CN104556040A - Amorphous monatomic silicon ball as well as preparation method and application thereof - Google Patents
Amorphous monatomic silicon ball as well as preparation method and application thereof Download PDFInfo
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- CN104556040A CN104556040A CN201410721677.4A CN201410721677A CN104556040A CN 104556040 A CN104556040 A CN 104556040A CN 201410721677 A CN201410721677 A CN 201410721677A CN 104556040 A CN104556040 A CN 104556040A
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Abstract
The invention belongs to technical field of semiconductor material preparation, and particularly relates to an amorphous monatomic silicon ball as well as a preparation method and an application thereof. The method comprises the following steps: putting Mg powder and SiO2 balls into a mortar at the weight ratio, grinding uniformly, and pouring the ground mixture into a porcelain crucible A; with an H2/Ar mixed gas as a protective gas, burning in a tube furnace at a certain temperature for a certain period of time to obtain an amorphous monatomic silicon ball B; and pickling and removing unreacted Mg and a by-product MgO, so as to obtain a pure-phase amorphous monatomic silicon ball C. The amorphous monatomic silicon ball has full water decomposition capacity in a Z-Scheme system, and has important theory and application significance in photocatalytic hydrogen generation.
Description
Technical field
The invention belongs to technical field of semiconductor material preparation, particularly amorphous elemental silicon ball of one and its production and use.
Background technology
Silicon is narrow bandgap semiconductor material, and energy gap only has 1.12ev, elemental silicon stable in properties under room temperature, but in temperature higher than 700
.during C, there is thermoplasticity, can plastic deformation be presented under stress, extremely sensitive to the external factor such as light, heat, therefore obtain the positive regard of Chinese scholars; Meanwhile, occurring in nature element silicon is only second to oxygen element in stratum standing stock, but mainly exists with the form of silicate and quartz sand, and there is not elemental silicon, the preparation therefore about elemental silicon seems particularly important; The Application Areas of elemental silicon is wide: silicone content be 95% ~ 99% metallurgical grade silicon be mainly used in steel-making, aluminum silicon alloy and superalloy; Silicone content be 99.9999% solar energy level silicon be mainly used in the manufacturing of solar battery chip; Silicone content be 99.999999999% electronic level silicon be mainly used in semi-conductor chip manufacture; In addition, silicon is also for fields such as military affairs, aerospace, motor car engine manufactures, and therefore, the preparation method about elemental silicon has great importance, particularly amorphous spherical morphology material.
In a large amount of bibliographical informations, all mention that the pattern of semiconductor material can have a huge impact performance, especially ball-like structure makes the specific surface area of semiconductor material increase, facilitate light induced electron to be separated with the effective of hole, improve the H2-producing capacity of semiconductor material; The method of synthesis elemental silicon conventional is at present magnesium reduction process, magnesium powder is put into porcelain crucible from silica precursor by different mass ratioes, in tube furnace, logical hydrogen-argon-mixed heat reduction forms, but, the elemental silicon synthesizing a kind of ball-like structure is still limited by the restriction of precursor synthesis method and material person's character, and this makes the novel amorphous elemental silicon ball of design and synthesis in theoretical investigation and practical application, be still a huge challenge.
Summary of the invention
The object of this invention is to provide the preparation method that a kind of amorphous elemental silicon ball is simple and practical, the method take tetraethyl orthosilicate as raw material, the mixing solutions of ammoniacal liquor, ethanol and pure water is solvent, utilizes sol-gel method, magnesium reduction process, obtained amorphous elemental silicon ball material; Methyl alcohol sacrifices reagent for producing hydrogen, and Platinic chloride does promotor, analyzes the H2-producing capacity of amorphous elemental silicon ball.
The invention provides a kind of preparation method of amorphous elemental silicon ball, its feature comprises the following steps:
The preparation of amorphous simple substance Si ball: get Mg powder and SiO by weight
2(SiO
2preparation method's reference literature of ball: T. Zhang, et al. A self-templated route to hollow silica microspheres,
the Journal of Physical Chemistry C, 2009,113,3168-3175) and ball puts into mortar grinding evenly, pours A in porcelain crucible into; In tube furnace, use H
2/ Ar gas mixture is as protection gas, and calcine certain hour under certain temperature and obtain amorphous silicon simple substance ball B, pickling removes unreacted Mg and by product MgO, obtains pure phase amorphous silicon simple substance ball C.
In step, in described A, Mg powder is 200 orders, with SiO
2the mass ratio of ball is 1:2 to 1:6.
In step, in described B, calcining temperature is 650
.c, temperature rise rate is 3-5
.c/min, calcination time is 2 ~ 3h, wherein protects gas by the H of content 10%
2mix with the Ar of content 90%.
In step, the pickling of described C process refers to adopt dilute hydrochloric acid to process, and dilute hydrochloric acid is that 1:20 ~ 1:30 is formulated with commercially available concentrated hydrochloric acid (massfraction is 36% ~ 38%) and ethanol according to volume ratio.
