CN107376974A - A kind of high-performance nonmetal doping Ti based photocatalysts and preparation method thereof - Google Patents
A kind of high-performance nonmetal doping Ti based photocatalysts and preparation method thereof Download PDFInfo
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- CN107376974A CN107376974A CN201710699933.8A CN201710699933A CN107376974A CN 107376974 A CN107376974 A CN 107376974A CN 201710699933 A CN201710699933 A CN 201710699933A CN 107376974 A CN107376974 A CN 107376974A
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- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 241000549556 Nanos Species 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 239000004570 mortar (masonry) Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010805 inorganic waste Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- B01J20/0262—Compounds of O, S, Se, Te
- B01J20/0266—Compounds of S
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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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
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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
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a kind of high-performance nonmetal doping Ti based photocatalysts and preparation method thereof, the high-performance nonmetal doping Ti based photocatalysts are that S/N co-doped nanos are modified TiO2Photochemical catalyst S/N TiO2；Contain a certain amount of N atoms in the body phase of the high-performance nonmetal doping Ti based photocatalysts, N: Ti mass ratio is 0.05~20%；There is S on the high-performance nonmetal doping Ti based photocatalysts surface6+(SO4 2‑).The preparation method includes pretreatment, calcining, impregnates, dries.The high-performance nonmetal doping Ti based photocatalysts of the present invention have high specific surface area, have stronger photocatalytic degradation capability and adsorption capacity to organic wastewater etc., are suitable for related organic wastewater COD improvement.
Description
Technical field
The present invention relates to inorganic functional material field, and in particular to a kind of high-performance nonmetal doping Ti based photocatalysts and
Its preparation method.
Background technology
Along with today's society expanding economy, concern of the people to field of Environment Protection waste water control is more and more.Chemical industry is given birth to
Many organic-inorganic waste water will necessarily be produced during production, so as to cause the COD of water body higher.In recent years, conductor photocatalysis
The application and development of technology so that Degradation of Organo-pollutants in Water with Photo-catalysis is possibly realized.TiO2As a kind of environmentally friendly
Semiconductor light-catalyst, because its is nontoxic, stability is good and cheap and wide concerned.Early in 1967 when, Teng Dao religion
Award and found that with TiO2For electrode, the characteristic with light irradiation with regard to energy light decomposition water.Although TiO2With above-mentioned advantage, but its
Energy gap is 3.2eV (anatase), is merely able to surface that is active under the higher light source of energy, therefore changing catalyst
Property and reduction bandwidth are very necessary.
Patent CN101367042A describes one kind using butyl titanate as titanium source, and urea is nitrogen source, nickel acetate or nitric acid
Nickel is nickel source, has obtained having the photoactive photochemical catalyst of the sun after stirring deposition separation drying and roasting in absolute ethyl alcohol.Should
The TiO of N doping is prepared using sol-gal process for patent2Photochemical catalyst, but catalytic inner lattice knot prepared by this method
Structure determines that its degradation effect still has much room for improvement.
The content of the invention
For problem above, it is an object of the invention to provide a kind of high-performance nonmetal doping Ti based photocatalysts and its system
Preparation Method, there can be the nano-photocatalyst of high efficiency photocatalysis degradation capability to organic pollution by the present invention.
To reach above-mentioned technical purpose, technical scheme is as follows：A kind of high-performance nonmetal doping Ti base light is urged
Agent, the high-performance nonmetal doping Ti based photocatalysts are that S/N co-doped nanos are modified TiO2Photochemical catalyst S/N-
TiO2；Contain a certain amount of N atoms in the high-performance nonmetal doping Ti based photocatalysts in its body phase, N: Ti mass ratio is
0.05~20%；There is S on the high-performance nonmetal doping Ti based photocatalysts surface6+(SO4 2-)。
The present invention also provides a kind of method for preparing high-performance nonmetal doping Ti based photocatalysts, methods described include with
Lower step：
1) pre-process：Titanium source and nitrogen source are dried rear finely ground, the nitrogen source is urea, thiocarbamide or ammonium sulfate, described
Titanium source is titanium dioxide；
2) calcine：Above-mentioned finely ground titanium source and nitrogen source are calcined under high temperature, obtain product N-TiO at initial stage2；
3) impregnate：The product that upper step obtains is impregnated in sulfate liquor；
4) dry：Dried after the product of upper step is separated by filtration, obtain final product S/N-TiO2。
Wherein, the drying condition of the step 1) is 80-110 DEG C of 4~6h of drying in baking oven.
