CN103785131B - A kind of method of catalyze and degrade organic pollutants - Google Patents
A kind of method of catalyze and degrade organic pollutants Download PDFInfo
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- CN103785131B CN103785131B CN201410054415.7A CN201410054415A CN103785131B CN 103785131 B CN103785131 B CN 103785131B CN 201410054415 A CN201410054415 A CN 201410054415A CN 103785131 B CN103785131 B CN 103785131B
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- aqueous solution
- nano material
- near infrared
- infrared light
- indium
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Abstract
The present invention relates to a kind of method of catalyze and degrade organic pollutants, belong to Photocatalyst field.Method of the present invention is β-In
2s
3nano material under near infrared light excites for catalyze and degrade organic pollutants.The invention provides β-In
2s
3a kind of novelty teabag exciting lower catalyzing and degrading pollutant near infrared light of nano material; That has widened the scope of application of many indium sulfides and sunshine utilizes scope; Also the scope of near infrared light catalysis material has been widened; β-In of the present invention
2s
3nano material has more excellent near infrared light catalytic performance, can effective degradable organic pollutant rapidly, and the degradation rate of 3 hours near-infrared photo-catalytic degradation of methyl-oranges can be reached for 70%, has broad application prospects.
Description
Technical field
The present invention relates to a kind of method of catalyze and degrade organic pollutants, belong to Photocatalyst field.
Background technology
Along with day by day increasing the weight of of energy crisis and environmental pollution, application clean energy resource as solar energy, and utilizes photocatalytic semiconductor material degradation of contaminant to receive increasing concern.Titanium dioxide is the semi-conducting material being found to have photocatalysis the earliest, due to its abundance, with low cost, stable chemical nature, have no side effect, photohole oxidisability is strong, is also semiconductor light-catalyst of greatest concern in current field of photocatalytic material.But titanium dioxide titanizing nano material is low to sunshine utilization rate, only in the ultraviolet light range accounting for sunshine gross energy about 5%, there is photoresponse, by doping, compound, load, deposit other metal, nonmetallic ion, noble metal, semi-conducting material etc. and limitedly can only widen its photoresponse scope.
Metal sulfide is very important part in semi-conducting material extended familys, and especially in structure cell, sulphur atom quantity is greater than the Metal polysulfide complex of metallic atom quantity (as MoS
2, WS
2deng) focus of semi-conducting material research field has been become owing to having special optics, machinery and catalytic performance.Many indium sulfide (In
2s
3), also known as indium sulfide, be a kind of typical III-VI family sulfide, there are three kinds of different crystalline forms: α-In
2s
3, β-In
2s
3with γ-In
2s
3.β-In wherein
2s
3be a kind of n-type semiconductor, have the spinel structure of cation defect, its energy gap is 2.0-2.2eV, is used widely in nano photoelectronic devices.Compared with titanium dioxide titanizing nano material, β-In
2s
3nano material can produce response to ultraviolet light and visible ray, and can excite at Uv and visible light and carry out catalytic degradation to organic pollution down; But, to the near infrared band of sunshine gross energy 44%, still not yet make full use of at present.
Summary of the invention
The present invention is found by research experiment, β-In
2s
3nano material can produce response near infrared light, thus excites lower degradable organic pollutant near infrared light.
So, the invention provides a kind of employing β-In
2s
3the method of nano material catalyze and degrade organic pollutants.
Technical scheme of the present invention
A method for catalyze and degrade organic pollutants, β-In
2s
3nano material under near infrared light excites for catalyze and degrade organic pollutants.
Concrete grammar is: by β-In
2s
3nano material is placed in organic pollution, then uses near infrared light.
Described β-In
2s
3nano material particle spherical in shape, particle diameter are 5-10nm; Describedly spherically comprise almost spherical.
After described near infrared light filters by filtered of infrared lamp light source the light that wavelength is 200nm-780nm, remaining light provides.
Described organic matter particularly methyl orange.
Said method, can use general quartz reactor to complete under the condition stirred.
In order to improve β-In
2s
3nano material to the degradation capability of organic pollution, described β-In
2s
3nano material preferably adopts following method to be prepared from:
Under agitation, the sulphur source aqueous solution is slowly joined in the aqueous solution of indium source, form yellow sol; Then, with nitric acid, sol pH is adjusted to 1-3; Again by adjustment pH after colloidal sol at 160-200
ohydro-thermal reaction 16-24 hour under C, then filters the sediment obtained; Sediment is through washing, being drying to obtain product;
This preparation method, by adjustment and the cooperation of parameter each in preparation process, makes the β-In of acquisition
2s
3nano material excites the lower degradation rate to organic pollution to significantly improve near infrared light.