Photocatalysis hydrogen production experiment of the present invention uses Lab-H
2photocatalysis hydrogen production system, operation steps is specific as follows: the present invention 300W xenon lamp is as light source, and the distance of light source and reactive system is 20 cm.
In photochemical catalysis experiment of the present invention, elementary silicon ball prepared by 50mg and 50mg BiVO
4(BiVO
4preparation method's reference literature Guan, M. L.; Ma, D. K.; Hu, S. W.; Chen, Y. J.; Huang, S. M. Inorganic chemistry 2011,50,800) FeCl being dispersed in the 2mmol of 200ml of photocatalyst
3in the aqueous solution, continuous stirring, on the surface of photocatalyst by the platinum plating of photoreduction sedimentation, the amount of platinum plating is 0.5% of catalyst quality mark, chloroplatinic acid aqueous solution as platinum source, at pre-irradiation, system is vacuumized the oxygen removing dissolving, in whole reaction process, carry out rapid stirring, to guarantee the uniform irradiation of photocatalyst suspension.The hydrogen produced is collected content gas chromatograph (TCD, nitrogen is as carrier gas and 5 dust molecular sieve columns for GC-SP7800, Beijing Jin Keruida, China) and analyzes.
Accompanying drawing explanation
The Raman figure of the Si simple substance ball material of Fig. 1 prepared by the present invention.
The TEM shape appearance figure of Fig. 2 material prepared by the present invention: left figure is SiO
2, right figure is amorphous silicon simple substance ball after reduction.
The Si simple substance ball material of Fig. 3 prepared by the present invention full water of decomposition hydrogen output curve in Z-Scheme system.
Fig. 4 is the XRD spectra of silicon metal simple substance ball prepared in comparative example of the present invention.
Can draw by the Raman figure of Fig. 1 the spherical elementary silicon that the present invention successfully synthesizes, can find out that the Raman spectrogram of Si is that 510 places have characteristic peak to occur in wave number; And be that the oxidation of 350-450 place occurs without peak at the Raman spectrogram medium wave number of Si, prove that reduction thoroughly further, the product obtained is spherical elementary silicon.
The TEM shape appearance figure of Fig. 2 material prepared by the present invention: left figure is SiO
2, right figure is amorphous silicon simple substance ball after reduction, the promising SiO of the information that can draw from the figure on the left side
2spherical morphology, the diameter of ball is approximately 340nm, spherical smooth surface; When after reduction, the elementary silicon obtained remains spherical pattern, but the surface of ball becomes coarse.
The Si material of Fig. 3 prepared by the present invention be full water of decomposition gas yield curve in Z-Scheme system, and this illustrates at Z-Scheme system Si-(Fe
2+/ Fe
3+)-BiVO
4can realize the ability of full water of decomposition, wherein, the output of 1h ~ 5h hydrogen is respectively 30 μm of ol/g, 110 μm of ol/g, 150 μm of ol/g, 190 μm of ol/g, 220 μm of ol/g, and the speed of hydrogen producing is about 44 μm of ol/hg.
The XRD figure of Fig. 4 spheroidal crystal elementary silicon synthesized by comparative example of the present invention, can determine that the pdf card number that product synthesized in comparative example is corresponding is JCPDS-27-1402, and product degree of crystallinity is very high by figure; Mg powder and SiO are described
2the mass ratio of presoma, not in 1:2 to 1:6 interval, can not get amorphous elemental silicon ball.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1:
The preparation of amorphous simple substance Si ball: get Mg powder (200 order) 0.1g and SiO
2porcelain crucible A is put into after ball 0.3g is even by ground and mixed; In tube furnace, use H
2(10%), Ar(90%) gas mixture as protection gas, 650 DEG C calcining 2h, the temperature rise rate of calcination process is 5
.c/min, obtains amorphous silicon simple substance ball B, finally uses dilute hydrochloric acid (concentrated hydrochloric acid: ethanol=1:20) to process removing unreacted Mg and by product MgO and obtains pure phase amorphous elemental silicon ball C.
embodiment 2:
The preparation of amorphous simple substance Si ball: get Mg powder (200 order) 0.1g and SiO
2porcelain crucible A is put into after ball 0.2g is even by ground and mixed; In tube furnace, use H
2(10%), Ar(90%) gas mixture as protection gas, 650 DEG C calcining 2.5h, the temperature rise rate of calcination process is 3
.c/min, obtains amorphous silicon simple substance ball B, finally uses dilute hydrochloric acid (concentrated hydrochloric acid: ethanol=1:30) to process removing unreacted Mg and by product MgO and obtains pure phase amorphous elemental silicon ball C.
embodiment 3:
The preparation of amorphous simple substance Si ball: get Mg powder (200 order) 0.1g and SiO
2porcelain crucible A is put into after ball 0.6g is even by ground and mixed; In tube furnace, use H
2(10%), Ar(90%) gas mixture as protection gas, 650 DEG C calcining 3h, the temperature rise rate of calcination process is 4
.c/min, obtains amorphous silicon simple substance ball B, finally uses dilute hydrochloric acid (concentrated hydrochloric acid: ethanol=1:25) to process removing unreacted Mg and by product MgO and obtains pure phase amorphous elemental silicon ball C.
comparative example:
The preparation of crystallization simple substance Si ball: get Mg powder (200 order) 0.1g and SiO
2porcelain crucible A is put into after ball 0.1g is even by ground and mixed; In tube furnace, use H
2(10%), Ar(90%) gas mixture as protection gas, 650 DEG C calcining 2h, the temperature rise rate of calcination process is 4
.c/min, obtains silicon metal simple substance ball B, finally uses dilute hydrochloric acid (concentrated hydrochloric acid: ethanol=1:20) to process removing unreacted Mg and by product MgO and obtains pure phase silicon metal simple substance ball C.
