CN104028285A - Preparation method of Cu2ZnSnS4/La2Ti2O7 heterojunction photocatalytic composite material - Google Patents
Preparation method of Cu2ZnSnS4/La2Ti2O7 heterojunction photocatalytic composite material Download PDFInfo
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- CN104028285A CN104028285A CN201410210334.1A CN201410210334A CN104028285A CN 104028285 A CN104028285 A CN 104028285A CN 201410210334 A CN201410210334 A CN 201410210334A CN 104028285 A CN104028285 A CN 104028285A
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- la2ti2o7
- czts
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Abstract
The invention discloses a preparation method of a Cu2ZnSnS4/La2Ti2O7 heterojunction photocatalytic composite material, and belongs to the field of photocatalytic composite material. The composite material is prepared by a hydrothermal method and through an in situ growth process. The preparation method comprises the steps: firstly, taking La(NO3)3.6H2O and Ti(SO4)2 as raw materials, preparing La2Ti2O7 nanosheets by the hydrothermal method, then successively adding CuCl2, ZnCl2, SnCl2 and thioacetamide into ethylene glycol containing La2Ti2O7 according to the ratio of 2:1:1:8, stirring and carrying out ultrasonic treatment, transferring into a hydrothermal kettle, carrying out high-pressure heating, and thus obtaining the CZTS/La2Ti2O7 composite. CZTS is uniformly dispersed and grows on the surface of La2Ti2O7, and a good combination of the two components is conducive to better separating photogenerated carriers. Through recombination of semiconductors, not only is a light response range of single semiconductors expanded, but also the photogenerated electron-hole pair recombination is suppressed due to transport and separation of the photogenerated carriers in the semiconductors with different band gaps, so that the photocatalytic activity of the composite semiconductor catalyst is improved.
Description
Technical field
The invention belongs to photocatalyst technology field, be specifically related to a kind of Cu
2znSnS
4(CZTS)/La
2ti
2o
7the preparation method of heterojunction photocatalysis composite.
Background technology
Environment and the energy have become the worldwide problem of common concern, and the exploitation of photocatalysis technology and associated materials becomes the focus of materialogy and catalytic science research gradually.But single photochemical catalyst is difficult to effectively absorb ultraviolet light and visible ray simultaneously, and photo-generated carrier recombination probability is high, and this has just limited its photocatalytic activity.
As a kind of stratified material with unique texture and excellent activity, N-shaped semiconductor La
2ti
2o
7in photocatalysis field, obtained paying close attention to widely.But La
2ti
2o
7can only under ultraviolet light, there is photocatalytic activity, and the ultraviolet light part not enough sunshine gross energy of wavelength below 400nm 5%, therefore reduced to a great extent its use value.
For improving photocatalysis efficiency, expand response wave length scope, it is to realize the effective ways that a certain wavelength had to better photocatalysis effect that the semiconducting compound of two or more band structure coupling is carried out to the compound heterojunction photocatalyst that builds.。
Summary of the invention
The object of the invention is to solve La
2ti
2o
7poor and the high problem of the compound probability of photo-generated carrier of light absorption, and a kind of CZTS/La is provided
2ti
2o
7hetero-junctions visible light photocatalysis composite provides a kind of simple and effective preparation method simultaneously.The present invention has realized CZTS/La
2ti
2o
7heterojunction photocatalysis composite good photocatalysis performance under visible ray.
Preparation method provided by the present invention, comprises following step:
Cu
2znSnS
4/ La
2ti
2o
7the preparation method of hetero-junctions visible light photocatalysis composite, is characterized in that, comprises the following steps:
1) by La (NO
3)
36H
2o and Ti (SO
4)
2for the ratio of 1:1 is dissolved in deionized water, under stirring condition, add NaOH in molar ratio, making NaOH concentration is 1mol/L; After fully stirring, solution is proceeded in the autoclave with teflon lined, at 200 ℃, heat 24 hours; Naturally after cooling, product is through washing, and centrifugation obtains La at 90 ℃ after dry
2ti
2o
7;
2) take La
2ti
2o
7join in ethylene glycol, stir and form suspension; La
2ti
2o
7with Cu
2znSnS
4mol ratio be 1:0.2～0.8;
3) under magnetic agitation, by CuCl
2, ZnCl
2, SnCl
2, thioacetamide adds in above-mentioned suspension successively by the mol ratio of 2:1:1:8;
4) will be through step 3) after after the ultrasonic 30min of suspension that obtains, transfer in water heating kettle in, heat 15 hours at 180 ℃; Naturally after cooling, cyclic washing, centrifugation, at 90 ℃ after dry CZTS/La
2ti
2o
7compound.