Wherein, the titanium source can be industrial grade anatase, industrial titanium dioxide.
Wherein, the calcination condition of the step 2) is in Muffle furnace under the conditions of 300-900 DEG C, calcines 1~8h.
Preferably, the calcination condition of the step 2) is in Muffle furnace under the conditions of 400-600 DEG C, calcines 5~8h.
Wherein, nitrogen source and titanium source are calcined after being mixed according to mass ratio N: Ti=0.05~20% in the step 2).
Wherein, sulfate is sodium sulphate, potassium sulfate in the step 3), is weighed according to mass ratio S: Ti=0.1~10%
Sulfate, prepare corresponding sulfate liquor.
Wherein, 12~24h of dip time in the step 3), shaking table dipping.
Wherein, drying condition is 80-110 DEG C of dry 4-8h in baking oven in the step 4).
Specifically, the step of the inventive method is as follows：
(1) pre-process：Titanium source and nitrogen source are heat-treated, 80-110 DEG C of 4~6h of drying in baking oven, then by titanium source
With nitrogen source in mortar it is finely ground respectively；The nitrogen source is urea, ammonium sulfate or thiocarbamide, and the titanium source is titanium dioxide；
(2) calcine：Above-mentioned finely ground raw material is mixed according to the ratio of mass ratio N: Ti=0.05~20%, and existed again
Mix finely ground in mortar, by it in Muffle furnace under the conditions of 300-900 DEG C, calcine 1~8h, obtain flaxen product N-
TiO2；
(3) impregnate：Ratio according to mass ratio S: Ti=0.1~10% weighs sulfate, and it is molten to prepare corresponding sulfate
Liquid, then to the N-TiO of above-mentioned synthesis in the way of solvent is excessive2It is impregnated in 12~24h in sulfate liquor；
(4) dry：The product obtained in step (3) is separated by filtration, dried in an oven under the conditions of 80-110 DEG C
4~8h is dried, obtains final high-performance nonmetal doping Ti based photocatalysts S/N-TiO2。
Using the raw material such as thiocarbamide, urea or ammonium sulfate, industrial grade anatase, industrial titanium dioxide in the present invention, by more
The modified Nano TiO with S/N codopes is made in simple synthetic method2Photochemical catalyst.After the present invention is using grinding solid phase method
It the method for dipping, more fully can be effectively bonded under high temperature action using raw material, form the lattice defect of inside, so as to
Make the degradation effect of catalyst product more preferable.The present invention photochemical catalyst by body phase part oxygen atom substituted by nitrogen-atoms
Lacking oxygen is shown, there is stronger oxidability, while the surface nature of material is by S6+(SO4 2-) modified, S (VI's) contains
Oxygen acid group form is SO4 2-, SO4 2-In two monovalent O just with Ti sills Ti be coordinated bonding, formed electron delocalization effect
Should, SO4 2-The surface that is supported on more tend towards stability, the chelation of its double oxygen atoms, be advantageous to improve material ratio superficiality
Matter, it is easy to the absorption of material and pollutant, there is efficient photolytic activity.
One aspect of the present invention by N by being doped to TiO2Lattice in, in TiO2Body phase in formed nonmetalloid lack
Fall into, make it have special redox ability；On the other hand, by S surface modification, the surface of composite photo-catalyst is improved
Acid and surface nature, improve the adsorption capacity of catalyst.
The invention provides a kind of high effective and modified TiO of normal temperature and pressure2The method of photochemical catalyst, it is real under ultraviolet light conditions
The COD handling rates of border industrial wastewater can reach 80-90%.Photochemical catalyst preparation method of the present invention is simple, is easy to extensive
Industrialized production.The inventive method simple production process, raw material are cheap and easy to get, and gained powder has efficient photocatalytic activity,
TiO is widened2Application in photocatalysis field, for design and development of new there is high photoactive photochemical catalyst to provide think of
Road.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after present disclosure has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within limited range of the present invention.
A kind of method for preparing high-performance nonmetal doping Ti based photocatalysts, the described method comprises the following steps：
1) pre-process：Titanium source and nitrogen source are dried rear finely ground, the nitrogen source is urea or thiocarbamide, and the titanium source is two
Titanium oxide；
2) calcine：Above-mentioned finely ground titanium source and nitrogen source are calcined under high temperature, obtain product N-TiO at initial stage2；
3) impregnate：The product that upper step obtains is impregnated in sulfate liquor；
4) dry：Dried after the product of upper step is separated by filtration, obtain final product.
