CN109277094A - A kind of method of modifying of visible light responsive photocatalyst and its application in artificial seawater system - Google Patents
A kind of method of modifying of visible light responsive photocatalyst and its application in artificial seawater system Download PDFInfo
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- CN109277094A CN109277094A CN201811215560.3A CN201811215560A CN109277094A CN 109277094 A CN109277094 A CN 109277094A CN 201811215560 A CN201811215560 A CN 201811215560A CN 109277094 A CN109277094 A CN 109277094A
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- 239000013535 sea water Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 186
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 178
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 235000019441 ethanol Nutrition 0.000 claims abstract description 81
- 230000009467 reduction Effects 0.000 claims abstract description 67
- 230000004048 modification Effects 0.000 claims abstract description 56
- 238000012986 modification Methods 0.000 claims abstract description 56
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
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- 238000002156 mixing Methods 0.000 claims abstract description 4
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- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- 229960004756 ethanol Drugs 0.000 claims description 78
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 57
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- 239000002245 particle Substances 0.000 claims description 11
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
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- 238000004566 IR spectroscopy Methods 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- 238000004876 x-ray fluorescence Methods 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 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 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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 method of modifying of visible light responsive photocatalyst and its application in artificial seawater system, modification includes: (1) by the TiO with duplex grain structure2Dehydrated alcohol mixing after nano-photocatalyst and ultrasonic treatment, ultrasonic disperse is until form stable suspension system；(2) suspension system is fully transferred in autoclave, carries out ethyl alcohol thermal reduction reaction after sealing at a constant temperature；(3) it will be separated after gained heat treatment reaction solution cooling, washed and drying and processing.Photochemical catalyst after modification is added in artificial seawater system, is irradiated 3~5 hours under visible light source after adsorption equilibrium (or so half an hour) at dark.The present invention heat-treats method using ethyl alcohol, can only complete to be modified the surface reduction of duplex grain structure TiO2 photochemical catalyst under mild conditions, obtains the photochemical catalyst of visible light activity, and method is easy and safe and reliable.
Description
Technical field
The present invention relates to seawer system organic pollutant processing technology fields, and in particular to a kind of visible light of duplex grain structure
The ethyl alcohol thermal reduction method of modifying of responsive photocatalyst and its application in artificial seawater system.
Background technique
Waste oil caused by the waste water of land discharge and shipping etc. brings a large amount of containing there are many organic of aromatic hydrocarbon to ocean
Pollution.Even if ocean area accounts for 70% or more of the earth gross area, but the marine pollution accumulated over a long period is the master that the whole world faces
Want problem of environmental pollution.More seriously, under the long-term illumination the effects of, the aromatic hydrocarbon in Marine System further acts on life
At highly toxic polycyclic aromatic hydrocarbon (PAHs) pollutant.In recent years, multiple maritime waters even deep-sea fish in vivo all
Have found the presence of PAHs.Due to vast area, a distinguishing feature of marine pollution is exactly that organic pollutant concentration is low, and difficult
Degradation.In addition, there is a large amount of different types of salt ions for seawer system itself (salinity is 3%~5%).Low concentration difficulty drop
The organic matter and salt ion of solution interfere the two features, so that solving ocean organic contamination using traditional water treatment technology such as absorption
Problem is faced with insoluble difficult point.Due to mineralising thoroughly, efficiently and non-selectivity degradation of organic substances advantage, TiO2For generation
The multiphase photocatalysis technology water resource advanced treating field of table has embodied very high wide big potentiality, also in removal seawater
Light concentration organic pollutant provides a very feasible research direction.
But TiO2Multiphase photocatalysis technology success is applied to the improvement of arene organic pollutant in seawater, also needs
Face two challenges.Firstly, generally believing that partial size is less than the TiO of 100nm2Particle just has photocatalytic activity, especially works as grain
Its photocatalytic activity is best when sub- size is less than 10nm.In addition to this, crystalline state TiO2(including rutile-type and Detitanium-ore-type)
It is also the key factor that particle has high efficiency photocatalysis activity.But the so small nanoparticle of partial size has great surface energy,
Easily reunite in process of production, and the small particle TiO with crystalline state2The production of particle is even more extremely difficult.Decades
Come, industrializes most successful, most widely used TiO2Nano-photocatalyst is exactly that Ying Chuan group (being originally goldschmidt chemical corporation) passes through gas
The commercial P25 photochemical catalyst that phase method is prepared.TiO in P252The average particle partial size of particle is in 20nm or so, but its mixed crystal
The carrier capture center that structure (~80% anatase crystal and~20% rutile crystal type) is formed, allows to highly effective
Light induced electron and hole are separated, to have efficient photocatalytic activity.In addition, the such small partial size of the catalyst but has very
Good stability makes it obtain most applying extensively in industries such as chemical industry, environmental protection and medicine.
Expanding second difficult point that multiphase photocatalysis technology is administered applied to organic contamination in seawater is, available in ocean
Light source be visible light source.Pure TiO2Nanoparticle is including P25, due to its wider energy band band gap (anatase TiO2About
3.2eV, rutile TiO2About 3.0eV), its light degradation pollutant could be only excited under the irradiation of ultraviolet light.And ocean etc. is certainly
The ultraviolet light that can be utilized in right environment only account for the 5% of solar source less than.How design stability, efficient visible light-responded urge
Agent is the key that by organic pollutant removal in multiphase photocatalysis technology practical application Yu Haiyang.
Existing hydrogen reduction is the roasting heat treatment catalyst fines under high pressure hydrogen atmosphere, or catalyst is normal
Temperature is lower to carry out prolonged high-pressure hydrogenation processing, and the hydrogen partial pressure that this method needs will be in 20bar or more, not only preparation cost
Height, and there is very big security risks for high pressure hydrogen.Stability in view of P25 photochemical catalyst and under ultraviolet-visible it is excellent
How P25 light absorption is expanded to visible region using the means such as modified, enables it with visible light activity by different photocatalysis effect
It is the hot spot direction of visible light response catalyst design and building.
