CN106732630B - Cu(I) modified photocatalytic material, preparation method and its application - Google Patents
Cu(I) modified photocatalytic material, preparation method and its application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 5
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003403 water pollutant Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 18
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011017 operating method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005253 cladding Methods 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 34
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 34
- 230000015556 catabolic process Effects 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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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Abstract
A kind of Cu (I) modified photocatalytic material, preparation method and its application.Cu (I) the modified photocatalytic material is prepared as follows: step 1, to be dissolved in mantoquita and bismuth nitrate be to be configured to solution in the ethylene glycol of 10% glacial acetic acid containing volume fraction；Potassium bromide solution is added in step 2, Xiang Shangshu solution；Step 3 is freeze-dried after reacting a period of time at high temperature.The present invention enters monovalence Copper-cladding Aluminum Bar in catalysis material, for the emerging pollutant in water of degrading；Operating method is simple, easy, raw material is easy to get, is low in cost, can be widely used in actual operation.
Description
Technical field
The present invention relates to catalyst technical fields, relate more specifically to a kind of Cu (I) modified photocatalytic material, can be obvious
Reduce the dosage of catalyst.
The invention further relates to the method and its application for preparing above-mentioned catalysis material.
Background technique
Reaction condition is mild, low energy consumption, easy to operate and make using sunlight because having for visible light photocatalysis technology
The features such as to react light source, increasingly important role is played in terms of environmental pollution improvement and energy development.Visible light is urged
The key of change technology is the preparation and its modification of novel visible catalyst, traditional visible light catalyst there are low efficiency and
How the disadvantages of recycling relative difficult, improve the efficiency of visible light catalyst, realizes that its sustainable is recycled as state
The research hotspot of inside and outside photocatalysis field.
In numerous pollutant abatement technologies, photocatalysis technology is environmentally friendly with its and can realize the spy of deep treatment
Point receives the concern of researcher.In general, hole (the h generated in photocatalytic process+), hydroxyl radical free radical (OH) and
Superoxide radical (O2 -) there is Strong oxdiative ability, redox reaction can occur with pollutant, realize the complete of contaminant molecule
Degradable, and it is finally decomposed to CO2、H2O and nontoxic inorganic matter etc..
Bismuth system catalysis material, due to good ultraviolet light and visible light photocatalysis active, unique layer structure
And high photostability, it has been to be concerned by more and more people.It is reported in spite of considerable research to urge with good light
Change activity, to realize that it plays value in practical applications, it is necessary to further increase the photocatalytic activity of bismuth system catalysis material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of catalysis materials with high efficiency photocatalysis effect.
Another object of the present invention is to provide a kind of method for preparing above-mentioned catalysis material.
To achieve the above object, as one aspect of the present invention, Cu (I) modified light is prepared the present invention provides a kind of
The method of catalysis material, comprising the following steps:
Step 1, to be dissolved in mantoquita and bismuth nitrate be to be configured to solution in the ethylene glycol of 10% glacial acetic acid containing volume fraction；
Potassium bromide solution is added in step 2, Xiang Shangshu solution；
Step 3 is freeze-dried after reacting a period of time at high temperature.
As another aspect of the present invention, it is modified by preparing Cu (I) as described above that the present invention also provides one kind
Cu (I) modified photocatalytic material that the method for catalysis material is prepared.
As another aspect of the invention, the present invention also provides a kind of Cu (I) modified photocatalytic materials as described above
Expect the application in visible light catalytic processing water pollutant field.
Based on the above-mentioned technical proposal it is found that Cu (I) modified photocatalytic material of the invention has a characteristic that
(1) Cu (I) is introduced in bismuth system catalysis material, and mantoquita is combined with bismuth system catalysis material, can be passed through
Metallic surface plasma resonance effect greatlys improve photocatalysis efficiency, and can increase the specific surface area of catalysis material, enhancing
Its absorption property；
(2) a possibility that operating method is simple and easy, and raw material is easy to get, low in cost, practical application is larger；
(3) existing for the hydrogen peroxide under the conditions of, photocatalytic degradation effect is very excellent.