Above-mentioned β-In
2s
3in the preparation process of nano material, the described sulphur source aqueous solution is dissolved in deionized water by dissolvable sulfide and forms, and e.g., is dissolved in deionized water forms by potassium sulfide, ammonium sulfide or vulcanized sodium; The described indium source aqueous solution is dissolved in deionized water is formed by indium nitrate, inidum chloride.In order to improve β-In further
2s
3nano material is to the catalytic performance of organic pollution, and preferably, the sulphur source aqueous solution is that vulcanized sodium is dissolved in that deionized water forms, the indium source aqueous solution is that indium nitrate is dissolved in deionized water and forms.
Above-mentioned β-In
2s
3, in the preparation process of its nano material, in order to improve β-In
2s
3degree of crystallinity, indium and be preferably 1:2.5 with the mol ratio of sulphur in the aqueous solution of sulphur source in the aqueous solution of described indium source.
Above-mentioned β-In
2s
3in the preparation process of nano material, described hydro-thermal reaction is carried out in hydrothermal reaction kettle, and the compactedness of colloidal sol in hydrothermal reaction kettle is the volume of 50%-80%; The washing lotion that described washing step uses is deionized water and alcohol; In order to reduce indium sulfide grain diameter, improve degree of crystallinity, described reaction temperature is preferably 180
oc; In order to improve the degree of crystallinity of indium sulfide, the described reaction time is preferably 24 hours.
About creationary plain statement of the present invention: according to β-In
2s
3the energy gap 2.0-2.2eV of nano material judges, β-In
2s
3the maximum absorption wavelength of nano material is about 600-650nm, in visible wavelength range; And the energy of infrared light is lower than the energy of ultraviolet with possibility light.So those skilled in the art can not according to " β-In
2s
3the energy gap of nano material and β-In
2s
3nano material can produce response to ultraviolet light and visible ray " predict " β-In
2s
3response can be produced " near infrared light.
Beneficial effect
Provide β-In
2s
3a kind of novelty teabag exciting lower catalyzing and degrading pollutant near infrared light of nano material; That has widened the scope of application of many indium sulfides and sunshine utilizes scope; Also the scope of near infrared light catalysis material has been widened;
β-In of the present invention
2s
3nano material has more excellent near infrared light catalytic performance, can effective degradable organic pollutant rapidly, and the degradation rate of 3 hours near-infrared photo-catalytic degradation of methyl-oranges can be reached for 70%, has broad application prospects;
The preparation method of many indium sulfide photocatalysts provided by the invention is simple to operate, be easy to promote.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of many indium sulfides nano particle prepared by the embodiment of the present invention 3;
Fig. 2 is transmission electron microscope (TEM) image of many indium sulfides nano particle prepared by the embodiment of the present invention 3;
Fig. 3 be the embodiment of the present invention 3 prepare many indium sulfides nano particle under near infrared light to the photocatalytic activity of methyl orange solution curve over time.
Fig. 4 is that many indium sulfides nano material of the different-shape of comparative example 1,2 and 3 of the present invention preparation is (to the photocatalytic activity of methyl orange solution curve over time under near infrared light; In Fig. 4, a is the change curve of comparative example 1, and b is the change curve of comparative example 2, and c is the change curve of comparative example 3.
Detailed description of the invention
Be clearly and completely described to the technical scheme in the embodiment of the present invention below.Obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Below in conjunction with specific embodiment, the invention will be further described; Except as otherwise indicating, the described number in comparative example and embodiment all in mass.
Comparative example 1
By 0.37 part of InCl
34H
2o and 0.23 part of thiosemicarbazides (CH
5n
3s) be under agitation dissolved in the mixed solvent be made up of 30 parts of deionized waters and 30 parts of absolute ethyl alcohols, after forming clear solution, load in reactor, make the compactedness of reactor be 60%, and react 24h at 160 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and ethanol wash, and vacuum drying at 55 DEG C, obtain the many indium sulfide photocatalysts of flower ball-shaped 0.2 part, bouquet diameter 1-2 μm, is about the β-In of 5-10nm by thickness
2s
3nanometer sheet forms.Many indium sulfide photocatalysts of 0.1 part of above-mentioned preparation are put in 100 parts of 20mg/L methyl orange solutions, with near infrared light, observe the degraded situation of methyl orange and draw degradation rate curve over time; React 3 hours, methyl orange degradation rate is only 18.9%.
