CN110292918A - A kind of preparation and application of oxygen defect titanium dioxide/Palygorskite Composite Materials - Google Patents
A kind of preparation and application of oxygen defect titanium dioxide/Palygorskite Composite Materials Download PDFInfo
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- CN110292918A CN110292918A CN201910617239.6A CN201910617239A CN110292918A CN 110292918 A CN110292918 A CN 110292918A CN 201910617239 A CN201910617239 A CN 201910617239A CN 110292918 A CN110292918 A CN 110292918A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000007547 defect Effects 0.000 title claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 239000004098 Tetracycline Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 229960002180 tetracycline Drugs 0.000 claims 1
- 229930101283 tetracycline Natural products 0.000 claims 1
- 235000019364 tetracycline Nutrition 0.000 claims 1
- 150000003522 tetracyclines Chemical class 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 42
- 101150072055 PAL1 gene Proteins 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 235000010215 titanium dioxide Nutrition 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000001055 reflectance spectroscopy Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000000763 evoking effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003012 network analysis Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of oxygen defect titanium dioxide/palygorskite (O2‑TiO2/ pal) composite material preparation method, butyl titanate is added in distilled water first, be stirred at room temperature hydrolysis generate TiO2Presoma；Again by TiO2It is added in 4 ~ 5 DEG C of distilled water after presoma washing, and oxidants hydrogen peroxide is added, be stirred to react 0.5 ~ 1 hour, form oxygen defect titanium dioxide O2‑TiO2；Then palygorskite is added, is heated to 45 ~ 50 DEG C, stirs 2.5 ~ 3 hours, washing is dry to get defect titanium dioxide/Palygorskite Composite Materials.The present invention uses and is oxidized to form oxygen defect titanium dioxide O by oxidizing process2‑TiO2Then it is combined with palygorskite, effectively its optical absorption edge has been widened to visible light, and improve the absorption intensity of composite material and the utilization rate to natural light, and using the strong adsorption property of palygorskite, composite material is allow to improve its removal effect to pollutant by absorption and photocatalysis coupled effect.
Description
Technical field
The present invention relates to a kind of preparation of titanium dioxide/Palygorskite Composite Materials more particularly to a kind of oxygen defect titanium dioxides
Titanium/Palygorskite Composite Materials (O2-TiO2/ pal) preparation method, be mainly used for photocatalytic degradation quadracycline, belong to multiple
Condensation material technical field and photocatalysis technology field.
Background technique
The fast development of science and technology keeps people's life more and more finer, but also brings while offering convenience to the mankind
A series of trouble.The fast development of medical career, but various difficult and complicated cases are also broken out in succession has relevant report to pretend illness the change of poison
Exactly because the abuse of different drug.The convenience of life but makes environment more and more worse, we cannot be using environmental disruption as cost
To develop science and technology, palpus promotion and ecological harmonious development.However, with the rapid development of society, problem of environmental pollution is already very
Prominent, other than traditional pollutant, the large-scale use of antibiotic newly to have added again in environment a kind of abuse of antibiotics and leads
The pollution of cause, makes environment can't bear the heavy load.Have numerous scientists at present using solar energy abundant in nature, by means of half
Conductor material passes through photocatalysis technology degradable organic pollutant.In the past several years, TiO2, the semiconductor light-catalysts such as ZnO
Constantly successfully it developed.However, solar energy turns during limiting its light-catalyzed reaction due to the defect of material itself
Change efficiency and practical application value, for example expensive material preparation cost, limited light absorpting ability, higher light induced electron are empty
Duration harm etc. is caused to compound probability, severe toxicity or to environment in cave.Therefore, have cheap, low toxicity, efficient photochemical catalyst at
For currently most urgent demand.
TiO was utilized for the first time from Japanese Scientists Honda and Fujishima in 19722Optoelectronic pole successful decomposition water generates H2With
O2Since, photocatalysis technology greatly develops, and has started depollution of environment new approaches.In recent years, Photocatalitic Technique of Semiconductor by
Function is applied to multiple fields.TiO2Photochemical catalyst is cheap, green non-poisonous, is praised highly by people always, however, TiO2Band
The disadvantages of gap is wider is it is also obvious that it can only absorb and account for the low solar energy utilization ratio of the ultraviolet light of sunlight 4 percent or so and allow
Related scholar very headache.Therefore, modified TiO how is explored2Photochemical catalyst widens its light abstraction width and has evoked researcher
Persons' greatly enthusiasm.
