CN100398453C - Method of burning gel of stearic acid for preparing Nano LaCo03 in type of perovskite - Google Patents
Method of burning gel of stearic acid for preparing Nano LaCo03 in type of perovskite Download PDFInfo
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- CN100398453C CN100398453C CNB2006101092152A CN200610109215A CN100398453C CN 100398453 C CN100398453 C CN 100398453C CN B2006101092152 A CNB2006101092152 A CN B2006101092152A CN 200610109215 A CN200610109215 A CN 200610109215A CN 100398453 C CN100398453 C CN 100398453C
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- stearic acid
- gel
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- lanthanum nitrate
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Abstract
This invention relates to a method for preparing nanoscale perovskite-type LaCoO3 by stearic acid gel combustion. The method comprises: (1) weighing lanthanum nitrate, cobalt nitrate and stearic acid at a mol ratio of 1 : 1 : (9.5-12.0); (2) heating in an oil bath, dissolving stearic acid, adding lanthanum nitrate and cobalt nitrate, magnetically stirring at 110-120 deg.C and reacting to obtain a gel; (3) combusting at 450 deg.C in a muffle furnace, taking out the product, milling and torrefying at 850 deg.C for 3 h in the muffle furnace to obtain 10-35 nm perovskite-type LaCoO3. The method is simple and suitable for mass production.
Description
Technical field
The invention belongs to perovskite typed nanometer LaCoO
3Preparing technical field specifically is to prepare perovskite typed nanometer LaCoO with the gel of stearic acid combustion method
3
Background technology
In recent years, nano science and nanotechnology were surging forward.The granular of nano-grain size, produced the not available small-size effect of block materials, surface effects, interfacial effect, quantum size effect and macro quanta tunnel effect etc., made them present the not available characteristic of a series of conventional materials at aspects such as magnetic, light, electricity and biomedicines.Nano material is in magnetic, electronics, optics, highdensity sintering, photochemical catalysis, sensing, especially all have wide application prospect in the fields such as biology, medical science.
LaCoO
3Belong to perovskite-type rare-earth composite oxides, it can be used as the catalyzer of environmental pollution treatment, oxygen sensor, solid fuel cell etc.Its most of performances depend on the production method of powder.So a good synthetic method often greatly changes its physical and chemical performance.LaCoO
3Nanometer its physical and chemical performance is better brought into play.
Preparation LaCoO
3Method adopt high temperature solid-state method, chemical coprecipitation, sol-gel method, hydrothermal synthesis method and low-temperature combustion synthesis usually.The properties of sample of high temperature solid-state method preparation is good, physical strength height, and have preferably active and anti-poisoning capability, but the product cut size and the homogeneity that make with this method are relatively poor, and easily introduce impurity, too high sintering and the reunion that causes product easily of temperature in the calcination process.The prepared perovskite typed powder of chemical coprecipitation has higher specific surface area and reactive behavior, but can't the realization response thing at the homodisperse of molecular level.Sol-gel method prepares perovskite-type rare-earth composite oxides to be had: (1) temperature of reaction is low, and reaction process is easy to control; (2) uniformity coefficient of goods, purity height (homogeneity can reach molecule or atomic level); (3) stoichiometry is accurate, is easy to modification, adulterated wide ranges (comprising adulterated amount and kind).But the preparation required time is longer, is difficult for realizing industrialization.
Combustion synthesis method is synthetic and propose with respect to self propagating high temperature.People such as Patil were raw material with the saturated aqueous solution (oxygenant) and the organic-fuel (reductive agent) of metal-salt first in 1988, each raw material is soluble in water, the Pyrex hard glass container that will fill solution then is positioned on the hot plate or in the retort furnace, be heated to 573～773K, solution seethes with excitement, concentrates, smolders, rapid burning on fire then obtains the loose oxide compound ultrafine powder of spumescence.The ultimate principle of this technology is: used oxygenant and fuel mixture have exothermic character, and the spontaneous generation redox reaction of energy finally obtains desired product under certain temperature trigger.The globule size of products obtained therefrom and distribution etc. and fuel used kind, synthesis condition etc. all have much relations.