Comparative example 2
By 0.46 part of In (NO
3)
34.5H
2o and 0.25 part (NH
4)
2s, is dissolved in respectively in 40 parts of deionized waters, is made into the indium nitrate aqueous solution and ammonium sulfide solution, under agitation added in the indium nitrate aqueous solution by ammonium sulfide hydrotropic solution, and controls to add speed to guarantee to form uniform colloidal sol; Afterwards, add 1mol/L salpeter solution 0.15 part, sol pH is adjusted to about 1-3; Finally, acidic sol is loaded in reactor, make the compactedness of reactor be about 80%, and react 24h at 180 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and ethanol wash, and vacuum drying at 55 DEG C, obtain the many indium sulfide photocatalysts of irregular particle shape 0.2 part of diameter 5-15nm.Many indium sulfide photocatalysts 0.1 part of above-mentioned preparation are put in 100 parts of 20mg/L methyl orange solutions, can the degraded of obvious catalysis methyl orange under the condition of near infrared light, react 3 hours, methyl orange degradation rate only reaches about 33.4%.
Comparative example 3
By 0.37 part of InCl
34H
2o and 0.63 part K
2s5H
2o, adds respectively in 25 parts of deionized waters, is made into the inidum chloride aqueous solution and potassium sulfide aqueous solution, under agitation added in the inidum chloride aqueous solution by potassium sulfide hydrotropic solution, and controls to add speed to guarantee to form uniform colloidal sol; Afterwards, add 1mol/L hydrochloric acid solution 0.25 part, sol pH is adjusted to about 1-3; Finally, acidic sol is loaded in reactor, make the compactedness of reactor be 50%, and react 24h at 160 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and alcohol, and vacuum drying at 55 DEG C, obtain the many indium sulfide photocatalysts of irregular particle shape 0.2 part of diameter 2-15nm.Indium sulfide photocatalyst more than 0.1 part is put in 100 parts of 20mg/L methyl orange solutions, can the degraded of obvious catalysis methyl orange under the condition of near infrared light, react 3 hours, methyl orange degradation rate only reaches about 46.7%.
Embodiment 1
By 0.23 part of In (NO
3)
34.5H
2o and 0.36 part Na
2s9H
2o, adds respectively in 25 parts of deionized waters, is made into the indium nitrate aqueous solution and sodium sulfide solution, under agitation added in the indium nitrate aqueous solution by vulcanized sodium hydrotropic solution, and controls to add speed to guarantee to form uniform colloidal sol; Afterwards, add 1mol/L salpeter solution 0.1 part, sol pH is adjusted to about 1-3; Finally, acidic sol is loaded in reactor, make the compactedness of reactor be 50%, and react 24h at 160 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and ethanol wash, and vacuum drying at 55 DEG C, obtain many indium sulfide photocatalysts 0.1 part.Put in 100 parts of 20mg/L methyl orange solutions, can the degraded of obvious catalysis methyl orange under the condition of near infrared light, react 3 hours, methyl orange degradation rate reaches about 70.2%.
Embodiment 2
By 0.46 part of In (NO
3)
34.5H
2o and 0.72 part Na
2s9H
2o, adds respectively in 35 parts of deionized waters, is made into the indium nitrate aqueous solution and sodium sulfide solution, under agitation added in the indium nitrate aqueous solution by vulcanized sodium hydrotropic solution, and controls to add speed to guarantee to form uniform colloidal sol; Afterwards, add with 1mol/L salpeter solution 0.2 part, sol pH is adjusted to about 1-3; Finally, acidic sol is loaded in reactor, make the compactedness of reactor be 70%, and react 16h at 200 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and ethanol wash, and vacuum drying at 55 DEG C, obtain many indium sulfide photocatalysts 0.2 part.Get 0.1 part, put in 200 parts of 20mg/L methyl orange solutions, can the degraded of obvious catalysis methyl orange under the condition of near infrared light, react 3 hours, methyl orange degradation rate reaches about 70.5%.
Embodiment 3
By 0.46 part of In (NO
3)
34.5H
2o and 0.72 part Na
2s9H
2o, adds respectively in 40 parts of deionized waters, is made into the indium nitrate aqueous solution and sodium sulfide solution, under agitation added in the indium nitrate aqueous solution by vulcanized sodium hydrotropic solution, and controls to add speed to guarantee to form uniform colloidal sol; Afterwards, add 1mol/L salpeter solution 0.2 part, sol pH is adjusted to about 1-3; Finally, acidic sol is loaded in reactor, make the compactedness of reactor be 80%, and react 20h at 180 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and ethanol wash, and vacuum drying at 55 DEG C, obtain many indium sulfide photocatalysts 0.2 part.Get 0.1 part, put in 200 parts of 20mg/L methyl orange solutions, can the degraded of obvious catalysis methyl orange under the condition of near infrared light, react 3 hours, methyl orange degradation rate reaches 70.9%.
