CN109701526A - A kind of hollow B-SiO2@TiO2The purposes of-Ag catalyst degradation green alga - Google Patents
A kind of hollow B-SiO2@TiO2The purposes of-Ag catalyst degradation green alga Download PDFInfo
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- CN109701526A CN109701526A CN201910011208.6A CN201910011208A CN109701526A CN 109701526 A CN109701526 A CN 109701526A CN 201910011208 A CN201910011208 A CN 201910011208A CN 109701526 A CN109701526 A CN 109701526A
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Abstract
The present invention provides a kind of hollow B-SiO2@TiO2The method of-Ag catalyst degradation green alga.Steps are as follows for degradation green alga: preparing certain density green alga solution, at different temperature, the different TiO of various dose is added2The hollow B-SiO of content2@TiO2- Ag catalyst is tested on light-catalyzed reaction instrument, continuous sampling 510min, and the absorbance of sample after reaction is measured with ultraviolet specrophotometer, calculates green alga degradation rate.The catalyst is used for the green alga under visible light conditions in photocatalytic degradation water.Significant feature of the invention is that used hollow B-SiO2@TiO2- Ag catalyst has the activity of very high photocatalytic degradation green alga.
Description
Technical field
The invention belongs to inorganic catalytic fields, are related to a kind of hollow B-SiO2@TiO2- Ag catalyst is under visible light illumination
The purposes of catalytic degradation green alga,.
Background technique
Algae pollution is because caused by the height cluster of algae.The toxic action of algae pollution is " red in coastal waters
Lake " harm, most significantly shows as largely killing fishes and shrimps shellfish and food organisms, the discussion to its reason has been made not both at home and abroad
Few research, but do not satisfactorily resolve yet so far.
Pollution caused by the substantial increase of fresh water algae can at least cause the influence of following four aspects in lake: 1.
Algae is largely proliferated, anaerobic decay reinforcement, water quality peculiar smell, loses fresh water consumption value and reduces lake as scenic spot
Value.2. the overgrowing of algae accelerates Succession of Five Lakes and bogginess process, the lake service life is shortened.3. a large amount of proliferation of algae,
Transpiration is reinforced, and lake water reserves reduce.4. a large amount of proliferation of algae necessarily lead to the generation of poisonous substance or after death decompose, to economy
Aquatic product culture brings harm.Primnesium saltans in brackish water contains ichtyhotoxisin, hemolysin and cell toxicant in metabolite
Deng, ichtyhotoxisin changes the selected area update strategy ability of gill cell surface, and it is easy to hemolysin and cell toxicant into people's animal body, so with
The gill is all extremely sensitive to the toxin of Prymnesium parvum Carter and Prymnesium saltans as the aquatic animal of respiratory apparatus.Hemolysin can destroy dynamic
The intracorporal red blood cell of object, and nucleus is dissolved, eventually lead to animal dead.Cation such as mg2+、Ca2+、Na+Have to toxin
Activation: the degree that it is activated is related with the pH value of water body.According to the test of (1964) Uitzur etc., pH increases to 8 from 7, fish
The toxicity of toxin about increases 2.5 times, when pH is increased to 9 by 8, and toxicity increases 4 times again.As a result, reduce water in algae content at
For an important topic.
Summary of the invention
The present invention is used TiO with hydro-thermal method2/ Ag is supported on hollow boron glass microballoon, it is seen that light is as light source, production
Hollow B-SiO2@TiO2- Ag heterojunction composite green alga and is shown in catalytic degradation green alga very good to degrade
Catalyst activity.