Summary of the invention
The present invention provides a kind of commercial TiO of the modification with duplex grain structure2The preparation method of photochemical catalyst, using ethyl alcohol heat
Restoring method can only be completed to be modified the surface reduction of duplex grain structure TiO2 photochemical catalyst under mild conditions, be obtained
To the photochemical catalyst of visible light activity, method is easy and safe and reliable, the TiO obtained using the present invention2Still keep small particle and
Good dispersibility, and maintain the duplex grain structure of anatase and rutile-type.
A kind of visible light-responded TiO of duplex grain structure2The method of modifying of photochemical catalyst, which is characterized in that including walking as follows
It is rapid:
(1) by the TiO with duplex grain structure2Dehydrated alcohol mixing after nano-photocatalyst and ultrasonic treatment, ultrasound point
It dissipates until forming stable suspension system；
(2) suspension system is fully transferred in autoclave, carries out ethyl alcohol heat also at a constant temperature after sealing
Original reaction；
(3) it will be separated after gained heat treatment reaction solution cooling, washed and drying and processing.
Dehydrated alcohol is for being first ultrasonically treated before reacting, in ultrasonic time 10 minutes, with remove wherein micro air or
The gases such as carbon dioxide, ethyl alcohol have the function of hot solvent and reducing agent simultaneously；When forming the ultrasound of stable suspension system
Between be 5 hours or more；Autoclave uses the steel autoclave with village in polytetrafluoroethylene (PTFE)；Baking in step (3)
Dry temperature is 60 DEG C~90 DEG C.
Under the conditions of the solvent heat of high pressure, ethyl alcohol is as reducing agent and TiO2Surface carries out reduction, will by reduction
TiO2Surface crystallization state disordering promotes a small amount of surface crystallization TiO2It is transformed into amorphous TiO2, to form heterojunction structure simultaneously
By part Ti4+It is reduced to Ti3+Reach auto-dope purpose, expands TiO2It is visible light-responded, and it is made to have efficient visible light
Activity.In addition, the Ti in catalyst can be made by changing reaction condition during the preparation process3+Content and surface heterogeneous medium junction
Structure changes.The visible light-responded TiO that the present invention obtains2Catalyst can remove seawater in efficient degradation under excited by visible light
In phenol pollutant, can Ti in Effective Regulation photochemical catalyst by adjusting preparation reaction and heat treatment parameter3+Content and can
Light-exposed response etc. and its visible light photocatalytic degradation performance.
Invention reaction principle:
Under the environment of high-pressure ethanol heat, ethyl alcohol both can be used as solvent or using the TiO as reducing agent and crystalline state2Grain
Reduction occurs for sublist face, and the reduction process under high temperature and pressure is by surface crystallization type TiO2Disordering forms amorphous TiO2, from
And in TiO2Particle surface constitutes heterojunction structure and introduces Ti in the catalyst3+Auto-dope is carried out, TiO is expanded2Photochemical catalyst
It is visible light-responded, finally obtain Ti3+The visible light-responded TiO of auto-dope2Photochemical catalyst.
This patent carries out reduction treatment to P25 in mild and easy-operating alcohol solvent thermal reduction process, obtains Ti3+From mixing
Miscellaneous has visible light-responded photochemical catalyst, and using the phenol in its seawater of degrading under visible light, further expands more
The practical application of phase photocatalysis technology.
The present invention has the TiO for stablizing duplex grain structure using ethyl alcohol thermal reduction one-step method processing2Photochemical catalyst (including commercialization
Photochemical catalyst), avoid carrier surface load TiO2The relatively complicated preparation step of particle, a step are stablized with regard to simplicity
Visible light-responded photochemical catalyst.Without additional third doping component, it is reduced directly modified expansion TiO2Photochemical catalyst can
Light-exposed response, method are easy and environmentally protective.
Preferably, TiO2The mass volume ratio of nano-photocatalyst and dehydrated alcohol is 0.50g~5.0g:120mL；Into one
Step is preferably 0.5g~1.5g:120mL, most preferably 0.8~1.2g:120mL.
Preferably, the TiO2Nano-photocatalyst is powdered, and the duplex grain structure of rutile and anatase is presented, than
Surface area is 50m2/ g~100m2/ g, particle diameter are 10~50nm.Exist with two kinds of crystalline states of rutile and anatase.It can be with
Stable suspension system is formed in ethanol, and the stable time, can be by commercially available at 5 hours or more.
Further preferably, the commercial TiO of Ying Chuan company of Germany production is selected2Nano-photocatalyst (P25) has mixed crystal knot
Structure (two kinds of crystal form ratios of rutile and anatase are 8:2), TiO2Partial size is 20nm, specific surface area 50m2/g。
Preferably, reaction temperature is 150 DEG C~180 DEG C in step (2)；Reaction time is 5~24 hours.Further preferably
5~12 hours, most preferably 12 hours.
The present invention also provides a kind of methods of organic pollutant in processing artificial seawater, include the following steps:
Photochemical catalyst after such as described ethyl alcohol thermal reduction method of modifying modification is added in artificial seawater system, it is black
It is irradiated 3~5 hours under visible light source after dark place adsorption equilibrium (or so half an hour).
Preferably, the dosage of the photochemical catalyst after modification is 0.5mg/L~5.0mg/mL.Further preferably
1.0~3.0mg/mL, most preferably 1.25mg/mL.
Preferably, organic pollutant is phenol in the artificial seawater system；Phenol content is 5.0mg/L~10mg/L.
Artificial seawater composition: magnesium chloride mass fraction is 1~2%, and the mass fraction of calcium chloride is 0.1~0.2%, sulfuric acid
The mass fraction of sodium is 0.2~0.5%, and the mass fraction of sodium chloride is 2~3%.
Preferably, it is seen that radiant is the LED white light of 30W, light intensity 10mW/cm2: utilize optical filter wavelength-filtered
Non-visible light light less than 400nm and greater than 760nm.
It can be in organic contamination in efficient degradation artificial seawater system under excited by visible light object of the present invention is to develop one kind
The visible light-responded TiO with duplex grain structure of object2Catalyst.It is of the present invention that visible light-responded refer to can to general interior
Visible light environment in light-exposed or natural environment, such as light intensity are weaker than for 10mW/cm2White composite visible light.
