CN1669913A - Non-template liquid phase reduction method for preparing elemental selenium nanotube - Google Patents
Non-template liquid phase reduction method for preparing elemental selenium nanotube Download PDFInfo
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Abstract
The invention provides a non-mold liquid phase method for reduction synthesizing the monatomic selenium nanotubes, which is characterized in that the monoatomic selenium nanotube is produced on one step by sodium selenite as the selenium source and glucose as the reducing agent using hydrothermal reaction. The top-quality nanotubes of 200-300 nm of outside diameter, 150-200 nm of inside diameter and 15-40 of length-diameter ratio are rapidly produced in the hydrothermal environment wherein the temperature is 150-200 Deg. C and the reaction time is 8-12 h without any mold or surfactant. The method uses glucoses which are much more environment friendly as the reducing agent, reduces the emission toxicity and glucoses is safer than hydrazines hydrate as reducing agent. Moreover one step deacidizing passes over lots of complicated steps, and nano-crystals grow up more rapidly in the hydrothermal environment. The method has the characteristics of simply art, convenient processing, cheap cost, friendly environment and so on.
Description
Technical field
The present invention relates to the preparation method of elemental selenium nanotube.Belong to field of nanometer material technology.
Background technology
Simple substance selenium is a kind of important elemental semiconductor, has numerous tempting performances in many aspects, as lower fusing point (～490K), high optical conductivity (～8 * 10
4Scm
-1), nonlinear optical response performance and high chemically reactive etc., on photocell, rectifier, mechanical sensing device, photosensor and reprography, have application market widely.Since S.Iijima discovery carbon nanotube in 1991, the tubular nanometer structure was because its unique feature and performance become the focus that the investigation of materials scholar pays close attention at once.Because Se self crystalline structure is a kind of chain-like structure, have unique unsymmetric structure, make it to possess spontaneous one-dimensional growth habit.Therefore, the research of simple substance selenium one-dimentional structure is carried out in a large number, as one-dimensional nano line, nanometer rod and nano belt etc.Prior preparation method has physical methods such as laser splash and gas-solid deposition, and wet chemical method such as solvent thermal.Wherein the typical case of wet chemistry method representative is the research of the nano wire carried out of Xia Younan and group member thereof, and they are with H
2SeO
3Be selenium source, hydrazine hydrate is a reductive agent, by forming the red selenium of amorphous behind the room temperature reaction, in ethanol medium, and room temperature is grown (week) for a long time under the lucifuge, perhaps the assisting ultrasonic technology growth goes out tripartite selenium nano wire (B.Gates, B.Mayers, the A.Grossman of high length-diameter ratio, Y.Xia, Advanced Materials, 2002,14 (23): 1749-1752).Other selenium sources commonly used have Na
2SeSO
3, Na
2SeO
3With Se etc., also applied to prepare elemental selenium nano line or nanometer rod in a large number, big quantity research with simple substance Te of similar structures has also prepared corresponding nano wire, nanometer rod even nanotube (B.Mayers, Y.Xia, Advanced Materials, 2002,14 (4): 279-282), but but there is very big difficulty in the preparation of elemental selenium nanotube always, and it is less to be seen in report.Lu Jun etc. are by the solvent-thermal method growth, and in ethanol medium, 200 ℃ of growth 12h obtain the micron single-transistor of diameter 30 μ m with simple substance selenium, big (the Jun Lu of size, Yi Xie, Fen Xu, Liying Zhu, J.Mater.Chem., 2002,12,2755-2761).Nearest Ma Yurong etc. are with Na
2SeSO
3Disproportionation reaction in the acidic medium of micellar solution successfully prepare external diameter 80-300nm length from several μ m to the above elemental selenium nanotube of 100 μ m, wherein use surfactant B rij-35 to form micella and make soft template, assisting ultrasonic means room temperature growth (Yurong Ma, Limin Qi, Jiming Ma, Humin Cheng, Advanced Materials, 2004,16 (12): 1023-1026).Zhang Hui etc. are selenium source with simple substance selenium, prepare precursor aqueous solution (NH earlier in 200 ℃ of thermal and hydric environments
4)
2SeO
3, with the hydrazine hydrate reductive agent again, the assisting ultrasonic technology growth goes out the nanotube of external diameter 200-500nm, thickness of pipe 50nm, but the curtailment of nanotube (Hui Zhang, Deren Yang, Yujie Ji, Xiangyang Ma, Jin Xu, DuanlingQue, J.Phys.Chem.B, 108,1179-1182).Also there are many potential safety hazards in the reductive agent hydrazine hydrate that uses, and experimental implementation is closed liquid waste disposal all must be very careful.This shows that existing wet-chemical prepares the means major part grows based on ultrasonic technique, perhaps use surfactant modified or the limit threshold.Carry out the research of elemental selenium nanotube preparation, demand developing safe and practical easy synthesizing mean urgently.