The present invention is directed to develop a kind of high catalytic activity catalyst, under visible light illumination, for water green algae of degrading.This
The described hollow B-SiO of invention2@TiO2The method of-Ag catalyst, TiO2- Ag is significant as the photocatalysis effect of catalyst, and
Hollow boron microballoon is that a kind of surface is non-porous, and the inside is filled with gases such as air, carbon dioxide, at the small ball of totally-enclosed hollow structure
Body, general particle diameter are 10~50 μm.Wherein, most commonly seen with silica, glass system microballoon.Since hollow microsphere has ratio
The special performances such as weight is small, thermal conductivity is low, do not absorb water, dielectric constant is low, this new material is by the great attention of people.This
Invention is achieved by the following technical solution:
A kind of hollow B-SiO2@TiO2- Ag catalyst, in the catalyst, hollow boron glass microballoon is as TiO2- Ag's
Carrier, TiO2Quality be hollow boron glass microballoon gross mass 1%~20%.Ag mass is TiO20.1%.
A kind of hollow B-SiO2@TiO2The preparation method of-Ag catalyst, includes the following steps:
(1) by TiCl4Pure solution is added slowly in the dilute hydrochloric acid of certain volume, obtains TiCl4Hydrochloric acid solution；Then again
Silver nitrate solution is added, wherein it is TiO that Ag content, which is added,20.1% silver nitrate of quality；
(2) a certain amount of hollow boron glass microballoon is weighed, distilled water is added and is uniformly dispersed, heating water bath, using peristaltic pump
NaOH solution, TiCl are added simultaneously4Hydrochloric acid solution and AgNO3Solution adjusts pH value of solution=2；After addition, the reaction was continued；Instead
It should be filtered after the completion with deionized water to neutrality, it is dry, it is prepared hollowB-SiO2 @TiO2- Ag catalyst.
The dilute hydrochloric acid concentration is 3mol/L, TiCl4The concentration of hydrochloric acid solution is 1.5mol/L, AgNO3The concentration of solution is
0.0011mol/L, the mass percentage concentration of the NaOH solution are 5wt.%.
The hollow B-SiO of product2@TiO2In-Ag catalyst, TiO2Quality is the gross mass of hollow boron glass microballoon
1%~20%.Ag content is TiO2The 0.1% of quality.
In step (2), the temperature of heating water bath is 85 DEG C.
In step (2), NaOH solution, TiCl are added using peristaltic pump simultaneously4Hydrochloric acid solution and AgNO3When solution, it is added
After half an hour, addition, the reaction was continued, the time is 3h for time control.
In step (2), drying temperature is 120 DEG C, and drying time is for 24 hours.
The hollow B-SiO2@TiO2The purposes of-Ag photocatalytic degradation green alga, steps are as follows:
The green alga solution of 5mg/L is prepared, at different temperature, the hollow B-SiO of various dose is added2@TiO2- Ag is urged
Agent is tested on light-catalyzed reaction instrument, continuous sampling 510min, and with ultraviolet specrophotometer measurement reaction after sample
Absorbance, calculate green alga degradation rate.
In the raw material, the hollow B-SiO2@TiO2It is 0.05~0.1g, the reaction that dosage, which is added, in-Ag catalyst
In initial green alga solution additional amount be 250mL, reaction carries out under normal pressure, and temperature is 25~35 DEG C, continuous sampling 510min.
The invention has the benefit that
(1) hollow B-SiO used by notable feature of the invention2@TiO2- Ag catalyst has good during the reaction
Good catalytic activity and stability；
(2) for example, using catalyst of the invention, normal pressure, catalyst charge 0.1g, under 35 DEG C of reaction conditions,
TiO2Mass fraction be 20% catalyst green alga high conversion rate up to 95.3%.
Specific embodiment
More present invention are described further combined with specific embodiments below:
Embodiment 1
Weigh 5g NaOH be dissolved in be configured in 95mL distilled water mass fraction be 5% NaOH solution, measure 300mL matter
Measuring score is that 37% concentrated hydrochloric acid solution is dissolved in the dilute hydrochloric acid for being configured to that mass fraction is 3mol/L in 700mL distilled water, by 165mL
TiCl4Pure solution is slowly added into the dilute hydrochloric acid of 500mL, need to be continued when dropwise addition to stir, be added dilute hydrochloric acid to 1L, made
Finish the TiCl of 1.5mol/L4Hydrochloric acid solution；Compound concentration is the AgNO of 0.0011mol/L simultaneously3Aqueous solution.