Compared with prior art, the visible light-responded TiO of duplex grain structure provided by the invention2Photochemical catalyst and ethyl alcohol heat
Modified with reduction preparation method has the advantage that
1) commercial photochemical catalyst technology of preparing is mature, performance is stable, is applied in multiple fields, such as urges
Agent P25 is having been obtained for extremely successful application using high-level oxidation technology advanced treatment of waste water field, but it makes
Excitation light source is ultraviolet light.It is directly modified using commercial catalyst as raw material, can utmostly keep being catalyzed
The stability of agent in application process accelerates application of the multiphase photocatalysis technology in seawater contamination improvement.
2) at present it is believed that the TiO of rutile-type and Detitanium-ore-type2The trap center that will form photo-generated carrier, because
And the TiO of duplex grain structure2Light urges agent to have high photocatalytic activity.Under the premise of not destroying duplex grain structure, expansion has
Duplex grain structure TiO2It is visible light-responded, can utmostly maintain the high activity of catalyst, can be high under excited by visible light
Imitate degradable organic pollutant.
3) it is to have reduction while ethyl alcohol is as solvent under high-temperature and high-pressure conditions that ethyl alcohol, which heat-treats modified the preparation method,
The effect of agent is completed at the same time by reduction reaction to crystalline state TiO2The disordering on surface acts on and by Ti4+It is reduced to Ti3+Mistake
Journey, in TiO2Surface forms heterojunction structure and introduces Ti3+Auto-dope is carried out, so that it is visible light-responded to expand catalyst.Liquid phase
In reduction process it is relatively mild, can utmostly reduce conventional H2High-temperature roasting reduction reaction under atmosphere causes TiO2
Surface even inner transition disordering, forms a large amount of amorphous TiO as photo-generated carrier trap center2, to reduce it
Photocatalytic activity.
4) preparation method is simple, easily operated, and energy consumption cost is low.Can easily it be passed through using preparation method of the invention
Change thermal reduction reaction condition to regulate and control the structure of composite photo-catalyst, visible light-responded and light degradation property.
5) preparation method is simple, easily operated, at low cost.Change can easily be passed through using preparation method of the invention
The structure for regulating and controlling composite photo-catalyst, visible light-responded and light degradation property are reacted with heat treatment condition.
Detailed description of the invention
Fig. 1 is the infrared spectroscopy (FT-IR) for the modification P25 photochemical catalyst that reference examples and the embodiment of the present invention are prepared
Figure.
Fig. 2 is that the transmission electron microscope (TEM) for the modification P25 photochemical catalyst that reference examples and the embodiment of the present invention are prepared shines
Piece.
Fig. 3 is the high-resolution-ration transmission electric-lens for the modification P25 photochemical catalyst that reference examples and the embodiment of the present invention are prepared
(HRTEM) photo.
Fig. 4 is X-ray diffraction (XRD) figure for the modification P25 photochemical catalyst that reference examples and the embodiment of the present invention are prepared.
The x-ray fluorescence point that Fig. 5 is the Ti2P for the modification P25 photochemical catalyst that reference examples and the embodiment of the present invention are prepared
Analyse (XPS) figure.
Fig. 6 is the UV-vis DRS figure for the modification P25 photochemical catalyst that reference examples and the embodiment of the present invention are prepared
Spectrum.
Phenol in the degradation artificial seawater for the modification P25 photochemical catalyst that Fig. 7 reference examples and the embodiment of the present invention are prepared
Degradation curve.
Fig. 8 is the modification P25 photochemical catalyst that is prepared of reference examples and the embodiment of the present invention to phenol in artificial seawater
Removal rate (2 hours reaction time).
Fig. 9 is that the modification P25 photochemical catalyst that the embodiment of the present invention is prepared repeats phenol reality in light degradation artificial seawater
It tests.
Specific embodiment
Being described below is the present invention more preferred embodiment, is not used to limitation of the invention.It is selected in embodiment
TiO2Photochemical catalyst is the commercial P25 photochemical catalyst with duplex grain structure, and Germany wins wound Evonik (former Degussa) company
Production, rutile and anatase crystal ratio are 8:2, partial size 20nm, specific area 50m2/g。
Reference examples
(1) catalyst preparation
According to the Ti in most document3+Auto-dope TiO2High-temperature roasting thermal reduction (the Chemical of photochemical catalyst
Society Reviews, 2015,44 (7), 1861-1885), by 1.0g TiO2Nano-photocatalyst (P25) is placed in Muffle furnace
In, in high-purity H2Atmosphere under, be warming up to 600 DEG C of progress high temperature thermal reduction processes, the recovery time 3 hours, take out catalyst and set
Powder sample is obtained after being cooled to room temperature in drier, for the Ti of high temperature thermal reduction3+The visible light-responded TiO of auto-dope2
(P25) photochemical catalyst is denoted as H-P25.
Infrared spectroscopy (FT-IR) figure for the modification P25 photochemical catalyst that reference examples are prepared is as shown in figure 1 shown in corresponding position；
Transmission electron microscope (TEM) photo for the modification P25 photochemical catalyst that reference examples are prepared is as shown in reference examples picture in Fig. 2；Control
High-resolution-ration transmission electric-lens (HRTEM) photo for the modification P25 photochemical catalyst that example is prepared in Fig. 3 as corresponded to shown in picture；It is right
X-ray diffraction (XRD) figure for the modification P25 photochemical catalyst being prepared as usual is as shown in corresponding position in Fig. 4；Reference examples are prepared into
X-ray fluorescence analysis (XPS) figure of the Ti2P of the modification P25 photochemical catalyst arrived is as shown in corresponding position in Fig. 5；Reference examples are prepared into
To modification P25 photochemical catalyst UV-vis DRS map as shown in corresponding position in Fig. 6.