Gel-burning synthetic method is a kind of low-temperature burning chemical process that sol-gel wet-chemical synthesis method and self-propagating combustion synthesis method are organically combined, and has simply fast, convenient, and easily realizes characteristics such as industrialization.Low-temperature combustion method prepares LaCoO at present
3And the employed organic-fuel of hotchpotch is Padil, glycine.The products obtained therefrom granularity is bigger.
The gel of stearic acid combustion method that we adopted is based on stearic acid fusing point lower (68-70 ℃), and itself also can be used as the solvent of metal-salt, and stearic acid has the dual function of Synergist S-421 95 and tensio-active agent concurrently, in building-up process, there is not or have only less water to participate in, thereby prevented the hydrolytic precipitation of metal ion, can reduce the agglomeration of product.The solid particulate that a large amount of gas percussions that produce in the combustion processes in addition form both can make powder granularity diminish, and also can prevent the reunion between the particle.So it is even to make size distribution under suitable condition, the nano-powder that particle diameter is little.Be expected to improve greatly the various physical and chemical performances of product.
Summary of the invention
The present invention has overcome present gel combustion synthesis method synthetic LaCoO
3It is big to have granularity, and shortcoming pockety adopts a kind of new fuel stearic acid, utilizes the gel of stearic acid combustion method to prepare perovskite typed nanometer LaCoO
3Provide stearic acid to prepare perovskite typed nanometer LaCoO
3Optimal conditions.
The present invention adopts with following scheme to realize, specifically may further comprise the steps: (1) is under the constant temperature oil bath heating condition, stearic acid is dissolved (2) lanthanum nitrate, the solid mixture of Xiao Suangu is dissolved in the fusion stearic acid, under the constant temperature magnetic agitation, the control certain temperature makes reaction system become gel behind the reaction certain hour.(3) gel continues dry back (dehydration), and gel is burnt at a certain temperature, after the burning, takes out product and grinds, and puts it in the retort furnace, calcines certain hour at a certain temperature, can obtain the uniform LaCoO of size distribution
3Powder.
The gel of stearic acid combustion method prepares perovskite typed nanometer LaCoO
3Suitable condition be: 1: 1: 9.5 in molar ratio～1: 1: 12 weighing lanthanum nitrate, Xiao Suangu, stearic acid.Under the oil bath heating condition, with the stearic acid dissolving, under the constant temperature magnetic agitation, with lanthanum nitrate, the solid mixture of Xiao Suangu is dissolved in the fusion stearic acid earlier, and 110～120 ℃ of temperature controls make it generate gel.Gel is placed retort furnace, make its burning in 450 ℃.After the burning, take out product and grind, again in retort furnace in 850 ℃ of calcining 3h, can get the LaCoO of 10nm-35nm
3Powder.
Lanthanum nitrate, Xiao Suangu, stearic mol ratio influences granularity, purity and the pattern of powder.Work as lanthanum nitrate, Xiao Suangu, stearic mol ratio was respectively 1: 1: 9.5～1: 1: 12 o'clock, can make the LaCoO of 10nm-35nm under optimum conditions
3Powder.Experimental result sees Table 1.This is because the stearic acid amount is crossed low owing to lack enough complexing agent molecules, all complexings of nitrate, the powder granularity skewness of preparation, powder reuniting.The stearic acid amount is big more, and the products obtained therefrom particle diameter is more little, and the reason that reduces can think that it is more tiny that this helps powder granularity owing to along with the increasing of stearic acid add-on, generated more gas.But the stearic acid amount is too high, and can make has more organic substance residues in the final product, for removing organism, needs the calcining longer time.Can cause waste on the other hand.So should select lanthanum nitrate, Xiao Suangu and stearic mol ratio for use is to be advisable in 1: 1: 9.5～1: 1: 12.