Claims (5)
1. an amorphous elemental silicon ball, is characterized in that described amorphous elemental silicon ball is adopted and prepares with the following method: get Mg powder and SiO by weight
2ball puts into mortar grinding evenly, pours A in porcelain crucible into; In tube furnace, use H
2/ Ar gas mixture is as protection gas, and calcine certain hour under certain temperature and obtain amorphous elemental silicon ball B, pickling removes unreacted Mg and by product MgO, obtains pure phase amorphous elemental silicon ball C, SiO
2preparation method's reference literature of ball: T. Zhang, et al. A self-templated route to hollow silica microspheres,
the Journal of Physical Chemistry C, 2009,113,3168-3175.
2. a kind of amorphous elemental silicon ball as claimed in claim 1, is characterized in that: described Mg powder is 200 orders, with SiO
2the mass ratio of ball is 1:2 to 1:6.
3. a kind of amorphous elemental silicon ball as claimed in claim 1, it is characterized in that: described calcining temperature is 650 DEG C, temperature rise rate is 3-5 DEG C/min, and calcination time is 2 ~ 3h, wherein protects gas by the H of content 10%
2mix with the Ar of content 90%.
4. a kind of amorphous elemental silicon ball as claimed in claim 1, is characterized in that: described pickling refers to adopt dilute hydrochloric acid to process, and dilute hydrochloric acid is that 1:20 ~ 1:30 is formulated with commercially available concentrated hydrochloric acid (massfraction is 36% ~ 38%) and ethanol according to volume ratio.
5. the purposes of a kind of amorphous elemental silicon ball as claimed in claim 1 in full water of decomposition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044777A (en) * | 2016-06-01 | 2016-10-26 | 北京大学 | Novel method for preparing nanometer silicon from silicon dioxide |
| CN113213483A (en) * | 2021-04-14 | 2021-08-06 | 三峡大学 | Preparation method of amorphous silicon powder for lithium ion battery cathode material |
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|---|---|---|---|---|
| JP4215126B2 (en) * | 2002-02-15 | 2009-01-28 | 株式会社東京大学Ｔｌｏ | Magnesium-based composite material and method for producing the same |
| CN101533907A (en) * | 2009-04-14 | 2009-09-16 | 北京科技大学 | Method for preparing silicon-based anode material of lithium-ion battery |
| CN102249239A (en) * | 2011-06-08 | 2011-11-23 | 浙江大学 | Preparation method for preparing high-purity simple substance silicon from agricultural wastes |
| CN103204506A (en) * | 2013-04-15 | 2013-07-17 | 上海应用技术学院 | Shape-controlled mesoporous silica nano-material and preparation method thereof |
| CN104030290A (en) * | 2014-06-30 | 2014-09-10 | 金之坚 | Method for producing nanometer silicon by adopting rice hull |
-
2014
- 2014-12-03 CN CN201410721677.4A patent/CN104556040A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4215126B2 (en) * | 2002-02-15 | 2009-01-28 | 株式会社東京大学Ｔｌｏ | Magnesium-based composite material and method for producing the same |
| CN101533907A (en) * | 2009-04-14 | 2009-09-16 | 北京科技大学 | Method for preparing silicon-based anode material of lithium-ion battery |
| CN102249239A (en) * | 2011-06-08 | 2011-11-23 | 浙江大学 | Preparation method for preparing high-purity simple substance silicon from agricultural wastes |
| CN103204506A (en) * | 2013-04-15 | 2013-07-17 | 上海应用技术学院 | Shape-controlled mesoporous silica nano-material and preparation method thereof |
| CN104030290A (en) * | 2014-06-30 | 2014-09-10 | 金之坚 | Method for producing nanometer silicon by adopting rice hull |
Non-Patent Citations (1)
| Title |
|---|
| TIERUI ZHANG ET AL.: "A Self-Templated Route to Hollow Silica Microspheres", 《J. PHYS. CHEM. C》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044777A (en) * | 2016-06-01 | 2016-10-26 | 北京大学 | Novel method for preparing nanometer silicon from silicon dioxide |
| CN113213483A (en) * | 2021-04-14 | 2021-08-06 | 三峡大学 | Preparation method of amorphous silicon powder for lithium ion battery cathode material |
| US11834339B2 (en) | 2021-04-14 | 2023-12-05 | China Three Gorges University | Method for preparing amorphous silicon powder for anode material of lithium ion battery |
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Application publication date: 20150429 |