CN100525905C - Nanometer semiconductor oxidation photocatalyst and preparation method thereof - Google Patents
Nanometer semiconductor oxidation photocatalyst and preparation method thereof Download PDFInfo
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- CN100525905C CN100525905C CNB2007101782398A CN200710178239A CN100525905C CN 100525905 C CN100525905 C CN 100525905C CN B2007101782398 A CNB2007101782398 A CN B2007101782398A CN 200710178239 A CN200710178239 A CN 200710178239A CN 100525905 C CN100525905 C CN 100525905C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
Disclosed is a photocatalyst of nanometer semiconductor oxide and process for preparing the oxide, belonging to the technical field of photocatalysts. The catalyst is composed of nanometer semiconductor metallic oxide, arizonite nanometer particle and spinel nanometer particle, wherein the nanometer semiconductor metallic oxide is nickel oxide and titanium dioxide, the arizonite nanometer particle is nickel titanate, and the spinel nanometer particle is nickel-titanium spinel. The composition and content of the catalyst can be adjusted by the weighing of nickel-titanium materials, by roasting temperature and by acid treatment. The catalyst of the invention is adaptable for purification treatment of the photodecomposition of organic pollutants in air and water.
Description
Technical field
The invention belongs to the photocatalyst technology field, particularly relate to a kind of nanometer semiconductor oxidation photocatalyst and preparation method thereof, can absorb the photochemical catalyst of ultraviolet light and visible light effectively.
Technical background
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.The photocatalytic activity of the conductor oxidate of nanostructured, the degree of depth of degradation of organic substances and selectivity and quantum yield all are greatly improved than general conductor oxidate, thereby nano-photocatalyst material is just becoming the strong instrument that nanosecond science and technology early directly promote the well-being of mankind.
Mainly based on the photocatalysis technology of nano titanium oxide semiconductor (energy gap 3.2eV), only under less than the ultraviolet light of 400nm, can show activity at present, thereby limit it in industrial extensive use.As everyone knows, (energy of wavelength 400～750nm) is about 43% of all sunshines, and the ultraviolet ray less than 5% of wavelength below 400nm to shine the visible light on the face of land.Therefore, exploitation can effectively utilize ultraviolet ray and the catalysis material of visible light simultaneously and realize that wastewater treatment or air cleaning are to environmental protection with energy-conservationly all have and important meaning.
Summary of the invention
The object of the present invention is to provide a kind of nanometer semiconductor oxidation photocatalyst and preparation method thereof, under ultraviolet light and visible light condition, all has active photochemical catalyst, this nanometer semiconductor oxidation photocatalyst, can keep advantages of high catalytic activity, manufacturing process is simple simultaneously, cost is lower.
Catalyst provided by the invention is made up of nano semi-conductor metal oxide, arizonite nano particle, spinel nano particle, it is characterized in that composition by changing catalyst and content realizes the response to visible light, reach the purpose of utilizing ultraviolet light and visible light simultaneously.
Described nano semi-conductor metal oxide is nickel oxide (NiO) and titanium dioxide (TiO
2), the arizonite nano particle is nickel titanate (NiTiO
3), the spinel nano particle is NiTi spinelle (Ni
2TiO
4).
To account for catalyst gross mass percentage be 15～45% to nickel oxide in the described photochemical catalyst, and particle diameter is 10～30nm; It is 0～55% that titanium dioxide accounts for catalyst gross mass percentage, and particle diameter is 10～20nm; It is 5～75% that nickel titanate accounts for catalyst gross mass percentage, and particle diameter is 10～40nm, and it is 4～45% that the NiTi spinelle accounts for catalyst gross mass percentage, and particle diameter is 5～20nm.
Preparation method with ultraviolet light and visible light-responded photochemical catalyst of the present invention is as follows:
(1) preparation of presoma: adopt the even coprecipitation of urea, soon nickel nitrate, titanium tetrachloride, urea, deionized water are after 1:0.2～0.4:10～20:555～1111 mix according to mol ratio, 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 photochemical catalyst: presoma roasting 4～8h in 600～900 ℃ of high temperature of preparation is got the Nano semiconductor photocatalyst powder.With two parts of quality such as catalyst is divided into, get a copy of it pressed powder be dissolved in 100～200ml sulfuric acid solution (5～10M), stir 8～24h, suction filtration, the deionized water washing, after the oven dry the photocatalyst powder that changes of content.
The photochemical catalyst of described different composition and content is to be achieved by amount of substance ratio, change sintering temperature and the acid treatment that changes reactant nickel nitrate and titanium tetrachloride.
In the step (1), prepared presoma has the crystal structure of layered double hydroxide (hydrotalcite).
Nanometer semiconductor oxidation photocatalyst of the present invention can keep efficiently under the ultraviolet light activity, forms and content makes catalyst effectively by excited by visible light by modulation, and Application of Catalyst is extended to the visible region.