Summary of the invention
It is an object of the invention to provide a kind of oxygen defect titanium dioxide/palygorskite (O2-TiO2/ pal) composite material preparation side
Method；
It is another object of the present invention to the O to above-mentioned preparation2-TiO2/ pal composite material photocatalytic degradation degradation quadracycline
Performance studied.
One, O2-TiO2The preparation of/pal composite material
Butyl titanate is added in distilled water first, hydrolysis is stirred at room temperature and generates TiO2Presoma；Again by TiO2Presoma
It is added to after washing in 4 ~ 5 DEG C of distilled water, and oxidants hydrogen peroxide is added, be stirred to react 0.5 ~ 1 hour, form oxygen defect two
Titanium oxide O2-TiO2；Then palygorskite is added, is heated to 45 ~ 50 DEG C, stirs 2.5 ~ 3 hours, washing is dry to get defect two
Titanium oxide/Palygorskite Composite Materials is labeled as O2-TiO2/pal。
The additional amount of hydrogen peroxide is 7.5 ~ 8 times of butyl titanate quality；The additional amount of palygorskite is butyl titanate
0.23 ~ 0.7 times of quality；In composite material obtained, O2-TiO2It is 1:1 ~ 1:3 with pal mass ratio.
In order to further increase the catalytic activity of composite material, by pal/O2-TiO2It is placed in Muffle furnace, at 280 ~ 300 DEG C
1.8 ~ 2h is calcined, the O of calcining is obtained2-TiO2/ pal composite material.
Analyze calcined O2-TiO2/ pal composite material, ABSORPTION EDGE probably in 420nm or so, compare commercial titanium dioxide
(P25) the obvious red shift of ABSORPTION EDGE, the O not calcined2-TiO2/ Pal composite sample compares the sample optical absorption edge calcined blue shift,
But absorption intensity is enhanced after 520nm.Show that calcined sample compares the sample before calcining to target dirt by testing
The degradation property of dye object is also declined.
Two, pal/O2-TiO2The structural characterization of composite material
1, X-ray diffractogram (XRD)
Fig. 1 is O2-TiO2Calcining front and back, pal and O2-TiO2The XRD spectrum of/Pal series composite materials (1:1,1:2,1:3).
It can be seen from the figure that O2-TiO2For without determining crystal form material, it is calcined after O2-TiO2(2) and TiO2Standard card comparison is basic
Unanimously.Meet in the main diffraction peak and document of palygorskite sample.Wherein, 2 θ are 26.8oWith 34.9oPeak intensity it is larger.Pal/
O2-TiO2Mainly occurring 2 θ in three kinds of composite samples is 26.8oDiffraction maximum, and as palygorskite content increase has enhancing
Trend.Due to the O in compound2-TiO2For without crystal form is determined, there is no diffraction maximums, so there was only the diffraction of palygorskite in compound
Peak.
2, scanning electron microscope (SEM) photograph (SEM)
Fig. 2 is the scanning electron microscope diagram of synthesized sample, and wherein Fig. 2 a is TiO2, Fig. 2 b, 2c O2-TiO2,Fig. 2 d, 2e,
2f is respectively O2-TiO2/ Pal 1:1, O2-TiO2/ Pal 1:2, O2-TiO2/Pal 1:3.It can be seen that TiO from Fig. 2 a2Pure sample
Product are mainly made of little particle, can be seen that O from Fig. 2 b, 2c2-TiO2It is and big and random block structure forms, this can
It can be the non-uniform reason of tetrabutyl titanate hydrolysis.It can be seen that the addition with palygorskite, material block from Fig. 2 d, 2e, 2f
Obviously become smaller, and is obviously dispersed with fine acicular texture thing (palygorskite)；And with the increase of palygorskite amount, block dispersibility is bright
Aobvious to improve, fine acicular texture thing also obviously becomes close, illustrates pal and O2-TiO2It is combined with each other well, and the needle-shaped knot of palygorskite
Structure will not change.