The present invention adopts the method for growth in situ to prepare CZTS/La
2ti
2o
7hetero-junctions visible light photocatalysis composite, CZTS disperses to be grown in La equably
2ti
2o
7surface, it is separated better that the good combination of the two is conducive to photo-generated carrier.Due to La
2ti
2o
7be the n-type semiconductor of broad-band gap, and CZTS is the p-type semi-conducting material of narrow band gap, and the very high (>10 of the absorption coefficient of light
4cm
-1), by semi-conductive compound, not only expanded the photoresponse scope of composite, and transporting with separated due to photo-generated carrier between different band gap semiconductor, suppress right compound in light induced electron-hole, thereby improved the photocatalytic activity of composite semiconductor catalyst.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1, embodiment 2 and embodiment 3 products.
Fig. 2 is the stereoscan photograph of the embodiment of the present invention 2 products.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate substantive distinguishing features of the present invention and remarkable advantage, the present invention is only confined to by no means stated embodiment.
Embodiment 1
1) by 2.165g La (NO
3)
36H
2o and 1.200g Ti (SO
4)
2be dissolved in successively in deionized water, under stirring condition, add NaOH, the concentration that makes NaOH is 1mol/L.After fully stirring, solution is proceeded in the autoclave with teflon lined, at 200 ℃, heat 24 hours.Naturally after cooling, product is through washing, and centrifugation obtains La at 90 ℃ after dry
2ti
2o
7.
2) take 0.4g La
2ti
2o
7join in 40mL ethylene glycol, stir and form suspension.
3) under magnetic agitation, by 0.0627g CuCl
2, 0.0251ZnCl
2, 0.0415gSnCl
2, 0.1106g thioacetamide adds in suspension successively.
4) by after the ultrasonic 30min of suspension, transfer in the water heating kettle of 50mL in, heat 15 hours at 180 ℃.Naturally after cooling, cyclic washing, centrifugation, at 90 ℃ after dry CZTS/La
2ti
2o
7compound.
B in Fig. 1 can find out because CZTS content is less, and and La
2ti
2o
7peak have the place of coincidence, so almost can't see the diffraction maximum of CZTS.A in Fig. 1 is pure La
2ti
2o
7xRD figure.E in Fig. 1 is pure Cu
2znSnS
4xRD figure.
Table 1 is the visible light photocatalytic degradation efficiency of this composite in 60min.
Table 1
| Reaction time/min | 0 | 10 | 20 | 30 | 40 | 50 | 60 |
| Degradation efficiency/% | 0 | 37.1 | 46.8 | 51.3 | 59.5 | 60.1 | 65.6 |
Embodiment 2
1) by 2.165g La (NO
3)
36H
2o and 1.200g Ti (SO
4)
2be dissolved in successively in deionized water, under stirring condition, add NaOH, the concentration that makes NaOH is 1mol/L.After fully stirring, solution is proceeded in the autoclave with teflon lined, at 200 ℃, heat 24 hours.Naturally after cooling, product is through washing, and centrifugation obtains La at 90 ℃ after dry
2ti
2o
7.
2) take 0.4g La
2ti
2o
7join in 40mL ethylene glycol, stir and form suspension.
3) under magnetic agitation, by 0.1568g CuCl
2, 0.0627ZnCl
2, 0.1038gSnCl
2, 0.2765g thioacetamide adds in suspension successively, what guarantee that each step obtains is settled solution.
4) by after the ultrasonic 30min of suspension, transfer in the water heating kettle of 50mL in, heat 15 hours at 180 ℃.Naturally after cooling, cyclic washing, centrifugation, at 90 ℃ after dry CZTS/La
2ti
2o
7compound.
C in Fig. 1 can find out La
2ti
2o
7the middle diffraction maximum that occurs CZTS.By Fig. 2, find out that CZTS is evenly grown in La
2ti
2o
7in nanometer sheet.Table 2 is the visible light photocatalytic degradation efficiency of this composite in 60min.
Table 2
| Reaction time/min | 0 | 10 | 20 | 30 | 40 | 50 | 60 |
| Degradation efficiency/% | 0 | 46.7 | 52.8 | 57.8 | 65.0 | 69.2 | 73.8 |
Embodiment 3
1) by 2.165g La (NO
3)
36H
2o and 1.200g Ti (SO
4)
2be dissolved in successively in deionized water, under stirring condition, add NaOH, the concentration that makes NaOH is 1mol/L.After fully stirring, solution is proceeded in the autoclave with teflon lined, at 200 ℃, heat 24 hours.Naturally after cooling, product is through washing, and centrifugation obtains La at 90 ℃ after dry
2ti
2o
7.
2) take 0.4g La
2ti
2o
7join in 40mL ethylene glycol, stir and form suspension.
3) under magnetic agitation, by 0.2509g CuCl
2, 0.1003ZnCl
2, 0.1661gSnCl
2, 0.4424g thioacetamide adds in suspension successively, what guarantee that each step obtains is settled solution.