The infrared spectrum of Fig. 1 shows that after ethyl alcohol heat-treats, oxide group significantly reduces in H-P25 catalyst, explanation
TiO2Surface have passed through modified with reduction processing.In TEM photo (Fig. 3) as can be seen that due to raw material TiO2(P25) stabilization of powder
Property, the topographical difference of powder entirety is little after high-temperature roasting heat-treats.The HRTEM photo of Fig. 3 shows that high-temperature roasting heat is also
Although TiO after original2Surface, which introduces disordering structure, can form heterojunction structure, but its surface even inside occurs largely
Disordering structure presents many clearly amorphous TiO2Pattern, a large amount of amorphous TiO in catalyst2It is anti-to photocatalysis
It should be unfavorable.The XRD spectrum of Fig. 4 shows after high-temperature roasting thermal reduction process, TiO2Still maintain rutile and anatase
The duplex grain structure of two kinds of crystallizations.The XPS map of the Ti2p of Fig. 5 catalyst shows occur in high-temperature roasting thermal reduction rear catalyst
Apparent Ti3+, this is because this is also composite catalyst with visible light-responded caused by mixed crystal forms heterojunction structure
Prerequisite.The UV Diffuse Reflectance Spectroscopy figure of Fig. 6 catalyst more obviously shows that the catalyst after high-temperature roasting reduction occurs
Apparent red shift and strong visible absorption.
(2) light degradation process in artificial seawater system
The H-P25 photochemical catalyst that 0.50g reference examples are prepared is weighed, the artificial seawater of 800mL phenol is uniformly mixed in
(phenol concentration is 5.0mg/L or so to system, and artificial seawater composition: magnesium chloride mass fraction is 1.1%, the quality point of calcium chloride
Number is 0.16%, and the mass fraction of sodium sulphate is 0.4%, and the mass fraction of sodium chloride is 2.5%), to be placed in magnetic agitation
In reactor, control bath temperature is 30 DEG C, absorption 0.5 hour of turning off the light.After adsorption equilibrium, (the 30W under visible light source irradiation
LED white light: have optical filter, light intensity 10mW/cm2), interval half an hour sampling (until reaction 5h) in reaction process,
Centrifuge separation, takes supernatant liquor, utilizes TU-19 series ultraviolet visible spectrophotometer (the general analysis all purpose instrument Limited Liability in Beijing
Company measures wavelength 510nm), it measures the absorbance of phenol and finds out the variation of its concentration.
The degradation curve of the phenol in light degradation artificial seawater system under excited by visible light of H-P25 prepared by this reference examples
As shown in Figure 7.The removal rate of the phenol in light degradation artificial seawater system under excited by visible light of H-P25 prepared by this reference examples
(reaction 2 hours) is as shown in Figure 8
As seen from Figure 7, although there is visible light-responded, and the portion in the artificial seawater that can degrade under excited by visible light
Divide phenol, but due to amorphous TiO a large amount of in catalyst2Presence, H-TiO2(P25) photochemical catalyst is to phenol in artificial seawater
Light degradation ability is obviously weaker.Fig. 8 shows that H-TiO is prepared in reference examples2(P25) photochemical catalyst is right under the excitation of visible light
2 hours removal rates of phenol are only 32% or so in artificial seawater.
Embodiment 1
(1) catalyst preparation
Dehydrated alcohol was ultrasonically treated in 10 minutes, to remove the gases such as wherein micro air or carbon dioxide.Then
By 1.0g commercialization TiO2(P25) dehydrated alcohol mixes after nano-photocatalyst and 120mL deaerate, and disperses in ultrasonication, until
Form stable suspension system (holding 5 hours or more stability).The suspension system is fully transferred to polytetrafluoro
It in ethylene in the steel autoclave in village, is smoothly put into air dry oven after sealing, ethyl alcohol thermal reduction is carried out at 150 DEG C
Reaction 12 hours.It takes out reaction kettle and is placed on being allowed to Temperature fall at room temperature, be then cooled to room temperature, removal suction filtration,
Powder sample is obtained after redisperse, washing and drying, heat-treats to obtain visible light-responded modified P25 photochemical catalyst for ethyl alcohol,
It is denoted as 150-P25 photochemical catalyst.
Infrared spectroscopy (FT-IR) figure for the modification P25 photochemical catalyst that the present embodiment is prepared is as shown in Figure 1；This implementation
Transmission electron microscope (TEM) photo for the modification P25 photochemical catalyst that example is prepared is as shown in Figure 2；What the present embodiment was prepared changes
High-resolution-ration transmission electric-lens (HRTEM) photo of property P25 photochemical catalyst is as shown in Figure 3.
Fig. 4 is that X-ray diffraction (XRD) figure for the modification P25 photochemical catalyst that the present embodiment is prepared is as shown in Figure 4；This
X-ray fluorescence analysis (XPS) figure of the Ti2P for the modification P25 photochemical catalyst that embodiment is prepared is as shown in Figure 5；The present embodiment
The UV-vis DRS map for the modification P25 photochemical catalyst being prepared is as shown in Figure 6.
The infrared spectrum of Fig. 1 shows that after ethyl alcohol heat-treats, oxide group is also reduced in 150-P25 catalyst,
Illustrate TiO during ethyl alcohol heat-treats2Surface also goes through modified with reduction processing.In the TEM photo of Fig. 2 as can be seen that by
In raw material TiO2(P25) stability of powder, also difference is little for the pattern by ethyl alcohol thermal reduction rear catalyst powder entirety.Figure
3 HRTEM photo shows that relatively-high temperature roasting process is more mild, and only the surface P25 is tied since ethyl alcohol thermal reduction process compares
Crystalline state TiO2Disordering is reduced as amorphous TiO2, and it has been formed on its surface heterojunction structure.The XRD diagram stave of Fig. 4
It is bright, after ethyl alcohol thermal reduction process, TiO2The same duplex grain structure for maintaining rutile and two kinds of anatase crystallizations.Fig. 5 catalysis
The XPS map of the Ti2p of agent shows apparent Ti also occur in ethyl alcohol thermal reduction rear catalyst3+, but due to reduction compared with
To be mild, Ti that surface is reduced4+Ti that is few, thus generating is heat-treated than high-temperature roasting3+Content is also less than H-P25, but
Ti3+Appearance also illustrate that ethyl alcohol thermal reduction process equally can achieve the purpose of auto-dope.The uv drs light of Fig. 6 catalyst
Spectrogram more obviously shows that certain red shift and apparent visible absorption equally occurs in the catalyst after ethyl alcohol thermal reduction.
