CN108620109A - The preparation method and applications of heterojunction photocatalyst are converted on a kind of cerium vanadate/modified attapulgite - Google Patents
The preparation method and applications of heterojunction photocatalyst are converted on a kind of cerium vanadate/modified attapulgite Download PDFInfo
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- CN108620109A CN108620109A CN201810598409.6A CN201810598409A CN108620109A CN 108620109 A CN108620109 A CN 108620109A CN 201810598409 A CN201810598409 A CN 201810598409A CN 108620109 A CN108620109 A CN 108620109A
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- modified attapulgite
- attapulgite
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- heterojunction photocatalyst
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- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 56
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 55
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 24
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 7
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000015096 spirit Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000005457 Black-body radiation Effects 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000009647 facial growth Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
-
- B01J35/39—
-
- B01J35/399—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention belongs to photocatalyst technology field, more particularly to the preparation method and applications of heterojunction photocatalyst are converted on a kind of cerium vanadate/modified attapulgite.Based on the attapulgite that the catalyst is handled with phosphoric acid modification, by cerous nitrate, ammonium metavanadate, deionized water is added in EDTA and modified attapulgite, it will transfer in microwave hydrothermal reaction kettle after heating stirring, be placed in microwave hydrothermal chemical reaction instrument and react, be then centrifuged for, washing obtains finished product after dry.The present invention has widened light abstraction width using phosphoric acid modification attapulgite, hetero-junctions is constructed with the semiconductor light-catalyst cerium vanadate with up-conversion luminescence property, it not only converts near infrared light and is converted to ultraviolet-visible, improve the absorption rate of light, and photo-generate electron-hole can be made to that can be efficiently separated, can effectively be degraded styrene, have larger application value in degrading volatile organic compounds field.
Description
Technical field
The invention belongs to photocatalyst technology field, it is related to phosphoric acid modification attapulgite and there is up-conversion luminescence property
Cerium vanadate build hetero-junctions as the nano material of active component, preparation method and its photocatalytic degradation styrene application.
Background technology
Volatile organic matter (volatile organic compounds, VOCs) is a kind of important air pollutants, is
The precursor of formation photochemical fog, gray haze.VOCs types are various, including alkanes, alkene, halogenated hydrocarbons, esters, aldehydes, ketone
With aromatic compound etc., it is mainly derived from the industries such as pharmacy, petrochemical industry, printing.VOCs has intense stimulus effect, right
Human body and animals and plants have strong carcinogenic, teratogenesis, can react generate photochemical fog and secondary dirt under light illumination
Object is contaminated, human health and ecological environment are seriously endangered.Therefore, have ten to the removal research of the VOCs existed in the environment
Divide significance.
Photocatalysis technology has the features such as low energy consumption, and reaction condition is mild, non-secondary pollution, in terms of atmospheric environment improvement
With prodigious development potentiality.Attapulgite (ATP) is also known as palygorskite, is a kind of rich magnesium silicate of natural 1-D fibre morphologies
Clay mineral, in needle-shaped or fibrous.Since it is with larger specific surface area, the faint alkali of negatively charged characteristic and surface
Property, has the function of inducing metal saline hydrolysis, thus attapulgite as active component carrier in mass transfer and reactivity
Collaborative party face has huge space.The iron oxide containing semiconductor property makes it have semiconductor property in concave convex rod body,
Ultraviolet region has good photoresponse, can be used as semiconductor light-catalyst.(Chen, et al, the Journal of of document 1
2,016 663 204-210 of Alloys and Compounds) report monomer CeVO4It can be harvested by black body radiation effect
Near-infrared photon, the property with up-conversion luminescence.Document 2 (Liu et al, RSC Adv., 2016,6,85779-85786)
Cerium vanadate is reported as a kind of to visible light-responded semiconductor light-catalyst, it is right by compound with redox graphene
Dyestuff has excellent photocatalytic degradation effect.
Due to the above characteristic, this research using phosphoric acid modification attapulgite as matrix, by microwave-hydrothermal method prepare vanadate/
Heterojunction composite photocatalyst is converted on modified attapulgite, not only takes full advantage of near infrared light, has widened the absorption profit of light
With rate, and photo-generate electron-hole can be made to that can be efficiently separated, volatile organic matter can be carried out effective
Catalytic degradation.
