CN102923762B - Biologically molecular assisted method for synthesizing hollow flower-shaped ZnIn2S4 balls - Google Patents
Biologically molecular assisted method for synthesizing hollow flower-shaped ZnIn2S4 balls Download PDFInfo
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- CN102923762B CN102923762B CN201210454845.9A CN201210454845A CN102923762B CN 102923762 B CN102923762 B CN 102923762B CN 201210454845 A CN201210454845 A CN 201210454845A CN 102923762 B CN102923762 B CN 102923762B
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- znin2s4
- indium
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Abstract
The invention belongs to the field of a preparation method of semiconductor material ZnIn2S4, and particularly relates to a biologically molecular assisted method for synthesizing hollow flower-shaped ZnIn2S4 balls, which comprises the following steps: using L-cysteine as a sulfur source, which is supplemented with an indium source and a zinc source; reacting under a solvothermal condition to synthesize the hollow flower-shaped ZnIn2S4 balls; then continuously carrying out filtering, washing and drying to obtain the target product. The indium source provided by the invention can be InCl3.4H2O; the zinc source can be Zn(CH3COO)2; the solvent can be glycol solution; the mole ratio of the zinc source to the indium source is 1:2-5; and the mole ratio of the zinc source to the sulfur source is 1:8-20. The method provided by the invention has the advantages of simple process, high target product yield, low cost and good dispersibility.
Description
Technical field
The invention belongs to semiconductor material ZnIn
2s
4preparation method field, relates in particular to the auxiliary synthetic ZnIn of a kind of biomolecules
2s
4the method of hollow bouquet.
Background technology
At present, developing visible light-responded novel semi-conductor catalyzer is one of important content of environmental pollution control and renewable energy source exploitation, and in order effectively to realize sun transformation of energy, people are to many oxide semiconductor (TiO
2srTiO
3wO
3) be studied as optoelectronic pole, but the with gap of oxide semiconductor is larger, the absorb light effectively in visible region, and sulfide semiconductor is because with gap is suitable, has good photoresponse in visible region, thereby be subject to paying attention to widely.Along with A II B
2iII C
4the broad research of IV type ternary semiconductor material, the dark resistance that it is extremely low, higher photoconductivity gain is paid much attention to, in same spectral range, it is more suitable for manufacturing optical detection device than Si, Ge and GaAs material, and it is also one solar cell material cheaply simultaneously.ZnIn
2s
4the energy gap of film is more satisfactory, and its homotype compound is prepared Cds-ZnIn by Garcia
2se
4solar cell, efficiency of conversion is 15%.ZnIn
2s
4belong to II-III
2-VI
4family's semiconductor material, has cubic spinel and six sides two kinds of typical structures mutually, and because its energy gap is narrow, visible region absorbs stronger, can improve well the efficiency of light energy utilization, and be widely used aspect electronics and optics.At present, mostly adopting the chemical reagent such as thiocarbamide, thioacetamide is both at home and abroad sulphur source, produces ZnIn
2s
4, the method productive rate is low, and toxicity is large, is not easy to production application.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provides a kind of technique simple, and target product yield is high, and cost is low, the auxiliary synthetic ZnIn of biomolecules of good dispersity
2s
4the method of hollow bouquet.
For solving the problems of the technologies described above, the present invention realizes like this.
The auxiliary synthetic ZnIn of a kind of biomolecules
2s
4the method of hollow bouquet, it is aided with Ji Xin source, indium source take Cys as sulphur source, reacts one-step synthesis ZnIn under solvent thermal condition
2s
4hollow bouquet, continues and filters, washs, is drying to obtain target product.
As a kind of preferred version, InCl can be selected in indium of the present invention source
34H
2o.
As another kind of preferred version, Zn (CH can be selected in zinc of the present invention source
3cOO)
2.
Further, solvent of the present invention can be selected ethylene glycol solution.
Further, the mol ratio in Yu Yin source, zinc of the present invention source is 1:2~5.
Further, the mol ratio in Yu Liu source, zinc of the present invention source is 1:8~20.
In addition, under solvent thermal condition of the present invention, reactions steps is that sulphur source, the mixed solution in Ji Xin source, indium source are packed in the autoclave take tetrafluoroethylene as liner, carries out high pressure solvent thermal reaction, and heat-up rate is 3~5 ℃/min.
