CN101816943B - High-efficiency nano silver/silver bromide sunshine photocatalytic material and preparation method thereof - Google Patents
High-efficiency nano silver/silver bromide sunshine photocatalytic material and preparation method thereof Download PDFInfo
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- CN101816943B CN101816943B CN2010101741811A CN201010174181A CN101816943B CN 101816943 B CN101816943 B CN 101816943B CN 2010101741811 A CN2010101741811 A CN 2010101741811A CN 201010174181 A CN201010174181 A CN 201010174181A CN 101816943 B CN101816943 B CN 101816943B
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Abstract
The invention discloses a high-efficiency nano silver/silver bromide sunshine photocatalytic material and a preparation method thereof. The material consists of the nano silver and the micron-sized silver bromide, and the chemical formula is Ag/AgBr; and the nano silver is uniformly distributed on the surface of the silver bromide, the grain size of the silver bromide is 1 to 3 mu m, and the grain size of the silver bromide is 8 to 14 nm. Compared with the prior art, the prepared nano silver/silver bromide sunshine photocatalytic material can be used for purifying pollutants in water and sterilizing; the effect is much better than that of the conventional commonly used photocatalytic material P25 and a recently developed 'Wang catalyst'; the material can directly use solar energy with high efficiency, the photocatalytic ability is almost not decreased after being recycled for many times; and meanwhile, the nano silver/silver bromide sunshine photocatalytic material has the advantages of simple and convenient preparation process, low cost, and suitability for industrial production.
Description
Technical field:
The invention belongs to sunshine photocatalytic material and preparation method thereof, belong to nano silver/silver bromide sunshine photocatalytic material that purifies water pollutant and sterilization and preparation method thereof especially.
Technical background:
People are being faced with shortage of water resources, with serious pollution challenge.Through investigation, only the chemical pollutant in the running water just reaches thousands of kinds more than, and direct threats human beings'health.Under the background of energy crisis worldwide, for seeking the purification approach of effective low consumption, solar energy is the abundant and green extensive concern that causes scientists that cleans because of its source.Solar energy can be described as the inexhaustible energy to the mankind, and the gross energy that arrived the earth in a year is catabiotic 10,000 times of present 1 year of the whole world approximately.But regrettably, solar energy utilization rate is extremely low, and this is greatly limited the utilization of solar energy, and simultaneously, as photolysis water hydrogen gas, the tempting technical fields such as pollutant in light degradation air and the water much still can only rest on the low-level level.Therefore, preparation can utilize the catalysis material of sunshine to become the solution key of problem efficiently, has also obtained many chemists' concern and research in recent years.
Current, studying maximum catalysis materials is titanium dioxide, and wherein anatase and rutile structure are the catalysis materials of using always, the commercially available P25 type that is mainly.Currently be used to explain that the theory of the light-catalyzed reaction principle of titanium dioxide is semi-conductive band theory: when semiconductor is penetrated in the illumination that is equal to or greater than energy gap (Eg) with energy; Electronics on the semiconductor valence band can be excited and transit to conduction band; Simultaneously produce corresponding hole in valence band, this is just at the inner electronics (e that generates of semiconductor
-)-hole (h
+) right, under effect of electric field, electronics (e
-)-hole (h
+) to separating, move to particle surface, with the material that is adsorbed on the catalyst pellets sub-surface reduction or oxidation reaction taking place, thereby realizes the degraded of photodissociation water or pollutant.
But the band gap width of the titanium dioxide of anatase and rutile structure is respectively 3.2eV and 3.0eV, can only utilize the ultraviolet light that only accounts for sunshine 4%, and it is lack scope for their abilities to account in the sunshine 43% abundant visible light resource.The modified photocatalytic material of the titanium dioxide that mixes can extend to the visible region with absorption region effectively, but cationic modification significantly reduces the transformation efficiency of light quantum, or the dye molecule that is used for sensitization can in use progressively be degraded and inactivation.Therefore, the photocatalysis performance of titanium dioxide can only be low-level.