Detailed description of the invention
Fig. 1 is the XPS map of x-CB sample prepared by the present invention；
Fig. 2A, Fig. 2 B are respectively the SEM spectrum of BiOBr and 0.025-CB sample:
Fig. 3 A is that different photochemical catalysts change C/C with the concentration of light application time to the degradation of sulfamethoxazole (SMX)0Song
Line chart；
Fig. 3 B is column of the different photochemical catalysts to the pseudo- first order kinetics reaction constant of the degradation of sulfamethoxazole (SMX)
Figure；
Fig. 4 A be under the conditions of different hydrogen peroxide concentrations, 0.01-CB to the degradation of sulfamethoxazole (SMX) with illumination when
Between SMX concentration change C/C0Curve graph；
Fig. 4 B is pseudo- level-one of the 0.01-CB to the degradation of sulfamethoxazole (SMX) under the conditions of different hydrogen peroxide concentrations
The histogram of kinetic reaction constant；
Fig. 5 A is under condition of different pH, and 0.01-CB is dense with the SMX of light application time to the degradation of sulfamethoxazole (SMX)
Degree variation C/C0Curve graph；
Fig. 5 B is under condition of different pH, and 0.01-CB reacts the pseudo- first order kinetics of the degradation of sulfamethoxazole (SMX)
The histogram of constant.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Attached drawing, the present invention is described in further detail.
The present invention provides a kind of methods for preparing Cu (I) modified photocatalytic material, comprising the following steps:
Step 1, to be dissolved in mantoquita and bismuth nitrate be to be configured to solution in the ethylene glycol of 10% glacial acetic acid containing volume fraction；
Potassium bromide solution is added in step 2, Xiang Shangshu solution；
Step 3 is freeze-dried after reacting a period of time at high temperature.
In the above method, the mantoquita in step 1 is copper nitrate or copper chloride.
In the above method, in step 1 molar ratio of mantoquita and bismuth nitrate be 0.005~0.01, preferably 0.025~
0.01。
In the above method, the potassium bromide solution in step 2 is using ethylene glycol as solvent.
In the above method, the reaction temperature in step 3 is 150-180 DEG C, reaction time 10-15h.
In the above method, all reactions are completed under the protection of argon gas, nitrogen or helium in step 1-3.
The present invention also provides the Cu that one kind is prepared by the above-mentioned method for preparing Cu (I) modified photocatalytic material
(I) modified photocatalytic material.
Wherein, which is in spherical, and partial size is 3-5 μm, specific surface area 15-25g/m2, aperture
Between 7-15nm, pore capacities 0.030-0.065cm3/ g, band gap 2.70-2.85eV.
The present invention also provides a kind of Cu (I) modified photocatalytic materials as described above to pollute in visible light photocatalysis water
The application in object field, application when being especially used cooperatively with hydrogen peroxide.
In order to further illustrate the present invention to the light degradation effect of water pollutant, the present invention investigates in conjunction with specific embodiments
Under the conditions of existing for the hydrogen peroxide, degradation of the photochemical catalyst prepared under different mantoquita additive amounts to sulfamethoxazole (SMX)
Effect, to preferably play the photochemical catalyst to the degradation capability of water pollutant.
Embodiment 1
Under the protection of argon gas, the copper nitrate and bismuth nitrate that are 0.005 by molar ratio, being dissolved in containing volume fraction is 10% ice
In the ethylene glycol of acetic acid, it is configured to solution；And the ethylene glycol solution containing 0.1 mol/L potassium bromide is added to above-mentioned solution；?
It is freeze-dried after reacting 12h at 160 DEG C.Resulting sample indicates that wherein x is the charging mole of copper nitrate and bismuth nitrate with x-CB
Than x is 0.005 in the present embodiment.
Embodiment 2
Experimental procedure is only that copper nitrate and bismuth nitrate with embodiment 1, difference, is fed according to molar ratio for 0.01.