Invention content
In order to solve the low technical problem of photochemical catalyst light absorption utilization ratio, the present invention provides a kind of fast and convenient
Heterojunction material is converted on method-microwave-hydrothermal method synthesis cerium vanadate/modified attapulgite, passes through optimizing raw material proportioning, hydro-thermal
The technological parameters such as temperature and hydro-thermal time obtain the best composite material of optical absorption, make its photocatalysis catalytic degradation effect most
It is good.The composition general formula of composite material of the present invention is：CeVO4/H-ATP.The present invention solves above-mentioned skill using following technological means
Art problem：
The present invention relates to the preparation method that heterojunction photocatalysis material is converted on a kind of cerium vanadate/modified attapulgite, packets
Include following steps：
(1) Concave-convex clay rod purified is taken to be added in 30% phosphoric acid solution of mass fraction, ultrasonic disperse is placed on
It in 70 DEG C of water-bath, is filtered after carrying out 10h stir process, washs, be dried to obtain modified attapulgite；Wherein, phosphoric acid solution
Volume and the mass ratio of attapulgite be：100mL：1g.
(2) by EDTA solution and Ce (NO3)3Solution is uniformly mixed, and is added and Ce (NO3)3The NH of the amount of equal substances4VO3, use
It is 8-10 that 1M ammonia spirits, which adjust pH, and modified attapulgite is added after adjusting, is stirred well to uniformly, obtains mixed liquor；Wherein, institute
EDTA, Ce (NO stated3)3And NH4VO3Molar ratio be 1~1.5:1:1；The CeVO4With the quality of modified attapulgite
Than 0.05:1~0.5:1.
(3) (2) mixed liquor is transferred in 100mL reaction kettles, is placed in microwave hydrothermal chemical reaction instrument, in 160-180
1-2h is reacted at DEG C, is cooled down after reaction, product is collected by centrifugation, by product by 3 washings, to eliminate impurity, and 60
Dry 12 at~100 DEG C~for 24 hours, obtain CeVO4Heterojunction photocatalyst is converted on/H-ATP.
The present invention also provides a kind of above-mentioned CeVO4The application of heterojunction photocatalyst is converted on/H-ATP, that is, using should
Photochemical catalyst carries out photocatalytic oxidation degradation styrene.
Compared with prior art, the present invention has the beneficial effect that：
1, CeVO is prepared using microwave attenuation materials method in the present invention4Heterojunction composite is converted on/H-ATP, is closed
It is quick at method, simply, to attapulgite phosphoric acid modification, it is possible to increase its photoresponse range, by suitable in its surface recombination
Cerium vanadate constructs hetero-junctions with it, make near infrared light can more than be converted to ultraviolet light and visible light, improve the utilization of sunlight
Rate；
2, in the present invention, addition EDTA, can be with metal ion Ce as complexing agent3+Complex reaction occurs, forms complexing
The compound of ion, protects, in order to avoid cerous cerium hydroxide precipitation is formed when adjusting pH value, it is advantageous under the conditions of microwave hydrothermal
In Ce3+And VO4 3-CeVO is grown in modified ATP surface in situ4, with modified attapulgite stone construction heterojunction photocatalyst, have upper
Convert the CeVO of luminosity4Absorbing the visible light that near infrared light conversion is sent out can excite modified attapulgite to generate phase in time
The electrons and holes answered；
3, the present invention uses microwave hydrothermal reaction and reaction temperature is arranged as 160-180 DEG C, and reaction effect not only can be improved
Rate generates the higher cerium vanadate of crystallinity, and is precipitated almost without other impurities compound, can make the small rodlike knot of well-crystallized
The cerium vanadate of structure is uniformly combined with each other with modified attapulgite, constructs heterojunction structure；
4, there is abundant hydroxyl group in modified attapulgite of the present invention, make cerium vanadate in its table by the adjusting of pH value
Face growth in situ, obtains CeVO4Heterojunction composite is converted on/H-ATP, effectively inhibits the compound of electron hole, further
Improve the photocatalysis performance of semiconductor；
5, it is catalyst substrate materials present invention employs cheap and easy to get, environmentally safe attapulgite, has
The excellent properties such as surface area big, the microcellular structure of molecular sieve analog, good adsorptivity, are conducive to the volatilization to being adsorbed on its surface
Property organic compound carry out catalytic degradation, while reducing cost, while saving energy consumption.