4) by after the ultrasonic 30min of suspension, transfer in the water heating kettle of 50mL in, heat 15 hours at 180 ℃.Naturally after cooling, cyclic washing, centrifugation, at 90 ℃ after dry CZTS/La
2ti
2o
7compound.
D in Fig. 1 can find out La
2ti
2o
7the diffraction maximum of middle CZTS is more obvious.Table 3 is the visible light photocatalytic degradation efficiency of the interior composite of 60min for this reason
Table 3
| Reaction time/min | 0 | 10 | 20 | 30 | 40 | 50 | 60 |
| Degradation efficiency/% | 0 | 32.6 | 44.7 | 50.1 | 57.3 | 60.0 | 66.7 |
Claims (1)
1.Cu
2znSnS
4/ La
2ti
2o
7the preparation method of heterojunction photocatalysis composite, is characterized in that, comprises the following steps:
1). by La (NO
3)
36H
2o and Ti (SO
4)
2for the ratio of 1:1 is dissolved in deionized water, under stirring condition, add NaOH in molar ratio, making NaOH concentration is 1mol/L; After fully stirring, solution is proceeded in the autoclave with teflon lined, at 200 ℃, heat 24 hours; Naturally after cooling, product is through washing, and centrifugation obtains La at 90 ℃ after dry
2ti
2o
7;
2). take La
2ti
2o
7join in ethylene glycol, stir and form suspension; La
2ti
2o
7with Cu
2znSnS
4mol ratio be 1:0.2～0.8;
3). under magnetic agitation, by CuCl
2, ZnCl
2, SnCl
2, thioacetamide adds in above-mentioned suspension successively by the mol ratio of 2:1:1:8;
4). by after the ultrasonic 30min of suspension, transfer in water heating kettle in, heat 15 hours at 180 ℃; Naturally after cooling, cyclic washing, centrifugation, at 90 ℃ after dry CZTS/La
2ti
2o
7compound.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391056A (en) * | 2016-09-30 | 2017-02-15 | 福建禹环境科技有限公司 | ZnxCdl-xS/TiO2 nanometer photocatalytic material and preparation thereof |
| CN109289883A (en) * | 2018-09-11 | 2019-02-01 | 同济大学 | A kind of preparation method of photocatalyst preparation |
| CN109534391A (en) * | 2018-12-04 | 2019-03-29 | 北京航空航天大学 | A kind of application method of lanthanium titanate nanometer sheet photocatalysis fixed nitrogen |
| CN111437834A (en) * | 2020-05-19 | 2020-07-24 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
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|---|---|---|---|---|
| CN101063232A (en) * | 2007-05-28 | 2007-10-31 | 上海晶生实业有限公司 | Lanthanum titanates single-crystal and upgrowth technology thereof |
| WO2014016489A2 (en) * | 2012-07-26 | 2014-01-30 | Imra Europe Sas | Large-grain crystallised metal chalcogenide film, colloidal solution of amorphous particles, and preparation methods |
| CN103613119A (en) * | 2013-11-21 | 2014-03-05 | 电子科技大学 | Preparation method and application of copper zinc tin sulfide |
-
2014
- 2014-05-17 CN CN201410210334.1A patent/CN104028285A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063232A (en) * | 2007-05-28 | 2007-10-31 | 上海晶生实业有限公司 | Lanthanum titanates single-crystal and upgrowth technology thereof |
| WO2014016489A2 (en) * | 2012-07-26 | 2014-01-30 | Imra Europe Sas | Large-grain crystallised metal chalcogenide film, colloidal solution of amorphous particles, and preparation methods |
| CN103613119A (en) * | 2013-11-21 | 2014-03-05 | 电子科技大学 | Preparation method and application of copper zinc tin sulfide |
Non-Patent Citations (1)
| Title |
|---|
| 田晓萌等: ""CZTS／La2Ti2O7纳米粉体的制备及光催化性能"", 《中国科技论文》, vol. 9, no. 3, 31 March 2014 (2014-03-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391056A (en) * | 2016-09-30 | 2017-02-15 | 福建禹环境科技有限公司 | ZnxCdl-xS/TiO2 nanometer photocatalytic material and preparation thereof |
| CN109289883A (en) * | 2018-09-11 | 2019-02-01 | 同济大学 | A kind of preparation method of photocatalyst preparation |
| CN109534391A (en) * | 2018-12-04 | 2019-03-29 | 北京航空航天大学 | A kind of application method of lanthanium titanate nanometer sheet photocatalysis fixed nitrogen |
| CN111437834A (en) * | 2020-05-19 | 2020-07-24 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
| CN111437834B (en) * | 2020-05-19 | 2022-07-12 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
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Application publication date: 20140910 |