CN104722315A - Preparation method for double-nest-shaped sulfo-metal cluster compound functional material with visible light catalysis performance - Google Patents
Preparation method for double-nest-shaped sulfo-metal cluster compound functional material with visible light catalysis performance Download PDFInfo
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- CN104722315A CN104722315A CN201510161651.3A CN201510161651A CN104722315A CN 104722315 A CN104722315 A CN 104722315A CN 201510161651 A CN201510161651 A CN 201510161651A CN 104722315 A CN104722315 A CN 104722315A
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Abstract
The invention discloses a preparation method for a double-nest-shaped sulfo-metal cluster compound functional material with a visible light catalysis performance. The method comprises the steps of introducing hydrogen sulfide into an ammonia-water solution of tungstic acid or sodium molybdate for reaction, and performing suction filtration and drying to obtain ammonium tri-thiotungstate or ammonium tri-thiomolybdate; adding the ammonium tri-thiotungstate or ammonium tri-thiomolybdate into an organic solution of cuprous halides to obtain a solution; and adding 1,10'-Ferroin into the obtained solution and stirring to obtain a solution containing the double-nest-shaped sulfo-metal cluster compound functional material, adding a precipitant after filtration, performing crystallization, performing filtration, washing and drying to obtain the double-nest-shaped sulfo-metal cluster compound functional material. The method has the advantage that the double-nest-shaped sulfo-metal cluster compound functional material with the performance of degrading methylene blue dyes through visible light catalysis.
Description
One technical field
The present invention relates to the preparation of catalysis material, be specifically related to a kind of preparation method with two nest like sulfo-metal cluster compound functional materials of visible light photocatalytic degradation organic dyestuff methylene blue.
Two background technologies
Along with the fast development of modern industry, the whole world faces the severe challenge of energy crisis and environmental pollution.And environment and the energy are the significant problems directly affecting human survival and development.Containing many harmful substances in industrial wastewater, waste gas, as organic agricultural chemicals, organic dyestuff, chlorine series solvent (dichloroethylene, trichloro-ethylene etc.), benzene series solvent and aldehyde, ketone etc.Traditional method for treating water is as absorption method, and in actual process, there is certain difficulty, effect is undesirable, is therefore badly in need of finding a kind of economy, effective method with organic dyestuff residual in water after conventional process of degrading further.In this context, people show keen interest to exploitation visible light responsive photocatalytic material.Photocatalysis technology directly can utilize solar energy, can process the harmful substance in most water body, low price, environmental friendliness, has therefore become and has solved one of most promising technology of environmental problem.
Among numerous photochemical catalysts, titanium dioxide (TiO
2), the advantage such as stable chemical performance, safe without toxic side effect, long service life excellent with its catalytic performance and being widely used.But TiO
2photocatalyst powder is superfine little, is easy to cohesion in aqueous, is difficult to separation and recovery.In addition, suspended particles stop the degree of depth that have impact on light radiation to the absorption of light, and these shortcomings make the application of this technology be restricted.In the last few years, the extensive concern of related discipline researcher is obtained based on metal-organic catalysis material.Such as document Chem.Commun., 2011,47,11715 and DaltonTrans., 2011,40,9299 all report the metal cluster compound with photocatalytically degradating organic dye performance, but most of cluster photochemical catalyst is wherein all effect related dye under UV-irradiation to photocatalytic degradation, makes it be restricted in actual applications.
Three summary of the invention
The object of the present invention is to provide a kind of preparation method of two nest like sulfo-metal cluster compound functional materials of the methylene blue of photocatalytically degradating organic dye under visible light.
