CN101502792B - Inorganic sensitized visible-light responsive photocatalyst and preparation method thereof - Google Patents

Inorganic sensitized visible-light responsive photocatalyst and preparation method thereof Download PDF

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CN101502792B
CN101502792B CN2009100773456A CN200910077345A CN101502792B CN 101502792 B CN101502792 B CN 101502792B CN 2009100773456 A CN2009100773456 A CN 2009100773456A CN 200910077345 A CN200910077345 A CN 200910077345A CN 101502792 B CN101502792 B CN 101502792B
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deionized water
presoma
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suction filtration
oxide
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CN101502792A (en
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何静
舒心
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Beijing University of Chemical Technology
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Abstract

The invention relates to an inorganic sensitized photo catalyst and a preparation method thereof, and belongs to the technical field of photo catalysts. The catalyst consists of two or three nano metal oxides, wherein one or two metal oxides are photocatalysis active species, and the other one or two metal oxides are photosensitizers. The photocatalysis active species are titanium dioxide, nitrogen-doped titanium dioxide, boron-doped titanium dioxide, phosphor-doped titanium dioxide and zinc oxide; and the photosensitizers are nickel oxide, dichromium trioxide and ferric oxide. The composition and content of the catalyst can be adjusted by a quantity ratio of precursor element substances. The catalyst of the invention is applicable to visible light decomposition and purification treatment of organic pollutants in air and water; and the preparing process is simple, the cost is lower, and the catalyst promotes photo-catalyzed reaction to be further practical.