Wherein, the drying condition of the step 1) is 80-110 DEG C of 4~6h of drying in baking oven.
Wherein, the titanium source can be industrial grade anatase.
Wherein, the calcination condition of the step 2) is in Muffle furnace under the conditions of 300-900 DEG C, calcines 1~8h.
Wherein, nitrogen source and titanium source are calcined after being mixed according to mass ratio N: Ti=0.05~20% in the step 2).
Wherein, sulfate is sodium sulphate, potassium sulfate in the step 3), is weighed according to mass ratio S: Ti=0.1~10%
Sulfate, prepare corresponding sulfate liquor.
Wherein, 12~24h of dip time in the step 3), shaking table dipping.
Wherein, drying condition is 80-110 DEG C of dry 4-8h in baking oven in the step 4).
Embodiment 1
By TiO2With urea in baking oven 80 DEG C of dry 6h, it is then finely ground respectively in agate mortar.By finely ground TiO2With
Urea, proportionally weigh 8g, 0.4g respectively, be well mixed after again by mixture in agate mortar it is finely ground uniformly, then fill
Enter in crucible and compress in fact, crucible is put into Muffle furnace under the conditions of 400 DEG C, calcine 5h, after it is cooled to room temperature, obtain yellowish
Color solid powder, is denoted as N-TiO2；0.16g Na are weighed in addition2SO4Solution is configured to, takes solution 50mL, will be obtained above
N-TiO2It is added thereto, ultrasound makes it be uniformly dispersed, and under the conditions of shaking table, shakes 24h, afterwards filters the mixed liquor of gained, dries
100 DEG C of dry 6h, obtain flaxen photochemical catalyst S/N-TiO in case2。
The sign of product of the present invention is mainly determined by the acid amount of product, first to N-TiO2The measure of sour amount is carried out, so
Afterwards again to SO42-Dopant material after dipping carries out acidimetric estimation, finds its obvious increase of acid amount of the catalyst after modification,
So it is defined as target product.
Embodiment 2
By TiO2With urea in baking oven 100 DEG C of dry 4h, it is then finely ground respectively in agate mortar.By finely ground TiO2
And urea, proportionally weigh 8g, 0.8g respectively, be well mixed after again by mixture in agate mortar it is finely ground uniformly, then
It is fitted into crucible and compresses in fact, crucible is put into Muffle furnace under the conditions of 600 DEG C, calcines 5h, after it is cooled to room temperature, obtain light
Yellow solid powder, N-TiO2；0.4g (NH are weighed in addition4)2SO4Certain density solution is configured to, takes solution 50mL, will
N-TiO obtained above2It is added thereto, ultrasound makes it be uniformly dispersed, and under the conditions of shaking table, 24h is shaken, afterwards by the mixing of gained
Liquid is filtered, and 6h is dried in baking oven, obtains flaxen photochemical catalyst S/N-TiO2。
Embodiment 3
By industrial titanium dioxide and thiocarbamide in baking oven 110 DEG C of dry 4h, it is then finely ground respectively in agate mortar.Then will
Industrial titanium dioxide and thiocarbamide weigh 12g, 0.96g respectively, be well mixed after again by mixture in agate mortar it is finely ground uniformly, so
It is fitted into afterwards in crucible and compresses in fact, crucible is put into Muffle furnace under the conditions of 500 DEG C, calcines 5h, after it is cooled to room temperature, obtain
Faint yellow solid powder；0.6g Na are weighed in addition2SO4Certain density solution is configured to, solution 50mL is taken, is obtained above-mentioned
Product be added thereto, ultrasound makes it be uniformly dispersed, and under the conditions of shaking table, shakes 24h, afterwards filters the mixed liquor of gained, dries
6h is dried in case, obtains flaxen photochemical catalyst S/N-TiO2。
Embodiment 4
By titanium dioxide and ammonium sulfate in baking oven 90 DEG C of dry 5h, it is then finely ground respectively in agate mortar.Then will
Titanium dioxide and ammonium sulfate weigh 12g, 2.4g respectively, be well mixed after again by mixture in agate mortar it is finely ground uniformly, so
It is fitted into afterwards in crucible and compresses in fact, crucible is put into Muffle furnace under the conditions of 600 DEG C, calcines 6h, after it is cooled to room temperature, obtain
Faint yellow solid powder；1.2g Na are weighed in addition2SO4Certain density solution is configured to, solution 50mL is taken, is obtained above-mentioned
Product be added thereto, ultrasound makes it be uniformly dispersed, and under the conditions of shaking table, shakes 24h, afterwards filters the mixed liquor of gained, dries
110 DEG C of dry 6h, obtain flaxen photochemical catalyst S/N-TiO in case2。
Embodiment 5
Gained S/N co-doped nanos are modified TiO in above-described embodiment 1-42Photochemical catalyst S/N-TiO2, be designated as respectively A,
B、C、D.Photochemical catalyst A, B, C, D obtained by embodiment are done into adsorption capacity contrast, embodiment synthesis material with commercially available commercial P25 respectively
Adsorption capacity of the adsorption capacity of material than commercially available commercial P25 is high, therefore photochemical catalyst of the present invention has higher specific surface area,
So as to there is more preferable degradation effect.