Realization the present invention includes following steps:
Hydrogen sulfide gas to be passed in wolframic acid or sodium molybdate ammonia spirit and to react, through suction filtration, dry obtained three sulfo-ammonium tungstates or three ammonium thiomolybdates by 1.1;
Three sulfo-ammonium tungstates obtained in 1.1 or three ammonium thiomolybdates add in the organic solution of cuprous halide by 1.2, stirred for several minute;
1,10 '-phenanthroline to join in solution obtained in step 1.2 and is stirred to whole dissolving by 1.3, and obtained solution containing two nest like sulfo-metal cluster compound functional material also filters;
1.4 in step 1.3 obtained two nest like sulfo-metal cluster compound functional material solution in add precipitating reagent, through crystallization, filtration, wash, be drying to obtain two nest like sulfo-metal cluster compound functional material.
The present invention has in the preparation method of two nest like sulfo-metal cluster compound functional materials of catalytic degradation methylene blue performance under visible light, cuprous halide comprises stannous chloride, cuprous bromide or cuprous iodide, and the mol ratio of three sulfo-ammonium tungstates or three ammonium thiomolybdates and cuprous halide is 1:3 ~ 6.
Compared with prior art, its remarkable advantage is in the present invention: (1) synthetic route is simple, process conditions are gentle, easily control; (2) raw material synthesized is easy to get; (3) photocatalysis performance of material is better; (4) chemistry of material, optical stability are good.
Four accompanying drawing explanations
Fig. 1: not in the same time, the absorption spectrogram of the aqueous solution of methylene blue of two nest like sulfo-metal cluster compound functional material catalysis.
Two nest like sulfo-metal cluster compound functional materials prepared by the present invention, under visible ray shines, have good photocatalytic Degradation to methylene blue.Along with the propelling of catalysis time, the absorbance of aqueous solution of methylene blue reduces gradually.
Fig. 2: the powder X-ray diffractogram of prepared two nest like sulfo-metal cluster compound functional materials.
Two nest like sulfo-metal cluster compound functional materials prepared by the present invention have good photostability and chemical stability.After carrying out the experiment of photocatalytic degradation methylene blue, compared with the sample spectrogram before experiment, there is not significantly change in the powder X-ray diffractogram of two nest like sulfo-metal cluster compound functional material.Describe two nest like sulfo-metal cluster compound functional material and there is good stability.
Five detailed description of the invention
Embodiment 1: the present invention has the preparation method of two nest like sulfo-metal cluster compound functional materials of visible light catalytic performance, comprises the following steps:
The first step, joins wolframic acid in ammonia spirit and stirs, the ammonia spirit of obtained wolframic acid;
Second step, is passed into hydrogen sulfide in wolframic acid ammonia spirit obtained in the first step and reacts, through suction filtration, dry obtained compound three sulfo-ammonium tungstate;
3rd step, 0.1mmol tri-sulfo-ammonium tungstate adds 7 milliliters of N of 0.4mmol stannous chloride, in N '-dimethyl formamide solution, stirs 20 minutes, obtained red clear solution;
4th step, takes 0.4mmol1, and 10 '-phenanthroline joins in solution obtained in the 3rd step and stirs 30 minutes, and obtained peony contains the solution of two nest like sulfo-metal cluster compound functional material and filters;
5th step, adds isopropyl alcohol in filtrate obtained in the 4th step, obtains yellow bulk crystals, filter, washs, is drying to obtain two nest like sulfo-metal cluster compound functional material through crystallization.
Photocatalysis performance is tested: two nest like sulfo-metal cluster compound functional materials (40 milligrams) of preparation are joined in the aqueous solution of methylene blue of 2.5 milligrams per liter and stirs dark treatment 30 minutes, balance to reach catalyst to the adsorption/desorption of dyestuff.Then under the condition of visible ray stirring, carry out the test of photocatalysis performance.
