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.The X-ray light of resulting materials
Electron spectrum is shown in that Fig. 4, UV-visible absorption spectrum and energy gap estimation result are shown in Fig. 5.
Embodiment 12
According to the preparation method in embodiment 9, monodisperse In2O3The addition of nanosphere powder sample reduce to
0.045g, other raw material dosages and experimental procedure remain unchanged, and In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
Material.
Embodiment 13
According to the preparation method in embodiment 9, monodisperse In2O3The addition of nanosphere powder sample increases to
0.180g, other raw material dosages and experimental procedure remain unchanged, and In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material
Material.
Embodiment 14
According to the preparation method in embodiment 9, the volume ratio of n,N-Dimethylformamide and absolute ethyl alcohol is increased to 5:
3, other parameters remain unchanged, and In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
Embodiment 15
According to the preparation method in embodiment 9, the volume ratio of n,N-Dimethylformamide and absolute ethyl alcohol is reduced to 3:
1, other parameters remain unchanged, and In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
Embodiment 16
According to the preparation method in embodiment 10, hydrothermal temperature is set as 120 DEG C, reaction time 8h, other parameters
It remains unchanged, In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
Embodiment 17
According to the preparation method in embodiment 10, hydrothermal temperature is set as 140 DEG C, reaction time 5h, other parameters
It remains unchanged, In is made2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
Embodiment 18
According to the preparation method of embodiment 10, setting calcination condition is 600 DEG C of calcining 2h, and heating rate is 2 DEG C/min,
Obtain In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material.
Embodiment 19
Nano heterojunction composite photocatalyst material under visible light illumination investigates the degrading activity of vapor phase toluene
Using vapor phase toluene as target contaminant, (λ under the conditions of radiation of visible light>400nm), to made in embodiment 10
Obtain In2O3/ZnFe2O4The light of nano heterojunction composite material urges activity to be investigated.Using in-situ ft-ir and gas-chromatography
Detect degradation rate of the hetero-junctions composite photocatalyst material to vapor phase toluene.
Embodiment 20
According to the investigation method in embodiment 19, to monodisperse In obtained in embodiment 52O3The visible light of nanosphere
Catalytic activity is investigated, and active testing result is shown in Fig. 7.As can be seen that after 8h radiation of visible light, In2O3/ZnFe2O4It receives
Rice hetero-junctions is apparently higher than In to the degradation rate of vapor phase toluene2O3Nanosphere.
Claims (9)
1. a kind of In2O3/ZnFe2O4The preparation method of nano heterojunction composite photocatalyst material, the In2O3/ZnFe2O4Nanometer is different
Matter knot composite photocatalyst material includes monodisperse In2O3Nanosphere and ZnFe2O4Nano particle；Monodisperse In2O3Nanosphere it is straight
Diameter is 150-300nm, is made of the primary nanoparticle that grain size is 15-30nm；ZnFe2O4The grain size of nano particle is 10-
30nm；ZnFe2O4Nano particle is supported on monodisperse In2O3The surface of nanosphere forms In2O3/ZnFe2O4Nano heterojunction is multiple
Closing light catalysis material；
The In2O3/ZnFe2O4The preparation method of nano heterojunction composite photocatalyst material, which is characterized in that steps are as follows：
(1) hydro-thermal method prepares monodisperse In2O3Nanosphere：By InCl3·xH2O and sodium citrate are with molar ratio for 1:3.5–1:1.5
It is dissolved into deionized water, stirring is until obtain mixed solution A, wherein InCl3·xH2A concentration of the 0.02-of O solution
0.06mol/L；Urea is added with the isometric deionized water of mixed solution A, stirring obtains clear solution B until dissolving,
The wherein a concentration of 0.1-0.2mol/L of urea liquid；Clear solution B is slowly added drop-wise in mixed solution A, continues to stir
20-60min, are then transferred in ptfe autoclave, the 16-22h of hydro-thermal reaction under the conditions of 120-180 DEG C；It is cooled to room
Wen Hou repeatedly washs the purifying removal complete reactant of unreacted with ethyl alcohol and deionized water, centrifuges and dry, obtain white
Color sediment In (OH)3, by white depositions In (OH)32h is calcined in 450-550 DEG C, monodisperse In is made2O3Nanosphere；
(2) solvent-thermal method prepares In2O3/ZnFe2O4Nano heterojunction composite photocatalyst material：By list obtained in step (1)
Disperse In2O3Nanosphere is added in the mixed solution of n,N-Dimethylformamide and absolute ethyl alcohol, then ultrasonic disperse 30-
90min, ultrasonic power are 40-100W, obtain In2O3The mixing suspension of nanosphere；Wherein, n,N-Dimethylformamide and nothing
The volume ratio of water-ethanol is 3:1–5:3, monodisperse In is added in the mixed solution of unit volume2O3The quality of nanosphere is 0.5-
2.0g/L；
(3) by zinc nitrate and ferric acetyl acetonade with molar ratio for 0.9:1 is added to the In of gained in step (2)2O3Nanosphere mixes
It closes in suspension, wherein a concentration of 6mmol/L of zinc nitrate solution stirs 30-90min, adds terephthaldehyde at room temperature
Acid obtains a concentration of 0.33-4.44g/L of terephthalic acid (TPA), continues 30-60min of stirring, be then transferred to polytetrafluoroethyl-ne alkene reaction
In kettle, hydro-thermal reaction is carried out, reaction temperature is 100-160 DEG C, 5-9h of reaction time, after cooled to room temperature, uses N successively,
Dinethylformamide and ethyl alcohol wash the sediment of collection repeatedly, after being centrifuged, collect sediment, dry,
And 2h is calcined in 500-600 DEG C, heating rate is 1-2 DEG C/min, obtains In2O3/ZnFe2O4Nano heterojunction composite photocatalyst
Material.
2. preparation method according to claim 1, which is characterized in that hydrothermal reaction condition is 150 DEG C in step (1), instead
It is 22h between seasonable；Calcination temperature is 500 DEG C, calcination time 2h.
3. preparation method according to claim 1 or 2, which is characterized in that in step (1), by InCl3·xH2O and lemon
Sour sodium is with molar ratio for 1:2 are dissolved into deionized water, and stirring is until obtain mixed solution A.
4. preparation method according to claim 1 or 2, which is characterized in that in step (2) in the mixed solution of unit volume
Monodisperse In is added2O3The quality of nanosphere is 0.5-2.0g/L；A concentration of 2g/L of terephthalic acid (TPA) in step (3).
5. preparation method according to claim 3, which is characterized in that add in the mixed solution of unit volume in step (2)
Enter monodisperse In2O3The quality of nanosphere is 0.5-2.0g/L；A concentration of 2g/L of terephthalic acid (TPA) in step (3).
6. according to the preparation method described in claim 1,2 or 5, which is characterized in that ultrasonic time 40min in step (2), ultrasound
Power is 60W.
7. preparation method according to claim 3, which is characterized in that ultrasonic time 40min in step (2), ultrasonic power
For 60W.
8. preparation method according to claim 4, which is characterized in that ultrasonic time 40min in step (2), ultrasonic power
For 60W.
9. according to the preparation method described in claim 1,2,5,7 or 8, which is characterized in that hydrothermal reaction condition is in step (3)
120 DEG C, reaction time 5h；Calcination condition is that 2h is kept at 550 DEG C, and heating rate is 1 DEG C/min.
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| CN111569856B (en) * | 2020-04-03 | 2023-06-09 | 清华-伯克利深圳学院筹备办公室 | In-Ga 2 O 3 Composite photocatalyst, preparation method and application thereof |
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