Photochemical catalyst of the present invention can utilize ultraviolet ray in the sunshine and the visible light photocatalysis treatment to 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.
The specific embodiment
Embodiment 1
A. photochemical catalyst preparation: 0.005mol Nickelous nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in 100ml (5.55mol) deionized water, change the 250ml there-necked flask after the dissolving over to, stirring and refluxing 10h.After reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.Precursor powder is put into the porcelain crucible, place muffle furnace to be heated to 700 ℃ from room temperature, 10 ℃/min of programming rate, insulation 4h is cooled to room temperature naturally and gets photocatalyst powder.
B. photocatalysis experiment: get the 25mg catalyst fines and add 100ml methylene blue (1 * 10
-5M) in the solution, evenly stir, place the quartzy photo catalysis reactor of logical cooling water, first dark reaction 30min.After the illumination of turning on light.The 500W high-pressure sodium lamp is selected in the ultraviolet lamp source for use, reaction time 120min; The visible lamp source is selected 125W fluorescent lamp (wavelength is greater than 400nm), reaction time 24h for use.Measure solution concentration with ultraviolet-visible spectrophotometer.
The results are shown in Table 1.
Embodiment 2
A. photochemical catalyst preparation: 0.005mol Nickelous nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in 100ml (5.55mol) deionized water, change the 250ml there-necked flask after the dissolving over to, stirring and refluxing 10h.After reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.Precursor powder is put into the porcelain crucible, place muffle furnace to be heated to 700 ℃ from room temperature, 10 ℃/min of programming rate, insulation 4h is cooled to room temperature naturally and gets pressed powder.With two parts of quality such as pressed powder is divided into, get a copy of it pressed powder and be dissolved in 100ml sulfuric acid solution (5M), stirring reaction 24h.Suction filtration then, spending deionised water is 7 to pH, filter cake gets photocatalyst powder in 60 ℃ of oven dryings.
B. photocatalysis experiment: get the 25mg catalyst fines and add 100ml methylene blue (1 * 10
-5M) in the solution, evenly stir, place the quartzy photo catalysis reactor of logical cooling water, first dark reaction 30min.After the illumination of turning on light.The 500W high-pressure sodium lamp is selected in the ultraviolet lamp source for use, reaction time 120min; The visible lamp source is selected 125W fluorescent lamp (wavelength is greater than 400nm), reaction time 24h for use.Measure solution concentration with ultraviolet-visible spectrophotometer.
The results are shown in Table 1.
Embodiment 3
A. photochemical catalyst preparation: 0.005mol Nickelous nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in 100ml (5.55mol) deionized water, change the 250ml there-necked flask after the dissolving over to, stirring and refluxing 10h.After reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.Precursor powder is put into the porcelain crucible, place muffle furnace to be heated to 900 ℃ from room temperature, 10 ℃/min of programming rate, insulation 4h is cooled to room temperature naturally and gets photocatalyst powder.
B. photocatalysis experiment: get the 25mg catalyst fines and add 100ml methylene blue (1 * 10
-5M) in the solution, evenly stir, place the quartzy photo catalysis reactor of logical cooling water, first dark reaction 30min.After the illumination of turning on light.The 500W high-pressure sodium lamp is selected in the ultraviolet lamp source for use, reaction time 120min; The visible lamp source is selected 125W fluorescent lamp (wavelength is greater than 400nm), reaction time 24h for use.Measure solution concentration with ultraviolet-visible spectrophotometer.
The results are shown in Table 2.
Embodiment 4
A. photochemical catalyst preparation: 0.005mol Nickelous nitrate hexahydrate, 0.002mol titanium tetrachloride and 0.1mol urea are added in 100ml (5.55mol) deionized water, change the 250ml there-necked flask after the dissolving over to, stirring and refluxing 10h.After reaction finishes, the product suction filtration, spending deionised water is 7 to pH, filter cake gets precursor powder in 60 ℃ of oven dryings.Precursor powder is put into the porcelain crucible, place muffle furnace to be heated to 900 ℃ from room temperature, 10 ℃/min of programming rate, insulation 4h is cooled to room temperature naturally and gets pressed powder.With two parts of quality such as pressed powder is divided into, get a copy of it pressed powder and be dissolved in 100ml sulfuric acid solution (5M), stirring reaction 24h.Suction filtration then, spending deionised water is 7 to pH, filter cake gets photocatalyst powder in 60 ℃ of oven dryings.
B. photocatalysis experiment: get the 25mg catalyst fines and add 100ml methylene blue (1 * 10
-5M) in the solution, evenly stir, place the quartzy photo catalysis reactor of logical cooling water, first dark reaction 30min.After the illumination of turning on light.The 500W high-pressure sodium lamp is selected in the ultraviolet lamp source for use, reaction time 120min; The visible lamp source is selected 125W fluorescent lamp (wavelength is greater than 400nm), reaction time 24h for use.Measure solution concentration with ultraviolet-visible spectrophotometer.