3, UV Diffuse Reflectance Spectroscopy figure
Light absorpting ability is the important indicator for evaluating semiconductor material photocatalysis performance, we use UV-Vis DRS light
Spectrum has carried out network analysis to a series of light absorpting ability of composite samples.Fig. 3 is pure sample TiO2With different palygorskite ratios
O2-TiO2The UV-Vis DRS of/Pal composite photo-catalyst is composed.As seen from the figure, pure O2-TiO2Compared to non-peroxidating
TiO2Red shift is to 420 nm, pure O2-TiO2Calcined sample O2-TiO2(2) ABSORPTION EDGE compares non-peroxidating in 420 nm or so
TiO2ABSORPTION EDGE also obvious red shift, O2-TiO2ABSORPTION EDGE is about in 540 nm or so before section is burnt.And with the addition of palygorskite,
All O2-TiO2The optical absorption edge of/Pal composite sample blue shift, but absorption intensity is enhanced after 520 nm, this explanation
The compound can excite generation photo-generated carrier using more light, and then the photocatalysis performance of sample is promoted to be promoted.
4, FTIR spectrum figure
Fig. 4 is TiO2, O2-TiO2, O2-TiO2(2) and O2-TiO2/ Pal 1:2 composite material FTIR spectrum figure.It is all
Sample all has 3400 cm-1Broadband and 1630 cm-1The sharp band at place, this is attributable to the stretching of surface OH groups generation
And bending vibration.O2-TiO2Spectrogram variation is unobvious before and after section is burnt, in 496 cm-1The bands of a spectrum at place are attributed to the vibration of Ti-O key
It is dynamic, in 891 cm-1Characteristic peak be attributed to O-O stretching vibration.And O2-TiO2Both there is O in/Pal 1:2 composite material2-TiO2
Characteristic peak, also there are 1082 cm-1, 478 cm-1Equal palygorskites characteristic peak.This has further confirmed that O2-TiO2With palygorskite
Exist in composite sample jointly.
5, photoluminescence spectra figure (PL)
Photoluminescence luminescent spectrum refers to that the electronics being excited releases entrained energy during returning to ground state from excitation state
It is formed, fluorescence signal intensity is stronger, it is meant that the number of electrons returned to ground state from excitation state is more, photo-generated carrier separation effect
Rate is low.Fig. 5 is O2-TiO2Pure sample and O2-TiO2The photoluminescence hair of/Pal 1:2 compound in the case where excitation wavelength is 469 nm
Spectrum.With O2-TiO2Pure sample compares, O2-TiO2The transmitting band edge Xiang Genggao wave number direction of/Pal 1:2 migrates, this may
It is due to caused by reuniting part pal in composite sample；Meanwhile the fluorescence intensity of composite sample is substantially reduced, this may be by
In pal and g-C3N4Between formed high forces it is related.Therefore, O2-TiO2Efficient charge migration means in/Pal composite sample
More photo-generated carriers are able to participate during light-catalyzed reaction.
6, photocatalysis performance test chart
In order to investigate the O of preparation2-TiO2/ Pal composite sample is to quadracycline photocatalytic activity, with xenon lamp simulated solar irradiation,
Carry out the Photocatalytic Degradation Property of study sample.All samples do degradation experiment under 800 watts of xenon lamps, adsorb 30 minutes early period, with
Reach adsorption/desorption balance, twice, experiment is 100 minutes total for sampling.Fig. 6 pal/O2-TiO2Serial photocatalysis performance test chart.
It will be appreciated from fig. 6 that pure O2-TiO2It is demonstrated by certain degradation property, absorption 10% or so.And palygorskite only shows 41% suction
Attached performance.O2-TiO2/ Pal series composite materials show good absorption and photocatalysis performance, especially O2-TiO2/
Pal 1:2 sample adsorption rate reaches 40%, and total removal rate reaches 78%, and excellent pollutant removal effect is shown compared to pure sample
Fruit has especially cashed out photocatalysis and adsorbing coupled effect, so that pollutant removal is more obvious.