Description

A kind of inorganic sensitized visible-light responsive photocatalyst and preparation method thereof
Technical field
The invention belongs to the photocatalyst technology field, particularly relate to a kind of inorganic sensitized photochemical catalyst and preparation method thereof, this catalyst can be activated in visible-range, the catalytic degradation organic matter.
Background technology
Photocatalysis technology is the focus of current scientific research, and its range of application is very extensive, as sewage disposal, air cleaning, solar energy utilization, antibiotic, antifog and self-cleaning function etc.Material with photocatalyst mainly is some semiconducting compounds at present.Common have a TiO 2, ZnO, WO 3, SnO 2Deng oxide, selenides such as CdS, ZnS sulfides and CdSe.TiO wherein 2Because have nontoxic, excellent characteristics such as catalytic activity is high, oxidability is strong, good stability, and becoming the photochemical catalyst of normal use, is a kind of very rising pollution control material.
TiO 2The subject matter of base optic catalytic material practicability is: TiO 2(3.0～3.2eV), the efficiency of light energy utilization is lower, and the absorption of sunshine is confined to the ultra-violet (UV) band, and the efficiency of light energy utilization is less than 5% for the forbidden band broad.As everyone knows, (energy of wavelength 400～750nm) is about 43% of all sunshines, and therefore, the catalysis material that exploitation can effectively utilize visible light is to environmental protection and energy-conservationly all have and important meaning to shine the visible light on the face of land.Domestic and international researcher has done number of research projects at this problem, has developed multiple modification TiO 2Method, expansion in various degree TiO 2The photoresponse scope, improved its visible light catalysis activity.Wherein photoactivate (inorganic sensitized, organic sensitization) and nonmetallic ion (N, C, S, B etc.) mix and are considered to the most promising method of modifying, have been widely used in visible light photocatalytic degradation organic contamination and area of solar cell.
Summary of the invention
The object of the present invention is to provide a kind of inorganic sensitized photochemical catalyst and preparation method thereof, can keep stable high catalytic activity under the radiation of visible light condition, manufacturing process is simple simultaneously, cost is lower.
Catalyst provided by the invention is made up of two or three metal oxide nanoparticles, and one or both metal oxides are as the photocatalytic activity species, for not mixing or nonmetallic ion-doped metal oxide; One or both metal oxides are as photosensitizer, for absorbing the metal oxide of visible light.This photochemical catalyst can effectively utilize the visible light in the sunshine that organic pollution in air, waste water, surface water and the drinking water is carried out photocatalytic degradation.
That be used as the photocatalytic activity species in the described metal oxide is titanium dioxide (TiO 2), nitrogen-doped titanium dioxide (N-TiO 2), boron doped titanic oxide (B-TiO 2), phosphorus doping titanium dioxide (P-TiO 2) and zinc oxide (ZnO), as photosensitizer is nickel oxide (NiO), chrome green (Cr 2O 3) and di-iron trioxide (Fe 2O 3).
The preparation method of inorganic sensitized visible-light responsive photocatalyst of the present invention is as follows:
(1) preparation of presoma one: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, urea, deionized water according to mol ratio: 0.2～0.4: 10～20: 555 mix after, under the stirring and refluxing condition, react 2～10h, obtain the solid precipitation.Suction filtration, deionized water washing then, dry pressed powder.
(2) preparation of presoma two: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, urea, deionized water according to mol ratio: 0.2～0.4: 10～20: 555 mix after, under the stirring and refluxing condition, react 1～3h, obtain the solid precipitation, spend deionised water behind the suction filtration, the sodium carbonate that adds 0.08～0.16 mol, put into HTHP hydro-thermal still, under 100～150 ℃ of conditions, react 5～10h, obtain the solid precipitation.Suction filtration, deionized water washing then, dry pressed powder.
(3) preparation of presoma three: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, NaOH, sodium hydrogen phosphate or ammonium borate, deionized water according to mol ratio: 0.2～0.4: 4.5～6: 0.2～0.4: 1111 slowly mix after, feed nitrogen, react 12～24h down in 40～80 ℃ of stirring conditions, obtain the solid precipitation.Suction filtration, deionized water washing then, dry pressed powder.
(4) preparation of presoma four: with zinc nitrate, chromium trichloride, ferric nitrate, NaOH, deionized water according to mol ratio be slowly mixed in 1: 0.1～0.15: 0.1～0.15: 4.5～6: 1111 after, react 10～24h down in 40～80 ℃ of stirring conditions, obtain the solid precipitation.Suction filtration, deionized water washing then, dry pressed powder.
(5) preparation of photochemical catalyst: the presoma of preparation is got the nano-metal-oxide photocatalyst powder respectively at roasting 4～8h in 400～500 ℃.
Step (1) is in (4), and prepared presoma has the crystal structure of atomic ordered.
In the step (5), prepared photochemical catalyst is for sharing the nano-metal-oxide of Lattice Oxygen.
Nano-metal-oxide photochemical catalyst of the present invention makes catalyst effectively by excited by visible light by the composition and the content of modulation presoma element, and keeps the visible light activity of efficient stable, and Application of Catalyst is extended to the visible region.
Photochemical catalyst of the present invention can effectively utilize visible light in the sunshine to the photocatalysis treatment of organic pollution in air, waste water, surface water and the drinking water, and manufacturing process is simple simultaneously, cost is lower, promotes light-catalyzed reaction further to push practicability to.
Description of drawings
Accompanying drawing 1 is the ultraviolet-visible absorption spectroscopy figure of nickel oxide sensitization titanium dioxide and nickel oxide sensitization nitrogen-doped titanium dioxide.
The specific embodiment
Embodiment 1
A. 0.005mol Nickelous nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in the 100mL deionized water, be stirred to evenly till;
B. change solution a over to the 250mL there-necked flask, react 10h under the stirring and refluxing condition;
C. after reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.
D. precursor powder is put into the porcelain crucible, placed muffle furnace to be heated to 500 ℃ from room temperature, insulation 4h reduces to room temperature naturally and promptly gets nickel oxide sensitization nitrogen-doped titanium dioxide photocatalyst (NiO-N-TiO 2).
Embodiment 2
A. 0.005mol Nickelous nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in the 100mL deionized water, be stirred to evenly till;
B. change solution a over to the 250mL there-necked flask, react 2h under the stirring and refluxing condition;
C. after reaction finishes, the product suction filtration, spend deionised water to pH be 8;
D. filter cake and 100mL 0.008mol sodium carbonate are stirred into suspension;
E. above-mentioned suspension is changed in the 200mL HTHP hydro-thermal still, place 100 ℃ of baking ovens to react 10h;
F. after reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.
G. precursor powder is put into the porcelain crucible, placed muffle furnace to be heated to 500 ℃ from room temperature, insulation 4h reduces to room temperature naturally and promptly gets nickel oxide sensitization titanium dioxide optical catalyst (NiO-TiO 2).
Embodiment 3
A. 0.0025mol Nickelous nitrate hexahydrate, 0.0025mol zinc nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in the 100mL deionized water, be stirred to evenly till;
B. change solution a over to the 250mL there-necked flask, react 10h under the stirring and refluxing condition;
C. after reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.
D. precursor powder is put into the porcelain crucible, placed muffle furnace to be heated to 500 ℃ from room temperature, insulation 4h reduces to room temperature naturally and promptly gets nickel oxide sensitized zinc oxide and nitrogen-doped titanium dioxide photocatalyst (NiO-ZnO and NiO-N-TiO 2).
Embodiment 4
A. 0.0025mol Nickelous nitrate hexahydrate, 0.0025mol zinc nitrate hexahydrate and 0.002mol titanium tetrachloride are added in the 100mL deionized water, be stirred to evenly till;
B. change solution a over to the 500mL four-hole boiling flask, under nitrogen protection,, react 24h down in 60 ℃ of stirring conditions with simultaneously slow Dropwise 5 0mL0.03mol sodium hydroxide solution of dropping funel and 50mL 0.004mol disodium phosphate soln.
C. after reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.
D. precursor powder is put into the porcelain crucible, placed muffle furnace to be heated to 500 ℃ from room temperature, insulation 4h reduces to room temperature naturally and promptly gets nickel oxide sensitized zinc oxide and phosphorus doping titanium dioxide optical catalyst (NiO-ZnO and NiO-P-TiO 2).
Embodiment 5
A. 0.005mol zinc nitrate hexahydrate, 0.00075mol six hydrated chromium trichlorides and 0.00075mol nine nitric hydrate iron are added in the 100mL deionized water, be stirred to evenly till;
B. change solution a over to the 500mL there-necked flask, slowly drip 100mL 0.03mol sodium hydroxide solution, react 24h down in 45 ℃ of stirring conditions with dropping funel.
C. after reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in drying at room temperature.
D. precursor powder is put into the porcelain crucible, placed muffle furnace to be heated to 500 ℃ from room temperature, insulation 4h reduces to room temperature naturally and promptly gets chrome green and di-iron trioxide sensitized zinc oxide photocatalyst (Cr 2O 3-Fe 2O 3-ZnO).