Embodiment 4
By 0.69 part of In (NO
3)
34.5H
2o and 1.0 part Na
2s9H
2o, adds respectively in 40 parts of deionized waters, is made into the indium nitrate aqueous solution and sodium sulfide solution, under agitation added in the indium nitrate aqueous solution by vulcanized sodium hydrotropic solution, and controls to add speed to guarantee to form uniform colloidal sol; Afterwards, add 1mol/L salpeter solution 0.25 part, sol pH is adjusted to about 1-3; Finally, acidic sol is loaded in reactor, make the compactedness of reactor be 80%, and react 24h at 180 DEG C; After question response still naturally cools to room temperature, product filtered, use deionized water and ethanol wash, and vacuum drying at 55 DEG C, obtain many indium sulfide photocatalysts 0.3 part.Get 0.1 part, put in 300 parts of 20mg/L methyl orange solutions, can the degraded of obvious catalysis methyl orange under the condition of near infrared light, react 3 hours, methyl orange degradation rate reaches 71.9%.
Claims (6)
1. a method for catalyze and degrade organic pollutants, is characterized in that, β-In
2s
3nano material under near infrared light excites for catalyze and degrade organic pollutants; Described organic pollution is methyl orange;
Described β-In
2s
3nano material adopts following method to be prepared from:
Under agitation, the sulphur source aqueous solution is slowly joined in the aqueous solution of indium source, form yellow sol; Then, with nitric acid, sol pH is adjusted to 1-3; Again by adjustment pH after colloidal sol at 160-200
ohydro-thermal reaction 16-24 hour under C, then filters and is precipitated thing; Sediment is through washing, being drying to obtain product;
The described sulphur source aqueous solution is dissolved in deionized water by dissolvable sulfide and forms, and described dissolvable sulfide is potassium sulfide, ammonium sulfide or vulcanized sodium; The described indium source aqueous solution is dissolved in deionized water is formed by indium nitrate, inidum chloride.
2. method according to claim 1, is characterized in that, by β-In
2s
3nano material is placed in organic pollution, then uses near infrared light.
3. method according to claim 1 and 2, is characterized in that, described β-In
2s
3nano material particle spherical in shape, particle diameter are 5-10nm.
4. method according to claim 1 and 2, is characterized in that, after described near infrared light filters by filtered of infrared lamp light source the light that wavelength is 200nm-780nm, remaining light provides.
5. method according to claim 1 and 2, is characterized in that, in the aqueous solution of described indium source, in indium and the sulphur source aqueous solution, the mol ratio of sulphur is 1:2.5.
6. method according to claim 5, is characterized in that, described hydro-thermal reaction is carried out in hydrothermal reaction kettle, and the compactedness of colloidal sol in hydrothermal reaction kettle is the volume of 50%-80%; The washing lotion that described washing step uses is deionized water and alcohol; Described reaction temperature is 180
oc; The described reaction time is 24 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069880A (en) * | 2014-07-21 | 2014-10-01 | 大连海事大学 | Composite catalyst and preparation method of composite catalyst as well as application of composite catalyst |
| CN104959151B (en) * | 2015-06-02 | 2017-06-06 | 福州大学 | A kind of indium sulfide catalyst and its preparation method and application |
| CN108993539B (en) * | 2018-08-06 | 2021-07-13 | 济南大学 | Method for improving indium sulfide photocatalysis |
| CN111822004B (en) * | 2020-06-23 | 2022-11-15 | 南通职业大学 | Preparation method of tungsten disulfide/indium sulfide composite nano material |
| CN111939936A (en) * | 2020-08-24 | 2020-11-17 | 安徽建筑大学 | In2S3/TiO2Preparation method and application of photocatalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491769A (en) * | 2009-03-16 | 2009-07-29 | 天津工业大学 | Strontium carbonate with visible photoresponse and preparation method thereof |
| CN101961655A (en) * | 2010-08-30 | 2011-02-02 | 天津工业大学 | Indium sulfide photocatalyst with visible light response and preparation method thereof |
| CN102335616A (en) * | 2011-07-21 | 2012-02-01 | 北京工业大学 | Synthesis method of novel visible-light photocatalyst indium sulfide |
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| GB0125725D0 (en) * | 2001-10-26 | 2001-12-19 | Johnson Matthey Plc | Photocatalytic reactor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491769A (en) * | 2009-03-16 | 2009-07-29 | 天津工业大学 | Strontium carbonate with visible photoresponse and preparation method thereof |
| CN101961655A (en) * | 2010-08-30 | 2011-02-02 | 天津工业大学 | Indium sulfide photocatalyst with visible light response and preparation method thereof |
| CN102335616A (en) * | 2011-07-21 | 2012-02-01 | 北京工业大学 | Synthesis method of novel visible-light photocatalyst indium sulfide |
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