In order to further investigate O2-TiO2The calcined catalytic performance of/Pal, section is burnt the O of front and back by we2-TiO2/Pal
1:2 and pure O2-TiO2Make photocatalysis contaminant degradation to compare.As shown in fig. 7, calcined O2-TiO2/ Pal 1:2 degradation effect
Fruit significantly decreases compared to before, or even not as good as pure O2-TiO2, this is also that I selects to determine crystal form using nothing in an experiment
The reason of compound palygorskite.
7, the cyclical stability test chart of photochemical catalyst
In order to further probe into synthesized O2-TiO2The stability of/Pal composite material and reusable property, we are to it
Stable circulation performance test has been done, i.e., has been separated and recovered the sample after primary degradation experiment, has been continued after washing drying
Test next time, such circulation experiment three times, as a result as shown in figure 8, in experiment three times, the absorption of sample and degradation effect base
This does not become, and general effect slightly decreases negligible, this illustrates that the composite material of synthesis has repeatable benefit well
With property, this is also one of the important performance that cost is reduced in sewage treatment.
In conclusion the present invention, which first passes through Hydrolysis At Room Temperature, is made TiO2Precursor, then pass through oxidizing process for TiO2Oxygen is oxidized to lack
Fall into titanium dioxide O2-TiO2, then combined with palygorskite, effectively widened its optical absorption edge to visible light, and mention accordingly
Its high absorption intensity, improves the utilization rate to natural light significantly.Also, it after palygorskite is added, is inhaled by force using palygorskite
The special property of attached property allows composite material by adsorbing the removal effect for improving it to pollutant with photocatalysis coupled effect
Fruit.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of synthesized sample.
Fig. 2 is the scanning figure of synthesized sample.
Fig. 3 is the UV Diffuse Reflectance Spectroscopy figure of synthesized sample.
Fig. 4 is the FTIR spectrum figure of synthesized sample.
Fig. 5 is the photoluminescence spectra figure of synthesized sample.
Fig. 6 is the photocatalysis performance test chart of synthesized sample.
Fig. 7 is the photocatalysis performance test chart of synthesized sample.
Fig. 8 is the cyclical stability test chart of the photochemical catalyst of synthesized sample.
Specific embodiment
Below by specific embodiment to pal/O of the present invention2-TiO2The preparation of composite material and photocatalytic degradation hydrochloric acid four
The performance of ring element is described further.
Embodiment 1
(1) by the raw ore palygorskite grind into powder of 10 g, mechanical stirring one in 1 L large beaker preparation removing palygorskite: is added
Hour, stop stirring, stand 24 hours, remove upper layer supernatant liquid, extract upper layer precipitating, 4 mol/ are added in 100 DEG C of drying overnight
It stirs 24 hours, washes five times in L hydrochloric acid, drying grinding is spare.
(2) O2-TiO2The preparation of/Pal 1:1: 5 ml butyl titanates are added in 50 ml distilled water, are stirred 30 minutes,
White precipitate is generated, precipitating washing 3 times is added in 50 ml, 5 DEG C of distilled water, 40 ml hydrogen peroxide are added, stirring one is small
When, the palygorskite that 1.17mg is added is heated to 50 DEG C, stirs 3 hours, washes three times, and 100 DEG C of drying both obtain O2-TiO2/Pal
1:1 sample；
(3) to the degradation property of quadracycline: doing degradation experiment under 800 watts of xenon lamps, the sample is to the total of quadracycline
Removal rate reaches 73%.
Embodiment 2
(1) preparation removing palygorskite: with embodiment 1；
(2) O2-TiO2The preparation of/Pal 1:2: 5 ml butyl titanates are added in 50 ml distilled water, are stirred 30 minutes, raw
Precipitating washing 3 times is added in 50 ml, 5 DEG C of distilled water at white precipitate, 40 ml hydrogen peroxide are added, stir one hour,
The palygorskite that 2.35 mg are added is heated to 50 DEG C, stirs 3 hours, washes three times, and 100 DEG C of drying both obtain O2-TiO2/Pal 1:2
Sample；
(3) to the degradation property of quadracycline: doing degradation experiment under 800 watts of xenon lamps, the sample is to the total of quadracycline
Removal rate reaches 78%.