The performance evaluation data that catalyst is tested by photocatalysis experimental probes see the table below.(note：The initial COD of waste water is
500mg/L；COD is tested using National Standard Method CODCr)
| Photochemical catalyst | Actual waste water water outlet CODCr(mg/L) |
| A (embodiment 1) | 63 |
| B (embodiment 2) | 68 |
| C (embodiment 3) | 61 |
| D (embodiment 4) | 65 |
It can be seen that removal of the photochemical catalyst of the present invention for COD has very high efficiency, COD handling rates can reach 80-
90%.
The high-performance nonmetal doping Ti based photocatalysts of the present invention have high specific surface area, have to organic wastewater etc.
There are stronger photocatalytic degradation capability and adsorption capacity, be suitable for related organic wastewater COD improvement.
It is above the description to the embodiment of the present invention, by the foregoing description of the disclosed embodiments, makes this area special
Industry technical staff can realize or using the present invention.A variety of modifications to these embodiments come to those skilled in the art
Say and will be apparent, generic principles defined herein can not depart from the situation of the spirit or scope of the present invention
Under, realize in other embodiments.Therefore, the present invention is not intended to be limited to the embodiments shown herein, but to accord with
Close the most wide scope consistent with principles disclosed herein and features of novelty.
Claims (9)
- A kind of 1. high-performance nonmetal doping Ti based photocatalysts, it is characterised in that the high-performance nonmetal doping Ti base light Catalyst is that S/N co-doped nanos are modified TiO2Photochemical catalyst S/N-TiO2；The high-performance nonmetal doping Ti base optic catalytics Contain a certain amount of N atoms in the body phase of agent, N: Ti mass ratio is 0.05~20%；In the high-performance nonmetal doping Ti bases Photocatalyst surface has S6+(SO4 2-)。
- A kind of 2. method for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that the high-performance is nonmetallic Doping Ti based photocatalysts are that S/N co-doped nanos are modified TiO2Photochemical catalyst S/N-TiO2, methods described includes following step Suddenly：1) pre-process：Titanium source and nitrogen source are dried rear finely ground, the nitrogen source is urea, thiocarbamide or ammonium sulfate, the titanium source It is titanium dioxide；2) calcine：Above-mentioned finely ground titanium source and nitrogen source are calcined under high temperature, obtain product N-TiO at initial stage2；3) impregnate：The product that upper step obtains is impregnated in sulfate liquor；4) dry：Dried after the product of upper step is separated by filtration, obtain final product S/N-TiO2。
- 3. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute The drying condition for stating step 1) is 80-110 DEG C of 4~6h of drying in baking oven.
- 4. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute The calcination condition for stating step 2) is in Muffle furnace under the conditions of 300-900 DEG C, calcines 1~8h.
- 5. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute Nitrogen source and titanium source in step 2) is stated to be calcined after mixing according to mass ratio N: Ti=0.05~20%.
- 6. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute It is sodium sulphate, potassium sulfate to state sulfate in step 3).
- 7. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute State in step 3) and weigh sulfate according to mass ratio S: Ti=0.1~10%, prepare corresponding sulfate liquor.
- 8. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute State 12~24h of dip time in step 3), shaking table dipping.
- 9. the method according to claim 2 for preparing high-performance nonmetal doping Ti based photocatalysts, it is characterised in that institute It is 80-110 DEG C of dry 4-8h in baking oven to state drying condition in step 4).
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