Table 1 lanthanum nitrate, Xiao Suangu, stearic mol ratio and LaCoO
3The relation of powder granularity size
| Lanthanum nitrate, Xiao Suangu and stearic mol ratio | 6 | 9 | 9.5 | 12 | 13 |
| Size distribution and pattern | Pattern is irregular, and reunion is arranged | 10nm-100nm, sphere, good dispersity | 10nm-35nm, sphere, good dispersity | 10nm-20nm, sphere, good dispersity | 2nm-10nm, sphere, good dispersity |
Temperature control is 110～120 ℃ in the oil bath, is because react in water bath with thermostatic control, and length not only consuming time (generally more than 12 hours) and reaction are not exclusively.As reaction conditions, through control experiment repeatedly, find constant temperature oil bath between 110～120 ℃ (edible beans system salad oil) with oil bath, reaction can be finished with fast speeds, and becomes glue respond well.
It is because gel sample is put into retort furnace that temperature of combustion is controlled to be 450 ℃, begins to heat up.When temperature reaches 400 ℃, rapidly catching fire, concentrate, be 4～6 minutes combustion time, for guaranteeing burning fully, temperature of combustion is controlled to be 450 ℃.
Experiment is found: when calcining temperature is lower than 850 ℃, can not become perovskite typed LaCoO fully
3Powder as at 700 ℃ of calcining 3h, has dephasign La inside the gained powder
2O
3, Co
2O
3, as accompanying drawing 1.. when calcining temperature is 850 ℃, behind the calcining 3h, can get perovskite typed LaCoO
3Powder.As accompanying drawing 2.
The present invention has following advantage and effect:
Raw material used in the present invention is easy to get, and nontoxic.The technology that is adopted has fast simple, and is convenient, and easily realize characteristics such as industrialization.Owing to use the stearic acid that can produce greater amount gas, make the products obtained therefrom even particle size distribution, size distribution is little.
Description of drawings
Fig. 1 is as lanthanum nitrate, Xiao Suangu, stearic mol ratio (n
La (NO3) 3: n
Co (NO3) 2: n
CH3-(CH2) 16-COOH) be 1: 1: 9.8, under 115 ℃ of the oil bath temperature controls, the gel that is generated is 450 ℃ of burnings and grind the back at 700 ℃ of calcinings 3 hours, gained powder LaCoO
3X-ray diffracting spectrum, in the gained powder La is arranged
2O
3, Co
2O
3Dephasign.Wherein indicate △ and represent LaCoO
3, indicate * represent La
2O
3, indicate zero and represent Co
2O
3
Fig. 2 is as lanthanum nitrate, Xiao Suangu, stearic mol ratio (n
La (NO3) 3: n
Co (NO3) 2: n
CH3-(CH2) 16-COOH) be 1: 1: 9.8, under 115 ℃ of the oil bath temperature controls, the gel that is generated grinds the back 850 ℃ of calcinings 3 hours in 450 ℃ of burnings, and gained powder X-ray diffracting spectrum fits like a glove with standard diagram PDF 40-1279 contrast, knows that products obtained therefrom is perovskite typed LaCoO
3
Fig. 3 is that lanthanum nitrate, Xiao Suangu, stearic mol ratio are 1: 1: 10, and under 115 ℃ of the temperature controls, the gel that makes generation is 450 ℃ of burnings, and the product after the burning is at 850 ℃ of transmission electron microscope pictures of 3 hours gained powders of calcining down
Fig. 4 is that lanthanum nitrate, Xiao Suangu, stearic mol ratio are 1: 1: 11.2.Under 113 ℃ of the temperature controls, the gel of generation is 450 ℃ of burnings, and the product after the burning is at 850 ℃ of transmission electron microscope pictures of calcining 3 hours gained powders down
Embodiment
Embodiment 1
A certain amount of lanthanum nitrate of difference weighing, Xiao Suangu, stearic acid, making its mol ratio is 1: 1: 10.At first under the constant temperature oil bath heating condition, with the stearic acid dissolving, under the constant temperature magnetic agitation, with lanthanum nitrate, the solid mixture of Xiao Suangu is dissolved in the fusion stearic acid, 115 ℃ of temperature controls, and the reaction times is to become gel after 3 hours.Make gel 450 ℃ of burnings, after the burning, take out product and grind and put it in the retort furnace, calcined 3 hours down, obtain nano-powder LaCoO as shown in Figure 3 at 850 ℃
3Pattern is spherical, even particle size distribution, and size is about 10nm-30nm.