In view of the above-mentioned shortcoming of titanium dioxide, the very responsive silver halide of light has been caused the concern of a lot of researchers.But silver halide only has strong absorption at ultraviolet band, does not have absorption basically in the visible region, and silver halide is unstable, is prone to decompose.Discovered after silver halide and simple substance silver or tungstic acid etc. are compound, strong absorption is arranged in the visible region afterwards, be hopeful to replace the high-efficiency photocatalysis material that titanium dioxide becomes a new generation.
Recently; The Wang Peng of Shandong University etc. has prepared some composite photocatalyst materials based on silver chlorate or silver bromide, is 200810016610.5 at number of patent application, 200810016611.X; 200810016609.2; 200810016612.4 in done introduction, at this general designation " Wang Shi catalyst ", its effect is much better than the current catalysis material P25 that generally uses.But its preparation method and process are numerous and diverse, and photocatalysis experiment is under 300w xenon lamp (light below the elimination 400nm), to carry out, and wave band and intensity all have bigger difference with sunshine, can not reflect the photocatalysis effect under the direct sunshine truly.
Summary of the invention:
It is low numerous and diverse with " Wang Shi catalyst " preparation method to solar energy utilization rate to the present invention is directed to the P25 catalysis material; And problems such as effect is not very good provide a kind of more efficient and direct sunshine photocatalytic material that preparation technology is very easy and preparation method thereof.
Nano silver/silver bromide sunshine photocatalytic material of the present invention is made up of Nano Silver and micron-sized silver bromide, and chemical formula is Ag/AgBr, and Nano Silver is evenly distributed in the silver bromide surface, and the particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
The preparation of nano silver/silver bromide sunshine photocatalytic material of the present invention comprises the following steps:
(1) prepares micron-sized silver bromide: in liquor argenti nitratis ophthalmicus, add softex kw (CTAB); After stirring 5-10min; Add formic acid and ammoniacal liquor successively, be transferred in the autoclave 100-130 ℃ of reaction 2-8 hour then, separate, washing; Promptly obtain flaxen micron-sized silver bromide, the mol ratio of silver nitrate, softex kw, formic acid, ammoniacal liquor is 1: 3-5: 750-1100: 80-110;
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the water or absolute ethyl alcohol of q.s; Be exposed under the room light 1-5 hour; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface; Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.
The weight concentration of described formic acid is greater than 88%;
The weight concentration of described ammoniacal liquor is 25%-28%;
In the described step (2), preferred exposure time is 2 hours.
Nano silver/silver bromide sunshine photocatalytic material of the present invention; Because the plasma effect of nano surface silver; Just stopping to continue to decompose as long as the surface has the fraction Nano Silver to produce silver bromide, is stable when sunshine purifies, and strong absorption is arranged in the visible region simultaneously.
Because the best metallic conductor of silver, electronics can be transferred to catalyst surface fast, reacts with the pollutant that is adsorbed on catalyst surface, and photocatalytic speed and efficient are greatly enhanced.
The present invention compared with prior art; Prepared nano silver/silver bromide sunshine photocatalytic material can be used for purifying water pollutant and sterilization; Its effect is much better than the current catalysis material P25 that generally uses and " the Wang Shi catalyst " developed recently; Can directly utilize solar energy efficiently, and photo-catalysis capability does not descend basically after repeatedly recycling.Simultaneously, the preparation technology of nano silver/silver bromide sunshine photocatalytic material of the present invention is very easy, and is with low cost, is fit to commercial production.
Description of drawings:
The high-efficiency nano silver/silver bromide sunshine photocatalytic material photo-catalysis capability sketch map that Fig. 1: embodiment 1 is made.
The high-efficiency nano silver/silver bromide sunshine photocatalytic material photocatalysis stability sketch map that Fig. 2: embodiment 2 is made.
In Fig. 2,11 is that the made catalyst, 12 of the present invention is commercially available P25 catalyst.
The specific embodiment:
Be the non-limiting preparation embodiment of the present invention below, the present invention further described through these embodiment.
Embodiment 1:
(1) prepares micron-sized silver bromide: at the silver nitrate (AgNO of 10mL 0.015mol/L
3) add the CTAB of 0.2g in the solution, stir 5min after, add 4mL formic acid (weight concentration is greater than 88%) successively; Described formic acid; With 2.5mL ammoniacal liquor (weight concentration is 25%-28%), be transferred in the autoclave 100 ℃ of reactions 2 hours then, at last the product separating, washing is promptly obtained flaxen micron-sized silver bromide (AgBr).