Description of the drawings
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is CeVO4, the 50%CeVO for preparing of H-ATP and embodiment 14The XRD spectrograms of/H-ATP samples；
Fig. 2 is CeVO prepared by embodiment 14The 50%CeVO prepared with embodiment 14The PL collection of illustrative plates of/H-ATP samples；
Fig. 3 is 50%CeVO prepared by embodiment 14The TEM photos of/H-ATP sample 100nm scale ranges；
Fig. 4 is 50%CeVO prepared by embodiment 14The TEM photos of/H-ATP sample 10nm scale ranges；
Fig. 5 is H-ATP, CeVO prepared by embodiment 14, 50%CeVO4/ H-ATP and embodiment 2 prepare 30%
CeVO420%CeVO prepared by/ATP, embodiment 34/ ATP, 10% CeVO prepared by embodiment 44It is prepared by/ATP and embodiment 5
5%CeVO4/ ATP samples are to styrene-degrading curve.
Specific implementation mode
The present invention is described in further detail with reference to embodiment：
Embodiment 1
It weighs the attapulgite that 2g was purified first to be dissolved in the phosphoric acid solution of 100mL mass fractions 30%, ultrasonic disperse
It is placed in water-bath, after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake is through fully washing, the 16h at 60 DEG C
Drying, obtains modified attapulgite product；By 0.73g EDTA and 0.86g Ce (NO3)3It is added to the water after mixing fully molten
Solution is solved, 0.23g NH are added4VO3To above-mentioned solution, it is 10 to adjust pH with 1M ammonia spirits, then by modified attapulgite 1g
It is added in above-mentioned mixed liquor, is stirred well to uniformly mixed, obtain mixed liquor；Above-mentioned mixed liquor is finally transferred to 100mL reactions
In kettle, it is placed in microwave hydrothermal chemical reaction instrument, 1h is reacted at 160 DEG C, cooling after reaction, centrifugation, washing, 80 DEG C of bakings
Dry, finally grinding obtains the CeVO that load capacity is 50%4/ H-ATP composite materials.
To the CeVO prepared by the present embodiment4/ H-ATP composite materials carry out X-ray powder diffraction experiment, luminescence generated by light light
Spectrum-up-conversion luminescence test, and its pattern and structure are observed under transmission electron microscope, with modified attapulgite, the XRD of cerium vanadate
Collection of illustrative plates is as shown in Figure 1：The characteristic diffraction peak of modified attapulgite and cerium vanadate, in CeVO4Occur in/H-ATP composite materials, says
The bright composite material is successfully synthesized；CeVO4And CeVO4The PL collection of illustrative plates of/H-ATP is as shown in Figure 2：In 790nm excitation wavelengths
Under, occur the feature up-conversion luminescence peak of cerium vanadate in composite material at 268nm, 488nm, 535nm and 638nm, success
Make near infrared light can more than be converted to ultraviolet light and visible light；In addition, 50%CeVO4The TEM photos of/H-ATP samples are as schemed
3, shown in Fig. 4.It can be seen from the figure that cerium vanadate is the small club shaped structure of well-crystallized and more uniform with modified attapulgite
It is combined with each other, it is consistent with the result of XRD.
The present invention also provides the methods that above-mentioned composite material is used for photocatalytic degradation styrene：In photocatalysis apparatus
H-ATP, CeVO of 3mL are separately added into quartz ampoule4、CeVO4/H-ATP.10min ventilate after styrene initial concentration stabilization,
Light source is opened, a data are recorded every 30min with U.S.'s Baseline VOCs detectors.Gas used in experiment is
The styrene of 55ppm, remaining is all nitrogen；Light source is the xenon lamp of 500W, can be with simulated solar irradiation.Degradation rate (η) is according to following
Formula is calculated：
η (%)=(1-C/C0) × 100%
Wherein C0The initial concentration of styrene after stabilization, C are the concentration of the styrene detected in reaction process.
The degradation effect in 2h is tested as shown in figure 5, it can be seen from the figure that H-ATP is about to the degradation rate of styrene
35%, CeVO4Degradation rate up to 55%, and 50%CeVO4The degradation rate of/H-ATP is up to 70% or more.