The distilled water of the hollow boron glass microballoon and 500mL that weigh 100g is put into 2L beaker, is then added in 85 DEG C of water-baths
The TiCl of NaOH solution and 1.5mol/L that mass fraction is 5% is added under conditions of heat and stirring simultaneously4Hydrochloric acid solution 84mL,
The AgNO of 0.0011mol/L3Aqueous solution 84mL controls pH value of solution=2, and the time is added in or so half an hour；After addition, instead
Answer 3h；It is filtered after the reaction was completed with deionized water to neutrality, drying for 24 hours, prepares TiO in 120 DEG C of drying box2Load capacity
For 10% hollow B-SiO2@TiO2- Ag catalyst.
Photocatalytic degradation green alga solution:
5mg green alga is weighed, is added in 1L deionized water, the green alga solution of 5mg/L is made；Using photocatalytic reaction device,
Catalyst 0.08g is added, continuous sampling 510min at being 30 DEG C in reaction temperature measures absorbance, calculates green alga degradation rate.It surveys
The result of examination is listed in table 1 by calculating.
Table 1.TiO2The hollow B-SiO that load capacity is 10%2@TiO2The difference of-Ag (pH=8) degradation 5mg/L green alga solution
The chlorophyll degradation rate result table of period
Embodiment 2
With embodiment 1, change TiO2Load capacity, photocatalytic degradation reaction 510min after acquired results be shown in Table 6.
The hollow B-SiO of 2. different loads amount of table2@TiO2- Ag photocatalytic degradation green alga solution degradation rate result table
Embodiment 3
With embodiment 1, change catalyst dosage, weighing dosage respectively is 0.05g, and the catalyst of 0.1g is reacted, instead
The conversion ratio acquired results after 510min are answered to be shown in Table 2.
The TiO of the addition various dose of table 2.2The hollow B-SiO that load capacity is 20%2@TiO2- Ag photocatalytic degradation green alga is molten
The degradation rate result table of liquid
Embodiment 4
With embodiment 1, but change the temperature of green alga solution reaction, the acquired results after degradation reaction 510min are shown in Table 5.
Table 5.TiO2The hollow B-SiO that load capacity is 20%2@TiO2- Ag photocatalytic degradation green alga solution degradation rate result table
Claims (9)
1. a kind of hollow B-SiO2@TiO2- Ag catalyst, which is characterized in that the material using hollow boron glass microballoon as
TiO2The carrier of-Ag, TiO2As photocatalytic activity component；TiO2Quality be hollow boron glass microballoon gross mass 1%~
20%, Ag are TiO2The 0.1% of quality.
2. a kind of hollow B-SiO according to claim 12@TiO2The preparation method of-Ag catalyst, which is characterized in that packet
Include following steps:
(1) by TiCl4Pure solution is added slowly in the dilute hydrochloric acid of certain volume, obtains TiCl4Hydrochloric acid solution；Then it adds
Silver nitrate solution, wherein it is TiO that Ag content, which is added,20.1% silver nitrate of quality；
(2) a certain amount of hollow boron glass microballoon is weighed, distilled water is added and is uniformly dispersed, heating water bath, simultaneously using peristaltic pump
NaOH solution, TiCl is added4Hydrochloric acid solution and AgNO3Solution adjusts pH value of solution=2；After addition, the reaction was continued；It has reacted
Cheng Houyong deionized water is filtered to neutrality, dry, and hollow B-SiO is prepared2@TiO2- Ag catalyst.