Embodiment 2: the present invention has the preparation method of the two nest like sulfo-metal cluster compound functional material of visible light catalytic performance, comprises the following steps:
The first step, joins wolframic acid in ammonia spirit and stirs, the ammonia spirit of obtained wolframic acid;
Second step, is passed into hydrogen sulfide in wolframic acid ammonia spirit obtained in the first step and reacts, through suction filtration, dry obtained compound three sulfo-ammonium tungstate;
3rd step, 0.1mmol tri-sulfo-ammonium tungstate adds 5 milliliters of N of 0.3mmol cuprous bromide, in N '-dimethyl acetamide solution, stirs 30 minutes, obtained red clear solution;
4th step, takes 0.4mmol1, and 10 '-phenanthroline joins in solution obtained in the 3rd step and stirs 20 minutes, and obtained peony contains the solution of two nest like sulfo-metal cluster compound functional material and filters;
5th step, adds ethanol in filtrate obtained in the 4th step, obtains yellow bulk crystals, filter, washs, is drying to obtain two nest like sulfo-metal cluster compound functional material through crystallization.
Photocatalysis performance is tested: two nest like sulfo-metal cluster compound functional materials (40 milligrams) of preparation are joined in the aqueous solution of methylene blue of 2.5 milligrams per liter and stirs dark treatment 30 minutes, balance to reach catalyst to the adsorption/desorption of dyestuff.Then under the condition of visible ray stirring, carry out the test of photocatalysis performance.
Embodiment 3: the present invention has the preparation method of the two nest like sulfo-metal cluster compound functional material of visible light catalytic performance, comprises the following steps:
The first step, joins wolframic acid in ammonia spirit and stirs, the ammonia spirit of obtained wolframic acid;
Second step, is passed into hydrogen sulfide in wolframic acid ammonia spirit obtained in the first step and reacts, through suction filtration, dry obtained compound three sulfo-ammonium tungstate;
3rd step, 0.1mmol tri-sulfo-ammonium tungstate adds in 10 milliliters of DMSO solution of 0.5mmol cuprous iodide, stirs 15 minutes, obtained red clear solution;
4th step, takes 0.4mmol1, and 10 '-phenanthroline joins in solution obtained in the 3rd step and stirs 20 minutes, and obtained peony contains the solution of two nest like sulfo-metal cluster compound functional material and filters;
5th step, adds ethanol in filtrate obtained in the 4th step, obtains yellow bulk crystals, filter, washs, is drying to obtain two nest like sulfo-metal cluster compound functional material through crystallization.
Photocatalysis performance is tested: two nest like sulfo-metal cluster compound functional materials (40 milligrams) of preparation are joined in the aqueous solution of methylene blue of 2.5 milligrams per liter and stirs dark treatment 30 minutes, balance to reach catalyst to the adsorption/desorption of dyestuff.Then under the condition of visible ray stirring, carry out the test of photocatalysis performance.
Embodiment 4: the present invention has the preparation method of the two nest like sulfo-metal cluster compound functional material of visible light catalytic performance, comprises the following steps:
The first step, joins sodium molybdate in ammonia spirit and stirs, the ammonia spirit of obtained sodium molybdate;
Second step, is passed into hydrogen sulfide in the molybdenum acid ammonia aqueous solution obtained in the first step and reacts, through suction filtration, dry obtained compound three ammonium thiomolybdate;
3rd step, 0.1mmol tri-ammonium thiomolybdate adds 10 milliliters of N of 0.3mmol cuprous iodide, in N '-dimethyl formamide solution, stirs 30 minutes, obtained red clear solution;
4th step, takes 0.4mmol1, and 10 '-phenanthroline joins in solution obtained in the 3rd step and stirs 15 minutes, and obtained peony contains the solution of two nest like sulfo-metal cluster compound functional material and filters;
5th step, adds methyl alcohol in filtrate obtained in the 4th step, obtains yellow bulk crystals, filter, washs, is drying to obtain two nest like sulfo-metal cluster compound functional material through crystallization.
Photocatalysis performance is tested: two nest like sulfo-metal cluster compound functional materials (40 milligrams) of preparation are joined in the aqueous solution of methylene blue of 2.5 milligrams per liter and stirs dark treatment 30 minutes, balance to reach catalyst to the adsorption/desorption of dyestuff.Then under the condition of visible ray stirring, carry out the test of photocatalysis performance.