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the water; Be exposed to room light following 1 hour; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface.Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.The particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
Embodiment 2:
(1) prepares micron-sized silver bromide: at the AgNO of 10mL 0.02mol/L
3The CTAB that adds 0.25g in the solution behind the stirring 8min, adds 5mL HCOOH and 3mL NH successively
3H
2O is transferred in the autoclave 120 ℃ of reactions 5 hours then, at last the product separating, washing is promptly obtained flaxen micron-sized AgBr.
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the absolute ethyl alcohol; Be exposed to room light following 1 hour; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface.Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.The particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
Embodiment 3:
(1) prepares micron-sized silver bromide: at the AgNO of 10mL 0.025mol/L
3The CTAB that adds 0.3g in the solution behind the stirring 10min, adds 6mL HCOOH and 3.5mL NH successively
3H
2O is transferred in the autoclave 130 ℃ of reactions 2 hours then, at last the product separating, washing is promptly obtained flaxen micron-sized AgBr.
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the water; Be exposed to room light following 5 hours; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface.Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.The particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
Embodiment 4:
(1) prepares micron-sized silver bromide: at the AgNO of 10mL 0.02mol/L
3The CTAB that adds 0.2g in the solution behind the stirring 10min, adds 5mL HCOOH and 3mL NH successively
3H
2O is transferred in the autoclave 120 ℃ of reactions 5 hours then, at last the product separating, washing is promptly obtained flaxen micron-sized AgBr.
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the absolute ethyl alcohol; Be exposed to room light following 1 hour; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface.Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.The particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
Embodiment 5:
(1) prepares micron-sized silver bromide: at the AgNO of 10mL 0.02mol/L
3The CTAB that adds 0.2g in the solution behind the stirring 10min, adds 5mL HCOOH and 3mL NH successively
3H
2O is transferred in the autoclave 130 ℃ of reactions 8 hours then, at last the product separating, washing is promptly obtained flaxen micron-sized AgBr.
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the water; Be exposed to room light following 1 hour; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface.Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.The particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
Embodiment 6:
(1) prepares micron-sized silver bromide: at the AgNO of 10mL 0.02mol/L
3The CTAB that adds 0.2g in the solution behind the stirring 10min, adds 5mL HCOOH and 3mL NH successively
3H
2O is transferred in the autoclave 100 ℃ of reactions 8 hours then, at last the product separating, washing is promptly obtained flaxen micron-sized AgBr.
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the absolute ethyl alcohol; Be exposed to room light following 3 hours; The faint yellow grey that is converted into, silver bromide partly resolves into silver-colored simple substance, is evenly distributed in the silver bromide surface.Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material.The particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
The evaluation method of nano silver/silver bromide sunshine photocatalytic material photocatalysis performance of the present invention:
(1) photo-catalysis capability:
Preparation 20mL reactant liquor; Wherein methyl orange concentration is 10mg/L; Add the 20mg embodiment of the invention 1 made nano silver/silver bromide sunshine photocatalytic material; Be placed directly in after the dispersion and carry out degradation experiment under the solar irradiation, the differential responses stage liquid of leaving away behind the catalyst is carried out ultraviolet-visible spectrum and follows the tracks of.Its result is as shown in Figure 1, and 1min is a degradable 86%, and 5min degrades basically fully.
(2) photocatalysis stability:
Adopting circulation catalysis to test estimates: prepare five parts of 20mL reactant liquors, wherein methyl orange concentration is 10mg/L.In first part of reactant liquor, add the made nano silver/silver bromide sunshine photocatalytic material of 20mg embodiment 2; Be placed directly in after the dispersion and carry out degradation experiment under the solar irradiation; Behind the 5min reactant liquor being carried out ultraviolet-visible spectrum characterizes; Isolate catalysis material, with used catalysis material respectively to second and third, four, five parts of reactant liquors degrade under the same conditions, use ultraviolet-visible spectrum to characterize successively.Its result is as shown in Figure 2, recycles through 5 times, and the catalytic capability of nano silver/silver bromide sunshine photocatalytic material of the present invention does not descend basically, all keeps very high photocatalysis level.