Summary of the invention
The object of the invention is to provide a kind of non-template liquid phase reduction legal system to be equipped with elemental selenium nanotube, it is a kind of method for preparing the elemental selenium nanotube of complete crystallization by a stage reduction method, simplify the experimental technique route, and use safer reductive agent, need not the promptly synthetic elemental selenium nanotube of template, make it more easy to use, environmental friendliness.
The present invention implements like this: with the Sodium Selenite is selenium source, is reductive agent with glucose, passes through hydro-thermal reaction 10h one-step synthesis elemental selenium nanotube at 180 ℃.
(1) mol ratio with Sodium Selenite and glucose is set in 1: 2-1: 4 scopes, in the teflon-lined stainless steel cauldron of packing into, adding distil water to 80% volume is stirred to dissolving with glass stick, forms water white mixing solutions.
(2) the reactor sealing is tightened, put into baking oven, temperature is set in 150-200 ℃, take out reactor behind the reaction 8-12h, make its naturally cooling.
(3) subsequently the reaction precipitation thing is poured out, it is inferior to give a baby a bath on the third day after its birth with distilled water, washes twice with dehydrated alcohol again.50-70 ℃ of following dry 3-6h in vacuum drying oven collects sample retention in moisture eliminator at last.
The method of the synthetic elemental selenium nanotube of a kind of non-template liquid phase reduction provided by the invention is characterized in:
(1) is water-soluble selenium source with Sodium Selenite, can obtains uniform reaction system;
(2) with glucose be reductive agent, toxicological harmless is a kind of green environment close friend's a weak reductant, avoids using dangerous big reductive agent, for example uses hydrazine hydrate as reductive agent than in the past, not only reduces toxin expelling, and safety;
(3) reaction need not any template limit threshold or adds any surfactant modifiedly, and next step can obtain elemental selenium nanotube at thermal and hydric environment;
(4) the experimental technique route is simple, and operation is convenient.
(5) preparation elemental selenium nano external diameter of pipe 200-300nm, internal diameter 150-200nm, length-to-diameter ratio is up to 15-40, the complete crystallization monocrystalline.
Description of drawings
Fig. 1 elemental selenium nano powder X ray diffracting spectrum
Fig. 2 nanotube transmission electron microscope photo and electron diffraction spot: (a) (b) embodiment 1, (c) (d) embodiment 2
The single nanotube EDS of Fig. 3 power spectrum collection of illustrative plates
Embodiment
Further specify embodiment and effect with following indefiniteness embodiment:
The mol ratio of Sodium Selenite and glucose was set in 1: 2, get 0.0025mol Sodium Selenite and 0.005mol glucose, the volume 80mL that packs into gets in the teflon-lined stainless steel cauldron, adding distil water to 80% volume, be stirred to dissolving with glass stick, form water white mixing solutions.The reactor sealing is tightened, put into baking oven, temperature is set in 180 ℃, take out reactor behind the reaction 10h, make its naturally cooling.Subsequently the reaction precipitation thing is poured out, it is inferior to give a baby a bath on the third day after its birth with distilled water, washes twice with dehydrated alcohol again.60 ℃ of following dry 4h in vacuum drying oven collect sample retention in moisture eliminator at last.Fig. 1 is the X-ray diffraction spectrogram of the nanometer selenium powder of present embodiment preparation, as seen the gained powder is tripartite phase simple substance selenium, and diffraction peak is successively corresponding to the crystal face diffraction peak of (100), (101), (111), (102), (111), (200), (201), (003), (112), (103), (202), (210), (211) and (113) in the spectrogram; Do not find the diffraction peak of any impurity in the spectrogram, diffraction peak intensity is high and sharp-pointed, has as seen obtained the intact tripartite phase simple substance selenium of purity higher crystalline.Fig. 2 a-b is the transmission electron microscope photo of prepared sample, and visible simple substance selenium presents the tubulose pattern, nanotube external diameter 200-300nm, and internal diameter 150-200nm, length-to-diameter ratio has exceeded field range up to more than 15 in transmission electron microscope photo.The electron diffraction spot explanation nanotube that is inserted in Fig. 2 (a) is the monocrystalline of complete crystallization.Fig. 3 is the single nanotube EDS energy of a sample spectrogram, and product purity is higher, except the peak from copper mesh back of the body end C and Cu occurring, all is the power spectrum peak of simple substance selenium.