Further, in ethylene glycol solution of the present invention, the volume ratio of ethylene glycol and water is 1:0~1.
Further, solvent thermal reaction temperature of the present invention is 80 ℃~180 ℃; Reaction times can be selected 12~48 hours.
Further, be 2~12 hours time of drying of the present invention; Drying temperature can be selected 40 ℃~80 ℃.
Cys (L-cysteine) is unique amino acid with reductibility group sulfydryl (SH) in 20 seed amino acids of constitutive protein matter, belong to aliphatic amino acid, at present widespread use in medicine, foodstuff additive and makeup.In addition, because the sulfydryl on Cys side chain (SH) polarity is very strong, except having the chemical reaction that all amino acid can occur, also have some special chemical reactions, in the present invention for reductive agent time, also play the effect in sulphur source, be compared to the sulphur sources such as thiocarbamide, Cys is nontoxic, green, is suitable for production practice application.
Compared with prior art, the present invention has following characteristics.
(1) technique of the present invention is simple, and cost is low, easy controlled operation.
(2) the target product ZnIn that prepared by the present invention
2s
4hollow bouquet, its purity is high, yield high (90%~95%), good dispersity.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
Fig. 1 is the SEM figure of target product of the present invention.
Fig. 2 is target product TEM shape appearance figure of the present invention.
Fig. 3 is the ultraviolet-visible absorption spectroscopy figure that target product of the present invention catalysis methyl orange solution under ultraviolet lighting obtains.
Embodiment
Utilize biomolecules to assist one-step synthesis ZnIn
2s
4the concrete grammar of hollow bouquet is as follows.
Take Zn (CH
3cOO)
2, InCl
34H
2o and Cys, in 100ml triangular flask, add 20ml ethylene glycol, and with magnetic apparatus stirring, then rapidly mixture is proceeded in 25ml autoclave, after sealing, under 160 ℃ of conditions, reacts 24 hours.After centrifugation, use a large amount of washing with alcohol, repeated centrifugation separates, washing for several times, product 60
oin the vacuum drying oven of C, be dried 12 hours.
Shown in Fig. 1 and Fig. 2, the present invention is by the ZnIn preparing
2s
4hollow bouquet carries out scanning electronic microscope (SEM) and transmission electron microscope (TEM) is analyzed, consequently products obtained therefrom good dispersity, and it is flower-shaped that surface is, and inside is hollow structure.
Shown in Figure 3, the present invention is by the ZnIn preparing
2s
4hollow bouquet carries out ultraviolet degradation tropeolin-D (30ml 15mg/L) experiment, and consequently at one hour, basic degraded completely, illustrated that target product has good photocatalysis performance to products obtained therefrom.
embodiment 1.
Take Zn (CH
3cOO)
2, InCl
34H
2o and Cys are in 100ml triangular flask, and its mol ratio is 1:2:8, add 20 ml ethylene glycol, and with magnetic apparatus stirring, then rapidly mixture are proceeded in 25ml autoclave, after sealing, under 160 ℃ of conditions, react 24 hours.After centrifugation, use a large amount of washing with alcohol, repeated centrifugation separates, washing for several times, product 60
oin the vacuum drying oven of C, be dried 8 hours.
embodiment 2.
Take Zn (CH
3cOO)
2, InCl
34H
2o and Cys are in 100ml triangular flask, and its mol ratio is 1:2:12, add 20 ml ethylene glycol solutions, and with magnetic apparatus stirring, then rapidly mixture are proceeded in 25ml autoclave, after sealing, under 180 ℃ of conditions, react 24 hours.After centrifugation, use a large amount of washing with alcohol, repeated centrifugation separates, washing for several times, product 60
oin the vacuum drying oven of C, be dried 8 hours.
embodiment 3.
Take Zn (CH
3cOO)
2, InCl
34H
2o and Cys are in 100ml triangular flask, and its mol ratio is 1:2:16, add 20 ml ethylene glycol solutions, and with magnetic apparatus stirring, then rapidly mixture are proceeded in 25ml autoclave, after sealing, under 140 ℃ of conditions, react 12 hours.After centrifugation, use a large amount of washing with alcohol, repeated centrifugation separates, washing for several times, product 60
oin the vacuum drying oven of C, be dried 8 hours.
embodiment 4.