(2) in artificial seawater system phenol light degradation process
The 150-P25 photochemical catalyst that 0.50g embodiment 1 is prepared is weighed, the artificial sea of 800mL phenol is uniformly mixed in
(phenol concentration is 5.0mg/L or so to aqueous systems, and artificial seawater composition: magnesium chloride mass fraction is 1.1%, the quality of calcium chloride
Score is 0.16%, and the mass fraction of sodium sulphate is 0.4%, and the mass fraction of sodium chloride is 2.5%), to be placed in band magnetic agitation
Reactor in, control bath temperature be 30 DEG C, turn off the light absorption 0.5 hour.After adsorption equilibrium, under visible light source irradiation
(the LED white light of 30W: have optical filter, light intensity 10mW/cm2), interval half an hour sampling is (until reaction in reaction process
5h), it is centrifugated, takes supernatant liquor, (the general analysis all purpose instrument in Beijing is limited using TU-19 series ultraviolet visible spectrophotometer
Responsible company measures wavelength 510nm), it measures the absorbance of phenol and finds out the variation of its concentration.
Degradation curve such as Fig. 7 of phenol in the degradation artificial seawater for the modification P25 photochemical catalyst that the present embodiment is prepared
It is shown；Removal rate (reaction time 2 hour) of the modification P25 photochemical catalyst that the present embodiment is prepared to phenol in artificial seawater
As shown in Figure 8；The modification P25 photochemical catalyst that the present embodiment is prepared repeats phenol experiment such as Fig. 9 in light degradation artificial seawater
It is shown.
As seen from Figure 7, after the preparation of ethyl alcohol thermal reduction obtained catalyst equally have it is visible light-responded, and can
Under light-exposed excitation can phenol in efficient degradation high slat-containing wastewater, since ethyl alcohol thermal reduction preparation process will not be to catalyst
Surface generates serious destruction, and generates a large amount of amorphous TiO2, what surface heterogeneous medium junction structure can be obviously improved catalyst can
Light-exposed catalytic activity.Thus 150-P25 photochemical catalyst is substantially better than H-TiO to phenol light degradation ability in artificial seawater2(P25)
Photochemical catalyst.Fig. 8 shows 150-P25 photochemical catalyst under the excitation of weakly visible light to 2 hours of phenol in artificial seawater system
Removal rate is more than 50%, hence it is evident that better than the H-P25 photochemical catalyst obtained after high-temperature roasting thermal reduction.And due to P25 raw material
Stability and the modified protection to catalyst structure of ethyl alcohol thermal reduction, Fig. 9 show that the stability of 150-P25 catalyst is very high,
The catalyst all shows very high and stable light degradation activity in repeating light degradation experiment three times.
Embodiment 2
(1) catalyst preparation
Dehydrated alcohol was ultrasonically treated in 10 minutes, to remove the gases such as wherein micro air or carbon dioxide.Then
By 1.0g commercialization TiO2(P25) dehydrated alcohol mixes after nano-photocatalyst and 120mL deaerate, and disperses in ultrasonication, until
Form stable suspension system (holding 5 hours or more stability).The suspension system is fully transferred to polytetrafluoro
It in ethylene in the steel autoclave in village, is smoothly put into air dry oven after sealing, ethyl alcohol thermal reduction is carried out at 160 DEG C
Reaction 12 hours.It takes out reaction kettle and is placed on being allowed to Temperature fall at room temperature, be then cooled to room temperature, removal suction filtration,
Powder sample is obtained after redisperse, washing and drying, heat-treats to obtain visible light-responded modified P25 photochemical catalyst for ethyl alcohol,
It is denoted as 160-P25 photochemical catalyst.
Fig. 1 is infrared spectroscopy (FT-IR) figure for the modification P25 photochemical catalyst that the present embodiment is prepared.
Fig. 2 is transmission electron microscope (TEM) photo for the modification P25 photochemical catalyst that the present embodiment is prepared.
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) photo for the modification P25 photochemical catalyst that the present embodiment is prepared.
Fig. 4 is X-ray diffraction (XRD) figure for the modification P25 photochemical catalyst that the present embodiment is prepared.
Fig. 5 is x-ray fluorescence analysis (XPS) figure of the Ti2P for the modification P25 photochemical catalyst that the present embodiment is prepared.
Fig. 6 is the UV-vis DRS map for the modification P25 photochemical catalyst that the present embodiment is prepared.
The infrared spectrum of Fig. 1 shows that after ethyl alcohol heat-treats, oxide group is also reduced in 160-P25 catalyst,
Illustrate TiO during ethyl alcohol heat-treats2Surface also goes through modified with reduction processing.As ethyl alcohol thermal reduction temperature increases,
Surface oxidation group is more reduced, thus absorption peak is relatively weaker.In the TEM photo of Fig. 2 as can be seen that due to raw material TiO2
(P25) stability of powder, also difference is little for the pattern by ethyl alcohol thermal reduction rear catalyst powder entirety.The HRTEM of Fig. 3 shines
Piece shows, due to only P25 surface crystallization state TiO after ethyl alcohol thermal reduction process2Disordering is reduced as amorphous TiO2, and
It has been formed on its surface heterojunction structure.The XRD spectrum of Fig. 4 shows after ethyl alcohol thermal reduction process, TiO2It is same to maintain gold
The duplex grain structure of red stone and two kinds of anatase crystallizations.The XPS map of the Ti2p of Fig. 5 catalyst is shown, is catalyzed after ethyl alcohol thermal reduction
Also occurs apparent Ti in agent3+, but since reduction is more mild, Ti that surface is reduced4+It is heat-treated than high-temperature roasting
The Ti for lacking, thus generating3+Content is also less than H-P25, but Ti3+Appearance also illustrate that ethyl alcohol thermal reduction process equally can be with
Achieve the purpose that auto-dope.Opposite 150-P26, ethanol reduction temperature is higher, more Ti4+It is reduced, the Ti of generation3+Also more
More, the effect of auto-dope is also better.The UV Diffuse Reflectance Spectroscopy figure of Fig. 6 catalyst more obviously shows that ethyl alcohol heat-treats
Equally there is certain red shift and apparent visible absorption in catalyst afterwards.Reduction temperature increases, and red shift and visible light are inhaled
Receipts obviously all enhance.