Embodiment 2
It weighs the attapulgite that 2g was purified first to be dissolved in the phosphoric acid solution of 100mL mass fractions 30%, ultrasonic disperse
It is placed in water-bath, after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake is through fully washing, the 16h at 60 DEG C
Drying, obtains sour modified attapulgite product；By 0.44g EDTA and 0.52g Ce (NO3)3It is added to the water after mixing fully
Solution is dissolved to obtain, 0.14g NH are added4VO3To above-mentioned solution, it is 9 to adjust pH with 1M ammonia spirits, then by modified attapulgite 1g
It is added in above-mentioned mixed liquor, is stirred well to uniformly mixed, obtain mixed liquor；Finally mixed liquor is transferred in 100mL reaction kettles,
It is placed in microwave hydrothermal chemical reaction instrument, 1.5h is reacted at 170 DEG C, cooling after reaction, centrifugation, washing, 60 DEG C of drying,
Finally grinding obtains the CeVO that load capacity is 30%4It is right to measure in 2h its for/H-ATP composite materials, subsequent detection such as embodiment 1
The degradation rate of styrene is up to 80% or more.
Embodiment 3
It weighs the attapulgite that 2g was purified first to be dissolved in the phosphoric acid solution of 100mL mass fractions 30%, ultrasonic disperse
It is placed in water-bath, after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake is through fully washing, the 16h at 60 DEG C
Drying, obtains sour modified attapulgite product；By 0.29g EDTA and 0.35g Ce (NO3)3It is added to the water after mixing fully
Solution is dissolved to obtain, 0.09g NH are added4VO3To above-mentioned solution, it is 8 to adjust pH with 1M ammonia spirits, then by modified attapulgite 1g
It is added in above-mentioned mixed liquor, is stirred well to uniformly mixed, obtain mixed liquor；Finally mixed liquor is transferred in 100mL reaction kettles,
It is placed in microwave hydrothermal chemical reaction instrument, 1.5h is reacted at 170 DEG C, cooling after reaction, centrifugation, washing, 90 DEG C of drying,
Finally grinding obtains the CeVO that load capacity is 20%4It is right to measure in 2h its for/H-ATP composite materials, subsequent detection such as embodiment 1
The degradation rate of styrene is up to 90% or more.
Embodiment 4
It weighs the attapulgite that 2g was purified first to be dissolved in the phosphoric acid solution of 100mL mass fractions 30%, ultrasonic disperse
It is placed in water-bath, after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake is through fully washing, the 16h at 60 DEG C
Drying, obtains sour modified attapulgite product；By 0.15g EDTA and 0.17g Ce (NO3)3It is added to the water after mixing fully
Solution is dissolved to obtain, 0.04g NH are added4VO3To above-mentioned solution, it is 9 to adjust pH with 1M ammonia spirits, then by modified attapulgite 1g
It is added in above-mentioned mixed liquor, is stirred well to uniformly mixed, obtain mixed liquor；Finally mixed liquor is transferred in 100mL reaction kettles,
It is placed in microwave hydrothermal chemical reaction instrument, 2h is reacted at 180 DEG C, cooling after reaction, centrifugation, washing, 70 DEG C of drying, most
Grinding obtains the CeVO that load capacity is 10% afterwards4/ H-ATP composite materials, subsequent detection such as embodiment 1 measure in 2h it to benzene
The degradation rate of ethylene is up to 75% or more.
Embodiment 5
It weighs the attapulgite that 2g was purified first to be dissolved in the phosphoric acid solution of 100mL mass fractions 30%, ultrasonic disperse
It is placed in water-bath, after handling 10h at 70 DEG C, is filtered with circulation vacuum pump, filter cake is through fully washing, the 16h at 60 DEG C
Drying, obtains sour modified attapulgite product；By 0.07g EDTA and 0.08g Ce (NO3)3It is added to the water after mixing fully
Solution is dissolved to obtain, 0.02g NH are added4VO3To above-mentioned solution, it is 8 to adjust pH with 1M ammonia spirits, then by modified attapulgite 1g
It is added in above-mentioned mixed liquor, is stirred well to uniformly mixed, obtain mixed liquor；Finally mixed liquor is transferred in 100mL reaction kettles,
It is placed in microwave hydrothermal chemical reaction instrument, 2h is reacted at 160 DEG C, cooling after reaction, centrifugation, washing, 100 DEG C of drying,
Finally grinding obtains the CeVO that load capacity is 5%4/ H-ATP composite materials, subsequent detection such as embodiment 1 measure in 2h it to benzene
The degradation rate of ethylene is up to 65% or more.