Claims (4)
1. the preparation method of a nano silver/silver bromide sunshine photocatalytic material comprises the following steps:
(1) prepares micron-sized silver bromide: in liquor argenti nitratis ophthalmicus, add softex kw; After stirring 5-10min; Add formic acid and ammoniacal liquor successively, be transferred in the autoclave 100-130 ℃ of reaction 2-8 hour then, separate, washing; Promptly obtain flaxen micron-sized silver bromide, the mol ratio of silver nitrate, softex kw, formic acid, ammoniacal liquor is 1: 3-5: 750-1100: 80-110;
(2) preparation nano silver/silver bromide sunshine photocatalytic material: the faint yellow silver bromide of gained in the step (1) is dispersed in the water or absolute ethyl alcohol of q.s; Be exposed under the room light 1-5 hour; The faint yellow grey that is converted into; Then product is separated drying, promptly get nano silver/silver bromide sunshine photocatalytic material;
Described nano silver/silver bromide sunshine photocatalytic material is made up of Nano Silver and micron-sized silver bromide, and chemical formula is Ag/AgBr, and Nano Silver is evenly distributed in the silver bromide surface, and the particle diameter of silver bromide is 1-3 μ m, and the particle diameter of Nano Silver is 8-14nm.
2. the preparation method of a kind of nano silver/silver bromide sunshine photocatalytic material according to claim 1, it is characterized in that: the weight concentration of described formic acid is greater than 88%.
3. the preparation method of a kind of nano silver/silver bromide sunshine photocatalytic material according to claim 1, it is characterized in that: the weight concentration of described ammoniacal liquor is 25%-28%;
4. the preparation method of a kind of nano silver/silver bromide sunshine photocatalytic material according to claim 1, it is characterized in that: in the described step (2), described exposure time is 2 hours.
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| CN102068999B (en) * | 2011-01-11 | 2012-11-07 | 中山大学 | Application of silver halide composite materials in preparing carbon dioxide into hydrocarbon under visible-light catalysis |
| CN102416335A (en) * | 2011-09-06 | 2012-04-18 | 华东理工大学 | Nano silver/cubic silver bromide photocatalysis material and preparation method thereof |
| CN102380405B (en) * | 2011-09-06 | 2013-10-16 | 华东理工大学 | Preparation method of nano silver/cube silver chloride photo-catalytic material |
| CN103007969A (en) * | 2012-03-16 | 2013-04-03 | 华东理工大学 | Nano-silver/flaky silver bromoiodide photocatalytic material and preparation method thereof |
| CN102939994B (en) * | 2012-11-26 | 2014-05-07 | 河海大学 | Method for preparing silver/copper modified K4Nb6O17 film |
| CN103028425A (en) * | 2012-12-11 | 2013-04-10 | 湖南大学 | Environmental functional nano-material Ag/AgBr nano-fibre, and preparation method and application method thereof |
| CN103623850A (en) * | 2013-11-05 | 2014-03-12 | 江苏大学 | Preparation method of high-activity silver bromide nano-photocatalytic material |
| CN103804549B (en) * | 2014-01-24 | 2015-08-05 | 中国科学院金属研究所 | Halogenation money base light trigger and the application at photoinduction unsaturated olefin monomer polymerization |
| CN103785421A (en) * | 2014-02-19 | 2014-05-14 | 东华大学 | Photocatalyst silver thiocyanate and preparation method thereof |
| CN103816926B (en) * | 2014-03-11 | 2019-11-08 | 鲁东大学 | A kind of silver bromate visible-light photocatalyst and preparation method thereof of load silver |
| CN103846096A (en) * | 2014-03-28 | 2014-06-11 | 安徽师范大学 | Silver/silver bromide/silver metavanadate plasma compound photocatalyst and preparation method thereof |
| CN108975383B (en) * | 2018-08-29 | 2020-08-11 | 淮阴师范学院 | Preparation method of porous Ag/AgBr nano material |
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| CN100396375C (en) * | 2005-09-21 | 2008-06-25 | 中国科学院生态环境研究中心 | Method for preparing visible light efficient multifunctional photocatalyst |
| CN101279274B (en) * | 2008-05-26 | 2010-08-04 | 山东大学 | Nano silver/silver bromide visible light photocatalysis material and preparation thereof |
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