3. a kind of hollow B-SiO according to claim 22@TiO2The preparation method of-Ag catalyst, which is characterized in that dilute
Concentration of hydrochloric acid is 3mol/L, TiCl4The concentration of hydrochloric acid solution is 1.5mol/L, AgNO3The concentration of solution is 0.0011mol/L, institute
The mass percentage concentration for stating NaOH solution is 5wt.%.
4. a kind of hollow B-SiO according to claim 22@TiO2The preparation method of-Ag catalyst, which is characterized in that institute
State the hollow B-SiO of product2@TiO2In-Ag catalyst, TiO2Quality is the 1%~20% of the gross mass of hollow boron glass microballoon；
Ag content is TiO2The 0.1% of quality.
5. a kind of hollow B-SiO according to claim 22@TiO2The preparation method of-Ag catalyst, which is characterized in that step
Suddenly in (2), the temperature of heating water bath is 85 DEG C.
6. a kind of hollow B-SiO according to claim 22@TiO2The preparation method of-Ag catalyst, which is characterized in that step
Suddenly in (2), NaOH solution, TiCl are added using peristaltic pump simultaneously4Hydrochloric acid solution and AgNO3When solution, time control is added and exists
After half an hour, addition, the reaction was continued, and the time is 3h.
7. a kind of hollow B-SiO according to claim 22@TiO2The preparation method of-Ag catalyst, which is characterized in that step
Suddenly in (2), drying temperature is 120 DEG C, and drying time is for 24 hours.
8. hollow B-SiO according to claim 12@TiO2The purposes of-Ag photocatalytic degradation green alga, which is characterized in that step
It is rapid as follows:
The green alga solution for preparing 5mg/L is separately added into a certain amount of hollow B-SiO at 25~35 DEG C of temperature2@TiO2- Ag is urged
Agent is tested on light-catalyzed reaction instrument, continuous sampling 510min, and spectrophotometer measurement reaction after sample extinction
Degree, calculates its green alga content.
9. purposes according to claim 8, which is characterized in that hollow B-SiO2@TiO2The use of-Ag photocatalytic degradation green alga
On the way, it is characterised in that the raw material, hollow B-SiO2@TiO2It is 0.05~0.1g, green alga solution that dosage, which is added, in-Ag catalyst
Dosage is 250mL.
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Citations (5)
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|---|---|---|---|---|
| CN101693790A (en) * | 2009-10-22 | 2010-04-14 | 江西理工大学 | Composite mica cerium titanium pearl pigment and preparation method thereof |
| CN102500366A (en) * | 2011-11-03 | 2012-06-20 | 合肥美菱股份有限公司 | Photo-catalytic nanomaterial |
| CN103007931A (en) * | 2012-11-22 | 2013-04-03 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN105753093A (en) * | 2014-12-15 | 2016-07-13 | 天津滨浦生产力促进有限公司 | Hollow glass bead-loading type sewage treatment agent |
| CN107486203A (en) * | 2017-09-11 | 2017-12-19 | 浙江工商大学 | A kind of recyclable float type composite photocatalyst ball and its preparation method and application |
-
2019
- 2019-01-07 CN CN201910011208.6A patent/CN109701526A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693790A (en) * | 2009-10-22 | 2010-04-14 | 江西理工大学 | Composite mica cerium titanium pearl pigment and preparation method thereof |
| CN102500366A (en) * | 2011-11-03 | 2012-06-20 | 合肥美菱股份有限公司 | Photo-catalytic nanomaterial |
| CN103007931A (en) * | 2012-11-22 | 2013-04-03 | 嘉兴学院 | Method for preparing nano silver and titanium dioxide thin films on surfaces of hollow glass beads |
| CN105753093A (en) * | 2014-12-15 | 2016-07-13 | 天津滨浦生产力促进有限公司 | Hollow glass bead-loading type sewage treatment agent |
| CN107486203A (en) * | 2017-09-11 | 2017-12-19 | 浙江工商大学 | A kind of recyclable float type composite photocatalyst ball and its preparation method and application |
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Application publication date: 20190503 |