Embodiment 3
For experimental procedure with embodiment 1, difference is only that copper nitrate and bismuth nitrate, according to molar ratio be 0.025 carry out into
Material.
Comparative example 1
For experimental procedure with embodiment 1, difference, which is only that, does not add copper nitrate.The thus obtained sample modified without copper
For BiOBr sample.
Illustrate the advantageous effects of the preferred embodiment of the present invention with reference to the accompanying drawing.
Fig. 1 is the XRD spectrum of prepared x-CB sample.As can be seen that in the combination energy of 932.8eV and 952.74eV
Peak corresponds respectively to Cu3p/2 and Cu1p/2.This explanation, during the preparation process, cupric is reduced to monovalence copper.
Using sem analysis prepared BiOBr sample and 0.025-CB sample.Fig. 2A, Fig. 2 B illustrate sweeping for sample
Retouch sem image.Fig. 2A shows that the outer surface of BiOBr microballoon is wrapped in by the nano particle of wheat shape.Fig. 2 B shows,
0.025-CB microballoon, it appears that be to be crowded together to be formed by by many nano flakes.This shows that the addition of copper ion can promote
Into the generation of nanometer sheet.This has not only promoted the increase of catalysis material surface apertures, but also specific surface area is become larger.
Fig. 3 A, Fig. 3 B are respectively that different photochemical catalysts are bent with the variation of light application time to the degradation of sulfamethoxazole (SMX)
Line chart, the concentration that wherein Fig. 3 A is SMX change (C/C0) curve graph, Fig. 3 B is the histogram of pseudo- first order kinetics reaction constant；
Experiment condition are as follows: catalysis material concentration: 0.5g/L；SMX:1mg/L；Hydrogen peroxide concentration: 5mM.By being 1mg/ to initial concentration
The degradation of the sulfamethoxazole (SMX) of L, to evaluate visible light-class Fenton catalytic activity of BiOBr sample and x-CB sample.It is real
The catalysis material using 0.5g/L is tested, is reacted under conditions of pH is neutral, first 30min is reacted under dark condition, makes
Catalysis material reaches saturation to the absorption of pollutant, and hydrogen peroxide is then added, and makes hydrogen peroxide initial concentration 5mmol/ in solution
L is reacted under conditions of > 400nm wavelength.Fig. 3 A shows during visible light-class Fenton catalytic degradation, SMX's
Concentration with light application time variation.It is shown by experiment, after 30 minutes absorption-desorption balances, adsorption capacity is strongest to be urged
Agent is 0.01-CB, adsorption efficiency 12%.After illumination in 120 minutes, SMX condition existing for 0.01-CB catalyst
Under, light degradation amount is maximum, almost degrades.Using pseudo- First order dynamic model: In (C/C0)=- kt drops to describe this catalysis
Solution preocess, wherein k is the observed rate constant of different catalysts, as basic dynamic parameter.Find out from Fig. 3 B, in H2O2By force
In photocatalysis reaction, the catalytic performance of 0.01-CB is most strong.
Fig. 4 A is illustrated under the conditions of different hydrogen peroxide concentrations, and 0.01-CB is to the degradation of sulfamethoxazole (SMX) with light
According to the change curve of time, wherein hydrogen peroxide concentration uses 0-20mM.By experiment as can be seen that being 1 in hydrogen peroxide concentration
Under conditions of~5mM, the performance of 0.01-CB catalysis material is most strong, and the kinetic constant of reaction is 0.032min-1.It is thus determined that
In visible light-Fenton-like reaction, the optimal concentration of hydrogen peroxide is 1mM.