Claims (4)

1. inorganic sensitized visible-light responsive photocatalyst, this catalyst is made up of two or three metal oxide nanoparticles, it is characterized in that: one or both metal oxides are nonmetallic ion-doped or unadulterated metal oxide as the photocatalytic activity species; One or both metal oxides are as photosensitizer, for absorbing the metal oxide of visible light; This photochemical catalyst can effectively utilize the visible light in the sunshine that organic pollution in air, waste water, surface water and the drinking water is carried out photocatalytic degradation;
What be used as the photocatalytic activity species in the described metal oxide is titanium dioxide, nitrogen-doped titanium dioxide, boron doped titanic oxide, phosphorus doping titanium dioxide or zinc oxide, and as photosensitizer is nickel oxide, chrome green or di-iron trioxide; Photochemical catalyst is for sharing the nano-metal-oxide of Lattice Oxygen;
Described photochemical catalyst is meant the photochemical catalyst of taking following method preparation:
(1) preparation of presoma
A, presoma one: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, urea, deionized water according to mol ratio: 0.2～0.4: 10～20: 555 mix after, under the stirring and refluxing condition, react 2～10h, obtain solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
B, presoma two: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, urea, deionized water according to mol ratio: 0.2～0.4: 10～20: 555 mix after, under the stirring and refluxing condition, react 1～3h, obtain the solid precipitation, spend deionised water behind the suction filtration, the sodium carbonate that adds 0.08～0.16 mol, put into HTHP hydro-thermal still, under 100～150 ℃ of conditions, react 5～10h, obtain the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
C, presoma three: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, NaOH, sodium hydrogen phosphate or ammonium borate, deionized water according to mol ratio: 0.2～0.4: 4.5～6: 0.2～0.4: 1111 slowly mix after, feed nitrogen, react 12～24h down in 40～80 ℃ of stirring conditions, obtain the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
D, presoma four: with zinc nitrate, chromium trichloride, ferric nitrate, NaOH, deionized water according to mol ratio be slowly mixed in 1: 0.1～0.15: 0.1～0.15: 4.5～6: 1111 after, react 10～24h down in 40～80 ℃ of stirring conditions, obtain the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
(2) preparation of photochemical catalyst
The presoma of preparation is got the nano-metal-oxide photocatalyst powder respectively at roasting 4～8h in 400～500 ℃.
2. a method for preparing the described photochemical catalyst of claim 1 is characterized in that, processing step is:
(1) preparation of presoma
A, presoma one: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, urea, deionized water according to mol ratio: 0.2～0.4: 10～20: 555 mix after, under the stirring and refluxing condition, react 2～10h, obtain solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
B, presoma two: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, urea, deionized water according to mol ratio: 0.2～0.4: 10～20: 555 mix after, under the stirring and refluxing condition, react 1～3h, obtain the solid precipitation, spend deionised water behind the suction filtration, the sodium carbonate that adds 0.08～0.16 mol, put into HTHP hydro-thermal still, under 100～150 ℃ of conditions, react 5～10h, obtain the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
C, presoma three: is 0.5～1: 0～0.5 with nickel nitrate, zinc nitrate, titanium tetrachloride, NaOH, sodium hydrogen phosphate or ammonium borate, deionized water according to mol ratio: 0.2～0.4: 4.5～6: 0.2～0.4: 1111 slowly mix after, feed nitrogen, react 12～24h down in 40～80 ℃ of stirring conditions, obtain the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
D, presoma four: with zinc nitrate, chromium trichloride, ferric nitrate, NaOH, deionized water according to mol ratio be slowly mixed in 1: 0.1～0.15: 0.1～0.15: 4.5～6: 1111 after, react 10～24h down in 40～80 ℃ of stirring conditions, obtain the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
(2) preparation of photochemical catalyst
The presoma of preparation is got the nano-metal-oxide photocatalyst powder respectively at roasting 4～8h in 400～500 ℃.
3. method according to claim 2 is characterized in that: prepared presoma has the crystal structure of atomic ordered.
4. method according to claim 2 is characterized in that: prepared photochemical catalyst is for sharing the nano-metal-oxide of Lattice Oxygen.
CN2009100773456A 2009-02-19 2009-02-19 Inorganic sensitized visible-light responsive photocatalyst and preparation method thereof Expired - Fee Related CN101502792B (en)

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CN104307549B (en) * 2014-11-13 2016-08-17 武汉钢铁(集团)公司 Titanium dioxide ultraviolet photocatalyst of curpic carbonate load and preparation method thereof
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