Embodiment 2
The mol ratio of preparation Sodium Selenite and glucose is 1: 4, and the volume 80mL that packs into gets in the teflon-lined stainless steel cauldron, and adding distil water to 80% volume is stirred to dissolving with glass stick, forms water white mixing solutions.The reactor sealing is tightened, put into baking oven, temperature is set in 180 ℃, take out reactor behind the reaction 10h, make its naturally cooling.Subsequently the reaction precipitation thing is poured out, it is inferior to give a baby a bath on the third day after its birth with distilled water, washes twice with dehydrated alcohol again.70 ℃ of oven dry down in vacuum drying oven are at last collected sample retention in moisture eliminator.Preparation selenium nanotube diameter 250-300nm, internal diameter 150-200nm, length-to-diameter ratio is up to 40.Fig. 2 c-d is the transmission electron microscope photo of prepared sample.
Embodiment 3
The mol ratio of preparation Sodium Selenite and glucose is 1: 2, and in the teflon-lined stainless steel cauldron of the volume 80mL that packs into, adding distil water to 80% volume is stirred to dissolving with glass stick, forms water white mixing solutions.The reactor sealing is tightened, put into baking oven, temperature is set in 150 ℃, take out reactor behind the reaction 12h, make its naturally cooling.Subsequently the reaction precipitation thing is poured out, it is inferior to give a baby a bath on the third day after its birth with distilled water, washes twice with dehydrated alcohol again.50 ℃ of oven dry down in vacuum drying oven are at last collected sample retention in moisture eliminator.Preparation selenium nanotube diameter 200-300nm, internal diameter 150-200nm, length-to-diameter ratio reaches 15.
Embodiment 4
The mol ratio of preparation Sodium Selenite and glucose is 1: 2, and the volume 80mL that packs into gets in the teflon-lined stainless steel cauldron, and adding distil water to 80% volume is stirred to dissolving with glass stick, forms water white mixing solutions.The reactor sealing is tightened, put into baking oven, temperature is set in 200 ℃, take out reactor behind the reaction 8h, make its naturally cooling.Subsequently the reaction precipitation thing is poured out, it is inferior to give a baby a bath on the third day after its birth with distilled water, washes twice with dehydrated alcohol again.50 ℃ of oven dry down in vacuum drying oven are at last collected sample retention in moisture eliminator.Prepared selenium nanotube length-to-diameter ratio reaches 20.All the other are with embodiment 1.
Claims (5)
1, a kind ofly need not the method that template liquid phase reduction prepares elemental selenium nanotube, it is characterized in that: with inorganic Sodium Selenite is selenium source, with glucose is reductive agent, reaction one-step synthesis tubulose elemental selenium nano crystalline substance under hydrothermal condition, the mol ratio that concrete processing condition are Sodium Selenite and glucose 1: 2～1: 4, pack in the teflon-lined stainless steel cauldron, add distilled water and form colourless transparent solution, reactor is tightened in sealing, under 150-200 ℃ of condition, react 8-12h, naturally cooling.Throw out takes out after washing in vacuum drying oven in 50-70 ℃ of dry 3-6h.
2, need not the method that template liquid phase reduction prepares elemental selenium nanotube by claim 1 is described, it is characterized in that adding and form colourless transparent solution behind the distilled water and account for stainless steel cauldron volume 80%.
3, describedly need not the method that template liquid phase reduction prepares elemental selenium nanotube by claim 1 or 2, it is characterized in that stainless steel cauldron is is liner with tetrafluoroethylene.