Take Zn (CH
3cOO)
2, InCl
34H
2o and Cys are in 100ml triangular flask, its mol ratio is 1:2:8, adds 20 ml ethylene glycol and water mixture (volume ratio is 1:1), and stirs with magnetic apparatus, then rapidly mixture is proceeded in 25ml autoclave, after sealing, under 140 ℃ of conditions, react 48 hours.After centrifugation, use a large amount of washing with alcohol, repeated centrifugation separates, washing for several times, product 80
oin the vacuum drying oven of C, be dried 4 hours.
embodiment 5.
Take Zn (CH
3cOO)
2, InCl
34H
2o and Cys are in 100ml triangular flask, its mol ratio is 1:2:8, adds 20 ml ethylene glycol and water mixture (volume ratio is 1:1), and stirs with magnetic apparatus, then rapidly mixture is proceeded in 25ml autoclave, after sealing, under 180 ℃ of conditions, react 12 hours.After centrifugation, use a large amount of washing with alcohol, repeated centrifugation separates, washing for several times, product 40
oin the vacuum drying oven of C, be dried 12 hours.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, it will be understood by those of skill in the art that the present invention can have various changes.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., use needs as long as meet, within all should being included in protection scope of the present invention.
Claims (1)
1. the auxiliary synthetic ZnIn of biomolecules
2s
4the method of hollow bouquet, is characterized in that, take Cys as sulphur source, is aided with Ji Xin source, indium source, reacts one-step synthesis ZnIn under solvent thermal condition
2s
4hollow bouquet, continues and filters, washs, is drying to obtain target product; Described indium source is InCl
34H
2o; Described zinc source is Zn (CH
3cOO)
2; Described solvent is ethylene glycol solution; The mol ratio in Yu Yin source, described zinc source is 1:2~5; The mol ratio in Yu Liu source, described zinc source is 1:8~20; Under described solvent thermal condition, reactions steps is that sulphur source, the mixed solution in Ji Xin source, indium source are packed in the autoclave take tetrafluoroethylene as liner, carries out high pressure solvent thermal reaction, and heat-up rate is 3~5 ℃/min; In described ethylene glycol solution, the volume ratio of ethylene glycol and water is 1:0~1; Described solvent thermal reaction temperature is 80 ℃~180 ℃; Reaction times is 12~48 hours; Be 2~12 hours described time of drying; Drying temperature is 40 ℃~80 ℃.
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CN107827158A (en) * | 2017-10-08 | 2018-03-23 | 南京邮电大学 | A kind of controllable preparation small size Cu2WS4The method of nanocube |
CN110624563A (en) * | 2019-09-03 | 2019-12-31 | 沈阳化工大学 | Preparation method of silver ion doped zinc thioindate heterojunction photocatalyst |
CN110721708A (en) * | 2019-10-25 | 2020-01-24 | 江西理工大学 | Full-spectrum absorption ZnIn2S4Preparation method and application of base heterojunction catalyst |
CN114988371B (en) * | 2022-06-10 | 2023-06-13 | 南昌航空大学 | Size-controllable solvothermal synthesized indium zinc selenide nano-sheet and preparation method and application thereof |
CN115403066A (en) * | 2022-09-27 | 2022-11-29 | 陕西科技大学 | Spherical ZnIn assembled by nanosheets 2 S 4 Material and method for the production thereof |
Citations (1)
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CN1884090A (en) * | 2006-05-23 | 2006-12-27 | 南开大学 | ZnIn2S4 nano materials and their synthesis method and application |
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Non-Patent Citations (9)
Title |
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《Biomolecule-assisted synthesis of ZnIn2S4 flower-like hollow microspheres》;Yanping Zhang et al.;《Materials Letters》;20130403;第105卷;第185-188页 * |
《Facile synthesis of ZnS nanostructured spheres and their photocatalytic properties》;Xiao Wu et al.;《Journal of Alloys and Compounds》;20090808;第487卷;第537–544页 * |
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