Embodiment 3
(1) preparation removing palygorskite: with embodiment 1；
(2) O2-TiO2The preparation of/Pal 1:3: 5 ml butyl titanates are added in 50 ml distilled water, are stirred 30 minutes, raw
Precipitating washing 3 times is added in 50 ml, 5 DEG C of distilled water at white precipitate, 40 ml hydrogen peroxide are added, stir one hour,
The palygorskite that 3.51 mg are added is heated to 50 DEG C, stirs 3 hours, washes three times, and 100 DEG C of drying both obtain O2-TiO2/Pal 1:3
Sample；
(3) to the degradation property of quadracycline: doing degradation experiment under 800 watts of xenon lamps, the sample is to the total of quadracycline
Removal rate reaches 71%.
Embodiment 4
(1) preparation removing palygorskite: with embodiment 1；
(2) O2-TiO2The preparation of/Pal 1:2: with embodiment 2；
(3) it is sintered O2-TiO2The preparation of/Pal 1:2: O prepared by 1 g embodiment 2 is taken2-TiO2/ Pal 1:2 sample is put into horse
Not in furnace, 300 degrees Celsius are calcined two hours, generate calcined O2-TiO2/ Pal 1:2 sample.
(4) to the degradation property of quadracycline: doing degradation experiment under 800 watts of xenon lamps, the sample is to quadracycline
Total removal rate reach 46%.
Claims (7)
1. a kind of preparation method of oxygen defect titanium dioxide/Palygorskite Composite Materials, is added to distillation for butyl titanate first
In water, hydrolysis is stirred at room temperature and generates TiO2Presoma；Again by TiO2It is added in 4 ~ 5 DEG C of distilled water, and is added after presoma washing
Oxidants hydrogen peroxide is stirred to react 0.5 ~ 1 hour, forms oxygen defect titanium dioxide O2-TiO2；Then palygorskite is added, heats
It to 45 ~ 50 DEG C, stirs 2.5 ~ 3 hours, washing, it is dry to get defect titanium dioxide/Palygorskite Composite Materials, it is labeled as O2-
TiO2/pal。
2. a kind of preparation method of oxygen defect titanium dioxide/Palygorskite Composite Materials as described in claim 1, it is characterised in that:
Defect titanium dioxide/Palygorskite Composite Materials are placed in Muffle furnace, in 280 ~ 300 DEG C of 1.8 ~ 2h of calcining, obtain the O of calcining2-
TiO2/ pal composite material.
3. a kind of preparation method of oxygen defect titanium dioxide/Palygorskite Composite Materials as claimed in claim 1 or 2, feature exist
In: the additional amount of hydrogen peroxide is 7.5 ~ 8 times of butyl titanate quality.
4. a kind of preparation method of oxygen defect titanium dioxide/Palygorskite Composite Materials as claimed in claim 1 or 2, feature exist
In: the additional amount of palygorskite is 0.23 ~ 0.70 times of butyl titanate quality；In composite material obtained, O2-TiO2With pal matter
Amount is than being 1:1 ~ 1:3.
5. a kind of preparation method of oxygen defect titanium dioxide/Palygorskite Composite Materials as claimed in claim 1 or 2, feature exist
In: palygorskite is the palygorskite for being stripped purifying.
6. a kind of preparation method of oxygen defect titanium dioxide/Palygorskite Composite Materials as claimed in claim 1 or 2, feature exist
In: the drying is dried at 80 ~ 100 DEG C.
7. oxygen defect titanium dioxide/Palygorskite Composite Materials of method preparation as described in claim 1 are in photocatalytic degradation hydrochloric acid
Application in tetracycline.
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| CN112246271A (en) * | 2020-10-23 | 2021-01-22 | 南京信息工程大学 | Attapulgite-based photocatalytic sewage treatment agent and preparation method thereof |
| CN113941321A (en) * | 2021-10-27 | 2022-01-18 | 吕梁学院 | Preparation method of photocatalyst oxidized titanium dioxide |
| CN115025802A (en) * | 2022-06-24 | 2022-09-09 | 昆明理工大学 | Preparation method of multi-effect coupling organic sulfur wide-temperature hydrolysis catalyst |
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