(2) in artificial seawater system phenol light degradation process
The 160-P25 photochemical catalyst that 0.50g embodiment 2 is prepared is weighed, the artificial sea of 800mL phenol is uniformly mixed in
(phenol concentration is 5.0mg/L or so to aqueous systems, and artificial seawater composition: magnesium chloride mass fraction is 1.1%, the quality of calcium chloride
Score is 0.16%, and the mass fraction of sodium sulphate is 0.4%, and the mass fraction of sodium chloride is 2.5%), to be placed in band magnetic agitation
Reactor in, control bath temperature be 30 DEG C, turn off the light absorption 0.5 hour.After adsorption equilibrium, under visible light source irradiation
(the LED white light of 30W: have optical filter, light intensity 10mW/cm2), interval half an hour sampling is (until reaction in reaction process
5h), it is centrifugated, takes supernatant liquor, (the general analysis all purpose instrument in Beijing is limited using TU-19 series ultraviolet visible spectrophotometer
Responsible company measures wavelength 510nm), it measures the absorbance of phenol and finds out the variation of its concentration.
Degradation curve such as Fig. 7 of phenol in the degradation artificial seawater for the modification P25 photochemical catalyst that the present embodiment is prepared
It is shown；Removal rate (reaction time 2 hour) of the modification P25 photochemical catalyst that the present embodiment is prepared to phenol in artificial seawater
As shown in Figure 8；The modification P25 photochemical catalyst that the present embodiment is prepared repeats phenol experiment such as Fig. 9 in light degradation artificial seawater
It is shown.
As seen from Figure 7, after the preparation of ethyl alcohol thermal reduction obtained catalyst equally have it is visible light-responded, and can
Under light-exposed excitation can phenol in efficient degradation high slat-containing wastewater, since ethyl alcohol thermal reduction preparation process will not be to catalyst
Surface generates serious destruction, and generates a large amount of amorphous TiO2, what surface heterogeneous medium junction structure can be obviously improved catalyst can
Light-exposed catalytic activity.Thus 160-P25 photochemical catalyst is equally better than H-TiO to phenol light degradation ability in artificial seawater2(P25)
Photochemical catalyst.And ethyl alcohol thermal reduction temperature increases, the Ti in catalyst3+Content increases, visible light-responded enhancing.Thus,
The visible light catalysis activity of 160-P25 photochemical catalyst is better than 150-P25.To artificial seawater system under the excitation of weakly visible light
2 hours removal rates of middle phenol are more than 65%, are 2 times of the H-P25 photochemical catalyst obtained after high-temperature roasting heat-treats.And by
In the modified protection to catalyst structure of stability and ethyl alcohol thermal reduction of P25 raw material, Fig. 9 shows 160-P25 catalyst
Stability is very high, and the catalyst also shows that very high and stable light degradation activity in repeating light degradation experiment three times.
Embodiment 3
(1) catalyst preparation
Dehydrated alcohol was ultrasonically treated in 10 minutes, to remove the gases such as wherein micro air or carbon dioxide.Then
By 1.0g commercialization TiO2(P25) dehydrated alcohol mixes after nano-photocatalyst and 120mL deaerate, and disperses in ultrasonication, until
Form stable suspension system (holding 5 hours or more stability).The suspension system is fully transferred to polytetrafluoro
It in ethylene in the steel autoclave in village, is smoothly put into air dry oven after sealing, ethyl alcohol thermal reduction is carried out at 170 DEG C
Reaction 12 hours.It takes out reaction kettle and is placed on being allowed to Temperature fall at room temperature, be then cooled to room temperature, removal suction filtration,
Powder sample is obtained after redisperse, washing and drying, heat-treats to obtain visible light-responded modified P25 photochemical catalyst for ethyl alcohol,
It is denoted as 170-P25 photochemical catalyst.
Infrared spectroscopy (FT-IR) figure for the modification P25 photochemical catalyst that the present embodiment is prepared is as shown in Figure 1；This implementation
Transmission electron microscope (TEM) photo for the modification P25 photochemical catalyst that example is prepared is as shown in Figure 2；What the present embodiment was prepared changes
High-resolution-ration transmission electric-lens (HRTEM) photo of property P25 photochemical catalyst is as shown in Figure 3；The modification P25 light that the present embodiment is prepared
X-ray diffraction (XRD) figure of catalyst is as shown in Figure 4；The X of the Ti2P for the modification P25 photochemical catalyst that the present embodiment is prepared
Ray fluorescence analysis (XPS) figure is as shown in Figure 5；The UV, visible light for the modification P25 photochemical catalyst that the present embodiment is prepared is unrestrained anti-
It is as shown in Figure 6 to penetrate map.
The infrared spectrum of Fig. 1 shows that after ethyl alcohol heat-treats, oxide group is also reduced in 170-P25 catalyst,
Illustrate TiO during ethyl alcohol heat-treats2Surface also goes through modified with reduction processing.As ethyl alcohol thermal reduction temperature increases,
Surface oxidation group is more reduced, thus absorption peak is relatively weaker.In the TEM photo of Fig. 2 as can be seen that due to raw material TiO2
(P25) stability of powder, also difference is little for the pattern by ethyl alcohol thermal reduction rear catalyst powder entirety.The HRTEM of Fig. 3 shines
Piece shows, due to only P25 surface crystallization state TiO after ethyl alcohol thermal reduction process2Disordering is reduced as amorphous TiO2, and
It has been formed on its surface heterojunction structure.The XRD spectrum of Fig. 4 shows after ethyl alcohol thermal reduction process, TiO2It is same to maintain gold
The duplex grain structure of red stone and two kinds of anatase crystallizations.The XPS map of the Ti2p of Fig. 5 catalyst is shown, is catalyzed after ethyl alcohol thermal reduction
Also occurs apparent Ti in agent3+, but since reduction is more mild, Ti that surface is reduced4+It is heat-treated than high-temperature roasting
The Ti for lacking, thus generating3+Content is also less than H-P25, but Ti3+Appearance also illustrate that ethyl alcohol thermal reduction process equally can be with
Achieve the purpose that auto-dope.Opposite 150-P25 and 160-P25 photochemical catalyst, ethanol reduction temperature is higher, more Ti4+It is reduced,
The Ti of generation3+Also more, thus Ti in 170-P253+Content obviously increases, and the effect of auto-dope is also better.Fig. 6 is urged
The UV Diffuse Reflectance Spectroscopy figure of agent more obviously shows, the catalyst after ethyl alcohol thermal reduction equally occur certain red shift and
Apparent visible absorption.Reduction temperature increases, and red shift and visible absorption obviously all enhance.