Embodiment 2
A certain amount of lanthanum nitrate of difference weighing, Xiao Suangu, stearic acid, making its mol ratio is 1: 1: 11.2.At first under the constant temperature oil bath heating condition, with the stearic acid dissolving, in the constant temperature magnetic agitation, with lanthanum nitrate, the solid mixture of Xiao Suangu is dissolved in the fusion stearic acid, 113 ℃ of temperature controls, and the reaction times is 3 hours, makes it become gel.Make gel 450 ℃ of burnings, after the burning, take out product and grind and put it in the retort furnace, calcined 3 hours down, obtain as nano-powder LaCoO among Fig. 4 at 850 ℃
3Pattern is spherical, even particle size distribution, and size is about 10nm-20nm.
Claims (1)
1. one kind is adopted the gel of stearic acid combustion method to prepare perovskite typed nanometer LaCoO
3Method, it is characterized in that comprising the steps: (1) 1: 1: 9.5 in molar ratio～1: 1: 12, respectively weighing lanthanum nitrate, Xiao Suangu, stearic acid; (2) under the oil bath heating condition, with the stearic acid dissolving, under the constant temperature magnetic agitation, with lanthanum nitrate, the solid mixture of Xiao Suangu is dissolved in the fusion stearic acid earlier, 110～120 ℃ of temperature controls, and reaction makes it generate gel; (3) gel is placed retort furnace, makes its burning in 450 ℃, take out products of combustion and grind, again in retort furnace in 850 ℃ of calcining 3h, can get the spherical perovskite typed LaCoO of 10nm-35nm
3
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| CN101927172A (en) * | 2010-07-07 | 2010-12-29 | 昆明理工大学 | Silver-containing perovskite type oxygen reduction catalyst, and preparation method thereof |
| CN101884930A (en) * | 2010-07-07 | 2010-11-17 | 昆明理工大学 | Perovskite-type LaxCa1-xCoO3/Ag compound powder oxygen reduction catalyst and preparation method |
| CN103214057A (en) * | 2012-01-20 | 2013-07-24 | 中北大学 | Photocatalytic degradation of dinitrochlorobenzene waste water |
| CN110120527B (en) * | 2019-04-15 | 2021-03-16 | 南京晓庄学院 | Controllable synthesized lanthanum-doped cobalt oxide nanosheet and preparation method and application thereof |
| CN114408986B (en) * | 2022-01-21 | 2024-02-13 | 陕西彩虹新材料有限公司 | Nanoscale monocrystal ternary cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050249653A1 (en) * | 2002-07-09 | 2005-11-10 | Hirohisa Tanaka | Method for producing perovskite-type composite oxide |
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| US20050249653A1 (en) * | 2002-07-09 | 2005-11-10 | Hirohisa Tanaka | Method for producing perovskite-type composite oxide |
Non-Patent Citations (2)
| Title |
|---|
| 硬脂酸凝胶法制备纳米Al2O3粉末及其表征. 张少明等.中国粉体技术，第5期. 2004 |
| 硬脂酸凝胶法制备纳米Al2O3粉末及其表征. 张少明等.中国粉体技术，第5期. 2004 * |
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