The results are shown in Table 2.
Table 1 photochemical catalyst is formed and the methylene blue degradation rate
Table 2 photochemical catalyst is formed and the methylene blue degradation rate
Claims (4)
1, a kind of nanometer semiconductor oxidation photocatalyst is characterized in that: this catalyst is made up of nano semi-conductor metal oxide, arizonite nano particle, spinel nano particle; Described nano semi-conductor metal oxide is nickel oxide and titanium dioxide, and the arizonite nano particle is a nickel titanate, and the spinel nano particle is the NiTi spinelle; Wherein, it is 15～45% that nickel oxide accounts for catalyst gross mass percentage, and it is 0～55% that titanium dioxide accounts for catalyst gross mass percentage, and it is 5～75% that nickel titanate accounts for catalyst gross mass percentage, and it is 4～45% that the NiTi spinelle accounts for catalyst gross mass percentage; The light reaction of catalyst is carried out under ultraviolet light, visible light or sunshine.
2, oxidation photocatalyst according to claim 1 is characterized in that: the nickel oxide particle diameter is 10～30nm, and the titanium dioxide granule diameter is 10～20nm; The nickel titanate particle diameter is 10～40nm; NiTi spinel particle diameter is 5～20nm.
3, a kind of method for preparing the described photochemical catalyst of claim 1 is characterized in that, processing step is:
The preparation of a, presoma: is after 1:0.2～0.4:10～20:555～1111 mix, to react 2～10h under the stirring and refluxing condition with nickel nitrate, titanium tetrachloride, urea, deionized water according to mol ratio, obtains the solid precipitation; Suction filtration, deionized water washing then, dry pressed powder;
The preparation of b, photochemical catalyst: roasting 4～8h in 600～900 ℃ gets the Nano semiconductor photocatalyst powder with presoma; With two parts of quality such as catalyst is divided into, get a copy of it and be dissolved in 5～10mol/L sulfuric acid solution, stir 8～24h, suction filtration, the deionized water washing gets the photocatalyst powder that content changes after the oven dry.
4, method according to claim 3 is characterized in that: prepared presoma has the crystal structure of layered double hydroxide.
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| US9757715B2 (en) | 2015-11-20 | 2017-09-12 | National Tsing Hua University | Composite photocatalyst, manufacturing method thereof, kits containing composite photocatalyst, and bactericide photocatalyst |
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| CN106179352B (en) * | 2016-07-08 | 2019-01-11 | 武汉理工大学 | A kind of Ni-based nano particle catalysis material of multiphase metatitanic acid and preparation method thereof |
| CN108597879B (en) * | 2018-03-19 | 2020-09-22 | 西北师范大学 | TiO 22Preparation method of nanowire/NiO nanosheet/porphyrin composite material |
| CN110745874A (en) * | 2018-07-23 | 2020-02-04 | 荆门市格林美新材料有限公司 | Cd (cadmium)2+Preparation method of basic nickel carbonate doped microspheres |
| CN110745879A (en) * | 2018-07-23 | 2020-02-04 | 荆门市格林美新材料有限公司 | Mg2+Preparation method of basic nickel carbonate doped microspheres |
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| CN110745877A (en) * | 2018-07-23 | 2020-02-04 | 荆门市格林美新材料有限公司 | Mn (manganese)2+Preparation method of basic nickel carbonate doped microspheres |
| CN110745873A (en) * | 2018-07-23 | 2020-02-04 | 荆门市格林美新材料有限公司 | Mo6+Preparation method of basic nickel carbonate doped microspheres |
| CN110745878A (en) * | 2018-07-23 | 2020-02-04 | 荆门市格林美新材料有限公司 | Ce3+Preparation method of basic nickel carbonate doped microspheres |
| CN110745880A (en) * | 2018-07-23 | 2020-02-04 | 荆门市格林美新材料有限公司 | Cu2+Preparation method of basic nickel carbonate doped microspheres |
| CN108993516B (en) * | 2018-08-17 | 2021-05-18 | 太原理工大学 | Composite oxide catalyst with nickel-titanium hydrotalcite as precursor and preparation method and application thereof |
| CN109529793B (en) * | 2018-11-14 | 2021-08-31 | 济南大学 | Preparation method and application of magnetic hydrotalcite loaded titanium dioxide composite material |
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2007
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| Formation of Ni–Ti-layered double hydroxides usinghomogeneous precipitation method. Xin Shu, Wenhui Zhang, Jing He, Fanxing Gao, YuexiangZhu.Solid State Sciences,Vol.8 . 2006 |
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| US9757715B2 (en) | 2015-11-20 | 2017-09-12 | National Tsing Hua University | Composite photocatalyst, manufacturing method thereof, kits containing composite photocatalyst, and bactericide photocatalyst |
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