(2) in artificial seawater system phenol light degradation process
The 170-P25 photochemical catalyst that 0.50g embodiment 3 is prepared is weighed, the artificial sea of 800mL phenol is uniformly mixed in
(phenol concentration is 5.0mg/L or so to aqueous systems, and artificial seawater composition: magnesium chloride mass fraction is 1.1%, the quality of calcium chloride
Score is 0.16%, and the mass fraction of sodium sulphate is 0.4%, and the mass fraction of sodium chloride is 2.5%), to be placed in band magnetic agitation
Reactor in, control bath temperature be 30 DEG C, turn off the light absorption 0.5 hour.After adsorption equilibrium, under visible light source irradiation
(the LED white light of 30W: have optical filter, light intensity 10mW/cm2), interval half an hour sampling is (until reaction in reaction process
5h), it is centrifugated, takes supernatant liquor, (the general analysis all purpose instrument in Beijing is limited using TU-19 series ultraviolet visible spectrophotometer
Responsible company measures wavelength 510nm), it measures the absorbance of phenol and finds out the variation of its concentration.
Degradation curve such as Fig. 7 of phenol in the degradation artificial seawater for the modification P25 photochemical catalyst that the present embodiment is prepared
It is shown；Removal rate (reaction time 2 hour) of the modification P25 photochemical catalyst that the present embodiment is prepared to phenol in artificial seawater
As shown in Figure 8；The modification P25 photochemical catalyst that the present embodiment is prepared repeats phenol experiment such as Fig. 9 in light degradation artificial seawater
It is shown.
As seen from Figure 7, after the preparation of ethyl alcohol thermal reduction obtained catalyst equally have it is visible light-responded, and can
Under light-exposed excitation can phenol in efficient degradation high slat-containing wastewater, since ethyl alcohol thermal reduction preparation process will not be to catalyst
Surface generates serious destruction, and generates a large amount of amorphous TiO2, what surface heterogeneous medium junction structure can be obviously improved catalyst can
Light-exposed catalytic activity.Thus 170-P25 photochemical catalyst is equally better than H-TiO to phenol light degradation ability in artificial seawater2(P25)
Photochemical catalyst.And ethyl alcohol thermal reduction temperature increases, the Ti in catalyst3+Content increases, visible light-responded enhancing.Thus,
The visible light catalysis activity of 170-P25 photochemical catalyst is better than 150-P25 and 160-P25 photochemical catalyst.In swashing for weakly visible light
It gives and 70% or more is reached to 2 hours removal rates of phenol in artificial seawater system, more than what is obtained after high-temperature roasting thermal reduction
More than 2 times of H-P25 photochemical catalyst.And stability due to P25 raw material and ethyl alcohol thermal reduction are modified to catalyst structure
Protection, Fig. 9 show that the stability of 170-P25 catalyst is very high, and the catalyst is equally shown in repeating light degradation experiment three times
Very high and stable light degradation activity.
Embodiment 4
(1) catalyst preparation
Dehydrated alcohol was ultrasonically treated in 10 minutes, to remove the gases such as wherein micro air or carbon dioxide.Then
By 1.0g commercialization TiO2(P25) dehydrated alcohol mixes after nano-photocatalyst and 120mL deaerate, and disperses in ultrasonication, until
Form stable suspension system (holding 5 hours or more stability).The suspension system is fully transferred to polytetrafluoro
It in ethylene in the steel autoclave in village, is smoothly put into air dry oven after sealing, ethyl alcohol thermal reduction is carried out at 180 DEG C
Reaction 12 hours.It takes out reaction kettle and is placed on being allowed to Temperature fall at room temperature, be then cooled to room temperature, removal suction filtration,
Powder sample is obtained after redisperse, washing and drying, heat-treats to obtain visible light-responded modified P25 photochemical catalyst for ethyl alcohol,
It is denoted as 180-P25 photochemical catalyst.
Infrared spectroscopy (FT-IR) figure for the modification P25 photochemical catalyst that the present embodiment is prepared is as shown in Figure 1；This implementation
Transmission electron microscope (TEM) photo for the modification P25 photochemical catalyst that example is prepared is as shown in Figure 2；What the present embodiment was prepared changes
High-resolution-ration transmission electric-lens (HRTEM) photo of property P25 photochemical catalyst is as shown in Figure 3；The modification P25 light that the present embodiment is prepared
X-ray diffraction (XRD) figure of catalyst is as shown in Figure 4；The X of the Ti2P for the modification P25 photochemical catalyst that the present embodiment is prepared
Ray fluorescence analysis (XPS) figure is as shown in Figure 5；The UV, visible light for the modification P25 photochemical catalyst that the present embodiment is prepared is unrestrained anti-
It is as shown in Figure 6 to penetrate map.
The infrared spectrum of Fig. 1 shows that after ethyl alcohol heat-treats, oxide group is also reduced in 180-P25 catalyst,
Illustrate TiO during ethyl alcohol heat-treats2Surface also goes through modified with reduction processing.As ethyl alcohol thermal reduction temperature increases,
Surface oxidation group is more reduced, thus absorption peak is relatively weaker.In the TEM photo of Fig. 2 as can be seen that due to raw material TiO2
(P25) stability of powder, also difference is little for the pattern by ethyl alcohol thermal reduction rear catalyst powder entirety.The HRTEM of Fig. 3 shines
Piece shows, due to only P25 surface crystallization state TiO after ethyl alcohol thermal reduction process2Disordering is reduced as amorphous TiO2, and
It has been formed on its surface heterojunction structure.The XRD spectrum of Fig. 4 shows after ethyl alcohol thermal reduction process, TiO2It is same to maintain gold
The duplex grain structure of red stone and two kinds of anatase crystallizations.The XPS map of the Ti2p of Fig. 5 catalyst is shown, is catalyzed after ethyl alcohol thermal reduction
Also occurs apparent Ti in agent3+, but since reduction is more mild, Ti that surface is reduced4+It is heat-treated than high-temperature roasting
The Ti for lacking, thus generating3+Content is also less than H-P25, but Ti3+Appearance also illustrate that ethyl alcohol thermal reduction process equally can be with
Achieve the purpose that auto-dope.The catalyst that heat-treats of several ethyl alcohol before relatively, Ti in 180-P25 catalyst3+Content highest.