Fig. 4 B is pseudo- level-one of the 0.01-CB to the degradation of sulfamethoxazole (SMX) under the conditions of different hydrogen peroxide concentrations
The histogram of kinetic reaction constant.Wherein, experiment condition are as follows: 0.01-CB:0.5g/L；Hydrogen peroxide concentration: 0-20mM；SMX:
1mg/L)。
Fig. 5 A is illustrated under condition of different pH, and 0.01-CB is to the degradation of sulfamethoxazole (SMX) with the change of light application time
Change curve graph, Fig. 5 B is under condition of different pH, and 0.01-CB is anti-to the pseudo- first order kinetics of the degradation of sulfamethoxazole (SMX)
Answer the histogram of constant.Wherein, pH uses 3-10；0.01-CB concentration: 0.5g/L；Hydrogen peroxide concentration: 1mM；SMX:1mg/L.It is logical
Experiment is crossed as can be seen that the performance of 0.01-CB catalysis material is most strong, and the kinetic constant of reaction is under conditions of pH is 3-7
0.033min-1.It is thus determined that optimal pH condition is 3-7 in visible light-embryonic stem-like cells.
The above results explanation, the copper modified photocatalytic material of the method preparation are 1mM in hydrogen peroxide concentration, and pH is 3-7's
Under the conditions of, it is seen that light-class Fenton catalytic degradation effect is optimal, can carry out efficient catalytic degradation to the pollutant in water body,
Popularization and application foreground is good.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention
Within the scope of.
Claims (10)
1. a kind of method for preparing Cu (I) modified photocatalytic material, comprising the following steps:
Step 1, to be dissolved in mantoquita and bismuth nitrate be to be configured to solution in the ethylene glycol of 10% glacial acetic acid containing volume fraction；Wherein,
The molar ratio of the mantoquita and bismuth nitrate is 0.005~0.01；
Potassium bromide solution is added in step 2, Xiang Shangshu solution；
Step 3 is freeze-dried after reacting a period of time at high temperature.
2. according to the method described in claim 1, wherein, the mantoquita in step 1 is copper nitrate or copper chloride.
3. according to the method described in claim 1, wherein, the molar ratio of mantoquita and bismuth nitrate is 0.025~0.01 in step 1.
4. according to the method described in claim 1, wherein, the potassium bromide solution in step 2 is using ethylene glycol as solvent.
5. according to the method described in claim 1, wherein, the reaction temperature in step 3 is 150-180 DEG C, reaction time 10-
15h。
6. according to the method described in claim 1, wherein, all reactions are under the protection of argon gas, nitrogen or helium in step 1-3
It completes.
7. a kind of method for preparing Cu (I) modified photocatalytic material by as described in claim 1 to 6 any one is prepared into
Cu (I) the modified photocatalytic material arrived.
8. Cu (I) modified photocatalytic material according to claim 7, Cu (I) the modified photocatalytic material is in spherical, grain
Diameter is 3-5 μm, specific surface area 15-25g/m2, aperture is between 7-15nm, pore capacities 0.030-0.065cm3/ g, can interband
Gap is 2.70-2.85eV.
9. a kind of Cu as claimed in claim 7 (I) modified photocatalytic material handles water pollutant field in visible light catalytic
Application.
10. application according to claim 9, which is characterized in that Cu (I) the modified photocatalytic material and hydrogen peroxide cooperate
It uses, wherein hydrogen peroxide concentration is 1mM, pH 3-7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710046902.2A CN106732630B (en) | 2017-01-18 | 2017-01-18 | Cu(I) modified photocatalytic material, preparation method and its application |
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| CN201710046902.2A CN106732630B (en) | 2017-01-18 | 2017-01-18 | Cu(I) modified photocatalytic material, preparation method and its application |
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| CN106732630B true CN106732630B (en) | 2019-08-20 |
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| Ag掺杂三维花状BiOBr光催化剂降解罗丹明B的研究;方琴琴 等;《广州化工》;20140630;第42卷(第11期);第100页第1.2节，第101页第1.3节 * |
| H2O2协同花球状BiOBr催化剂可见光下降解4-氯苯酚的研究;陈晓芳 等;《第十三届全国太阳能光化学与光催化学术会议》;20130528;第320页 * |
| 方琴琴 等.Ag掺杂三维花状BiOBr光催化剂降解罗丹明B的研究.《广州化工》.2014,第42卷(第11期), * |
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