Claims (6)
1. there is the preparation method of the two nest like sulfo-metal cluster compound functional material of visible light catalytic performance, comprise the following steps:
Hydrogen sulfide gas to be passed in the ammonia spirit of wolframic acid or sodium molybdate and to react, through suction filtration, dry obtained three sulfo-ammonium tungstates or three ammonium thiomolybdates by 1.1;
Three sulfo-ammonium tungstates obtained in 1.1 or three ammonium thiomolybdates add in the organic solution of cuprous halide by 1.2, stirred for several minute;
1,10 '-phenanthroline to join in solution obtained in step 1.2 and is stirred to whole dissolving by 1.3, and obtained solution containing two nest like sulfo-metal cluster compound functional material also filters;
Add precipitating reagent in the solution of 1.4 two nest like sulfo-metal cluster compound functional materials obtained in step 1.3, through crystallization, filtration, wash, be drying to obtain two nest like sulfo-metal cluster compound functional material.
2. the preparation method with two nest like sulfo-metal cluster compound functional materials of visible light catalytic performance according to claim 1, is characterized in that cuprous halide comprises stannous chloride, cuprous bromide or cuprous iodide.
3. the preparation method with two nest like sulfo-metal cluster compound functional materials of visible light catalytic performance according to claim 1, is characterized in that the mol ratio of three sulfo-ammonium tungstates or three ammonium thiomolybdates and cuprous halide is 1:3 ~ 6.
4. the preparation method with two nest like sulfo-metal cluster compound functional materials of visible light catalytic performance according to claim 1, is characterized in that organic solvent comprises N, N '-dimethyl formamide, N, N '-dimethyl acetamide, DMSO.
5. the preparation method with two nest like sulfo-metal cluster compound functional materials of visible light catalytic performance according to claim 1, is characterized in that precipitating reagent comprises alcohols solvent, second eyeball, acetone and ether.
6. the preparation method with two nest like sulfo-metal cluster compound functional materials of visible light catalytic performance according to claim 5, is characterized in that alcohols solvent comprises methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105586639A (en) * | 2016-02-29 | 2016-05-18 | 江南大学 | Preparation method of second-order nonlinear optical crystal material {[Tb(NMP)7][WS4Ag3I4]} |
| CN107597145A (en) * | 2017-09-21 | 2018-01-19 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of carbon composite sulfur for wolframic acid Mn catalyst |
| CN108383169A (en) * | 2018-04-04 | 2018-08-10 | 三峡大学 | A kind of preparation method and applications of ternary layered Transition-metal dichalcogenide |
Citations (2)
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| JP2000256489A (en) * | 1999-03-10 | 2000-09-19 | Agency Of Ind Science & Technol | Preparation of polymer/metal cluster composite |
| CN1888969A (en) * | 2006-07-17 | 2007-01-03 | 南京理工大学 | Method for producing isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials |
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2015
- 2015-04-07 CN CN201510161651.3A patent/CN104722315A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256489A (en) * | 1999-03-10 | 2000-09-19 | Agency Of Ind Science & Technol | Preparation of polymer/metal cluster composite |
| CN1888969A (en) * | 2006-07-17 | 2007-01-03 | 南京理工大学 | Method for producing isomorphous heterocaryosis cubic alkane type metal cluster compound molecular functional materials |
Non-Patent Citations (1)
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| JINFANG ZHANG ET AL: ""Two distinct dimeric heterothiometallic W/S/Cu clusters: syntheses, crystal structures, and photocatalytic properties"", 《POLYHEDRON》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105586639A (en) * | 2016-02-29 | 2016-05-18 | 江南大学 | Preparation method of second-order nonlinear optical crystal material {[Tb(NMP)7][WS4Ag3I4]} |
| CN107597145A (en) * | 2017-09-21 | 2018-01-19 | 柳州若思纳米材料科技有限公司 | A kind of preparation method of carbon composite sulfur for wolframic acid Mn catalyst |
| CN108383169A (en) * | 2018-04-04 | 2018-08-10 | 三峡大学 | A kind of preparation method and applications of ternary layered Transition-metal dichalcogenide |
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Application publication date: 20150624 |