4, need not the method that template liquid phase reduction prepares elemental selenium nanotube by claim 1 is described, it is characterized in that it is to use earlier distilled water that throw out takes out washing, after use ethanol.
5, describedly need not the method that the template liquid phase reduction legal system is equipped with elemental selenium nanotube by claim 1,2 or 4, it is characterized in that elemental selenium nano external diameter of pipe 200-300nm, internal diameter 150-200nm, length-to-diameter ratio can reach 15-40.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885475A (en) * | 2010-07-26 | 2010-11-17 | 南京理工大学 | Method for synthesizing elemental selenium nano-belt |
| WO2011001246A3 (en) * | 2009-06-29 | 2011-05-19 | Pacific Rare Specialty Metals & Chemicals, Inc. | A process for the recovery of selenium from minerals and/or acidic solutions |
| US8268285B2 (en) | 2009-06-29 | 2012-09-18 | Pacific Rare Specialty Metals and Chemicals, Inc. | Process for the recovery of tellurium from minerals and/or acidic solutions |
| CN102730651A (en) * | 2012-07-08 | 2012-10-17 | 桂林理工大学 | Solvothermal method for regulating morphology of elemental nano-selenium |
| CN103302304A (en) * | 2013-06-07 | 2013-09-18 | 上海交通大学 | Preparation method of nickel or nickel alloy nanotube |
| CN103420344A (en) * | 2012-05-14 | 2013-12-04 | 武汉理工大学 | Preparation method for nano-selenium |
| CN108793099A (en) * | 2018-07-17 | 2018-11-13 | 武汉理工大学 | A kind of radial selenium nanotube and preparation method thereof |
| CN109911869A (en) * | 2019-03-12 | 2019-06-21 | 湖南工业大学 | A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition |
-
2005
- 2005-02-25 CN CN 200510024071 patent/CN1289387C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8268285B2 (en) | 2009-06-29 | 2012-09-18 | Pacific Rare Specialty Metals and Chemicals, Inc. | Process for the recovery of tellurium from minerals and/or acidic solutions |
| WO2011001246A3 (en) * | 2009-06-29 | 2011-05-19 | Pacific Rare Specialty Metals & Chemicals, Inc. | A process for the recovery of selenium from minerals and/or acidic solutions |
| US8092776B2 (en) | 2009-06-29 | 2012-01-10 | Pacific Rare Specialty Metals and Chemicals, Inc. | Process for the recovery of selenium from minerals and/or acidic solutions |
| US8361431B2 (en) | 2009-06-29 | 2013-01-29 | Pacific Rare Specialty Metals & Chemicals, Inc. | Process for the recovery of selenium from minerals and/or acidic solutions |
| CN101885475B (en) * | 2010-07-26 | 2012-05-16 | 南京理工大学 | Method for synthesizing elemental selenium nano-belt |
| CN101885475A (en) * | 2010-07-26 | 2010-11-17 | 南京理工大学 | Method for synthesizing elemental selenium nano-belt |
| CN103420344A (en) * | 2012-05-14 | 2013-12-04 | 武汉理工大学 | Preparation method for nano-selenium |
| CN103420344B (en) * | 2012-05-14 | 2015-07-22 | 武汉理工大学 | Preparation method for nano-selenium |
| CN102730651A (en) * | 2012-07-08 | 2012-10-17 | 桂林理工大学 | Solvothermal method for regulating morphology of elemental nano-selenium |
| CN103302304A (en) * | 2013-06-07 | 2013-09-18 | 上海交通大学 | Preparation method of nickel or nickel alloy nanotube |
| CN103302304B (en) * | 2013-06-07 | 2015-07-08 | 上海交通大学 | Preparation method of nickel or nickel alloy nanotube |
| CN108793099A (en) * | 2018-07-17 | 2018-11-13 | 武汉理工大学 | A kind of radial selenium nanotube and preparation method thereof |
| CN108793099B (en) * | 2018-07-17 | 2021-12-07 | 武汉理工大学 | Radial selenium nanotube and preparation method thereof |
| CN109911869A (en) * | 2019-03-12 | 2019-06-21 | 湖南工业大学 | A kind of method that selenium is extracted in the cleaning of selenic acid scum reduction decomposition |
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