Ethanol reduction temperature is higher, more Ti4+It is reduced, the Ti of generation3+Also more, the effect of auto-dope is also better.Fig. 6
The UV Diffuse Reflectance Spectroscopy figure of catalyst more obviously shows that certain red shift equally occurs in the catalyst after ethyl alcohol thermal reduction
With apparent visible absorption.Reduction temperature increases, and red shift and visible absorption obviously all enhance.
(2) in artificial seawater system phenol light degradation process
The 180-P25 photochemical catalyst that 0.50g embodiment 4 is prepared is weighed, the artificial sea of 800mL phenol is uniformly mixed in
(phenol concentration is 5.0mg/L or so to aqueous systems, and artificial seawater composition: magnesium chloride mass fraction is 1.1%, the quality of calcium chloride
Score is 0.16%, and the mass fraction of sodium sulphate is 0.4%, and the mass fraction of sodium chloride is 2.5%), to be placed in band magnetic agitation
Reactor in, control bath temperature be 30 DEG C, turn off the light absorption 0.5 hour.After adsorption equilibrium, under visible light source irradiation
(the LED white light of 30W: have optical filter, light intensity 10mW/cm2), interval half an hour sampling is (until reaction in reaction process
5h), it is centrifugated, takes supernatant liquor, (the general analysis all purpose instrument in Beijing is limited using TU-19 series ultraviolet visible spectrophotometer
Responsible company measures wavelength 510nm), it measures the absorbance of phenol and finds out the variation of its concentration.
Degradation curve such as Fig. 7 of phenol in the degradation artificial seawater for the modification P25 photochemical catalyst that the present embodiment is prepared
It is shown；Removal rate (reaction time 2 hour) of the modification P25 photochemical catalyst that the present embodiment is prepared to phenol in artificial seawater
As shown in Figure 8；The modification P25 photochemical catalyst that the present embodiment is prepared repeats phenol experiment such as Fig. 9 in light degradation artificial seawater
It is shown.
As seen from Figure 7, after the preparation of ethyl alcohol thermal reduction obtained catalyst equally have it is visible light-responded, and can
Under light-exposed excitation can phenol in efficient degradation high slat-containing wastewater, since ethyl alcohol thermal reduction preparation process will not be to catalyst
Surface generates serious destruction, and generates a large amount of amorphous TiO2, what surface heterogeneous medium junction structure can be obviously improved catalyst can
Light-exposed catalytic activity.Thus 180-P25 photochemical catalyst is equally better than H-TiO to phenol light degradation ability in artificial seawater2(P25)
Photochemical catalyst.And ethyl alcohol thermal reduction temperature increases, the Ti in catalyst3+Content increases, visible light-responded enhancing.Thus,
The catalyst that several ethyl alcohol heat-treat before the visible light catalysis activity of 180-P25 photochemical catalyst is better than.In weakly visible light
Excitation under 80% or more is reached to 2 hours removal rates of phenol in artificial seawater system, be more than high-temperature roasting thermal reduction after
More than 2 times of the H-P25 photochemical catalyst arrived.And stability due to P25 raw material and ethyl alcohol thermal reduction are modified to catalyst knot
The protection of structure, Fig. 9 show that the stability of 180-P25 catalyst is very high, and the catalyst is same in repeating light degradation experiment three times
Show very high and stable light degradation activity.
The foregoing is merely the specific implementation cases of the invention patent, but the technical characteristic of the invention patent is not limited to
This, within the field of the present invention, made changes or modifications all cover of the invention special any those skilled in the relevant art
Among sharp range.
Claims (8)
1. a kind of visible light-responded TiO of duplex grain structure2The method of modifying of photochemical catalyst, which comprises the steps of:
(1) by the TiO with duplex grain structure2Nano-photocatalyst and ultrasonic treatment after dehydrated alcohol mixing, ultrasonic disperse until
Form stable suspension system；
(2) suspension system is fully transferred in autoclave, it is anti-carries out ethyl alcohol thermal reduction after sealing at a constant temperature
It answers；
(3) it will be separated after gained heat treatment reaction solution cooling, washed and drying and processing.
2. method of modifying according to claim 1, which is characterized in that TiO2The mass body of nano-photocatalyst and dehydrated alcohol
Product is than being 0.50g~5.0g:120mL.
3. method of modifying according to claim 1, which is characterized in that the TiO2Nano-photocatalyst is powdered, and is presented
The duplex grain structure of rutile and anatase, specific surface area 50m2/ g~100m2/ g, particle diameter are 10~50nm.
4. method of modifying according to claim 1, which is characterized in that reaction temperature is 150 DEG C~180 DEG C in step (2)；Instead
It is 5~24 hours between seasonable.
5. a kind of method of organic pollutant in processing artificial seawater, which comprises the steps of:
Photochemical catalyst after the method for modifying modification as described in any one of Claims 1 to 4 claim is added to manually
In seawer system, irradiated 3~5 hours under visible light source after adsorption equilibrium at dark.
6. method according to claim 5, which is characterized in that the dosage of the photochemical catalyst after modification is 0.5mg/L
~5.0mg/mL.
7. method according to claim 5, which is characterized in that organic pollutant is phenol in the artificial seawater system；Benzene
Phenol content is 5.0mg/L~10mg/L.
8. method according to claim 5, which is characterized in that visible light source is the LED white light of 30W, and light intensity is
10mW/cm2。
Priority Applications (1)
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