Comparative example 1
Comparative example 1 compared with Example 1, using original attapulgite after purification, does not carry out phosphoric acid modification, other
Step is same as Example 1, is prepared into CeVO4/ ATP composite materials.
Detect CeVO prepared by comparative example 14Its only absorbable ultraviolet light is found after/ATP composite materials.
Comparative example 2
Comparative example 2 compared with Example 1, in preparation process, EDTA complexing agents, other steps and implementation is not added
Example 1 is identical, is prepared into CeVO4/ H-ATP composite materials.
CeVO prepared by comparative example 2 is found after detection4Contain a certain amount of CeO in/H-ATP2And V2O5Impurity is deposited
It is attached to attapulgite surface in, particulate oxidation object impurity, destroys heterojunction structure between cerium vanadate and modified attapulgite.
Claims (8)
1. converting the preparation method of heterojunction photocatalyst on a kind of cerium vanadate/modified attapulgite, which is characterized in that specific system
It is for step：
(1) Concave-convex clay rod purified is taken to be added in phosphoric acid solution, ultrasonic disperse is placed in water-bath, is stirred
It filters, washs after processing, it is dry, obtain modified attapulgite；
(2) by EDTA solution and Ce (NO3)3Solution is uniformly mixed, and is added and Ce (NO3)3The NH of the amount of equal substances4VO3, use ammonium hydroxide
PH is adjusted, modified attapulgite is added after adjusting, is stirred well to uniformly, obtains mixed liquor；
(3) step (2) mixed liquor is transferred in reaction kettle, is placed in microwave hydrothermal chemical reaction instrument and reacts, after reaction
It is cooling, product is collected by centrifugation, washs, is dried to obtain CeVO4Heterojunction photocatalyst is converted on/H-ATP.
2. the preparation method of heterojunction photocatalyst is converted on cerium vanadate/modified attapulgite as described in claim 1, it is special
Sign is：The mass fraction 30% of phosphoric acid solution described in step (1)；The volume of the phosphoric acid solution and attapulgite
Mass ratio is：100mL：1g.
3. the preparation method of heterojunction photocatalyst is converted on cerium vanadate/modified attapulgite as described in claim 1, it is special
Sign is：Water-bath pot temperature described in step (1) is 70 DEG C；The stir process time is 10h.
4. the preparation method of heterojunction photocatalyst is converted on cerium vanadate/modified attapulgite as described in claim 1, it is special
Sign is：EDTA, Ce (NO described in step (2)3)3And NH4VO3Molar ratio be 1~1.5:1:1；The CeVO4With change
The mass ratio 0.05 of property attapulgite:1~0.5:1.
5. the preparation method of heterojunction photocatalyst is converted on cerium vanadate/modified attapulgite as described in claim 1, it is special
Sign is：Ammonia concn described in step (2) is 1mol/L, and adjusting pH is 8-10.
6. the preparation method of heterojunction photocatalyst is converted on cerium vanadate/modified attapulgite as described in claim 1, it is special
Sign is：Reaction temperature described in step (3) is 160-180 DEG C, reaction time 1-2h.
7. the preparation method of heterojunction photocatalyst is converted on cerium vanadate/modified attapulgite as described in claim 1, it is special
Sign is：Washing described in step (3), dry concrete operations are：By product by 3 washings, to eliminate impurity, and 60
Dry 12 at~100 DEG C~for 24 hours.
8. photochemical catalyst prepared by the preparation method as described in claim 1-7 any one is in photocatalytic oxidation degradation styrene
In application.
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| CN115069249A (en) * | 2022-07-20 | 2022-09-20 | 常州大学 | Application of metal alloy/attapulgite composite material in reaction for converting cellulose into 5-hydroxymethylfurfural |
| CN115069249B (en) * | 2022-07-20 | 2023-08-22 | 常州大学 | Application of metal alloy/attapulgite composite material in cellulose conversion reaction of 5-hydroxymethylfurfural |
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