CN105152225A - Preparation method of nanometer transition metal oxide and metal elementary substance material - Google Patents

Preparation method of nanometer transition metal oxide and metal elementary substance material Download PDF

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CN105152225A
CN105152225A CN201510404102.4A CN201510404102A CN105152225A CN 105152225 A CN105152225 A CN 105152225A CN 201510404102 A CN201510404102 A CN 201510404102A CN 105152225 A CN105152225 A CN 105152225A
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metal oxide
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王一菁
袁华堂
焦丽芳
张昊
胥亚楠
汪晓峰
董艳影
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Nankai University
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Abstract

一种纳米化的过渡金属氧化物和金属单质材料的制备方法,包括Cr2O3、TiO2、MnO、Fe3O4、CoO、NiO、ZnO、Cu、Au和Ag纳米颗粒,步骤如下:1)将金属盐和长链氨基有机物溶液混合,在氮气或氩气气氛下进行冷凝回流反应,冷却至室温后得到反应液;2)将低沸点溶剂A加入上述反应液中搅拌均匀后静置沉降,将离心得到的颗粒产物用正己烷分散并保存在通风干燥处。本发明的优点是:制备的产物颗粒粒径小、粒径分布较窄、分散度好且易于控制、催化活性高、电化学性能和循环性能好;其制备方法工艺简单,成本低廉、易于操作、能耗低且绿色环保,适合大规模生产。

A method for preparing nano-sized transition metal oxides and metal elemental materials, including Cr 2 O 3 , TiO 2 , MnO, Fe 3 O 4 , CoO, NiO, ZnO, Cu, Au and Ag nanoparticles, the steps are as follows: 1) Mix the metal salt and the long-chain amino organic compound solution, carry out condensation and reflux reaction under nitrogen or argon atmosphere, and obtain the reaction liquid after cooling to room temperature; 2) Add the low boiling point solvent A into the above reaction liquid and stir evenly, then let stand After settling, the granular product obtained by centrifugation was dispersed with n-hexane and stored in a ventilated and dry place. The invention has the advantages of small particle size, narrow particle size distribution, good dispersion and easy control, high catalytic activity, good electrochemical performance and cycle performance; the preparation method has simple process, low cost and easy operation , low energy consumption and environmental protection, suitable for large-scale production.

Description

一种纳米化的过渡金属氧化物和金属单质材料的制备方法A kind of preparation method of nano-sized transition metal oxide and metal elemental material

技术领域technical field

本发明涉及金属氧化物纳米颗粒的制备方法,特别是一种纳米化的过渡金属氧化物和金属单质材料的制备方法。The invention relates to a method for preparing metal oxide nanoparticles, in particular to a method for preparing nanometerized transition metal oxides and metal elemental materials.

背景技术Background technique

金属氧化物是一类重要的多功能材料,在能源领域方面的应用备受关注。其中,粒径小、高分散的纳米化廉价过渡金属氧化物因其具有高活性、结构简单等优点而被广泛研究和应用。但是目前的合成方法中,水热法、溶胶-凝胶法等因其制备的产物粒径大和较高的反应温度而限制了实际应用。因此,开发一种操作简单、成本低廉,环境友好的方法来合成纳米化的过渡金属氧化物材料具有重要的意义。Metal oxides are an important class of multifunctional materials, and their applications in the energy field have attracted much attention. Among them, the nano-sized and cheap transition metal oxides with small particle size and high dispersion have been widely studied and applied because of their high activity and simple structure. However, the current synthetic methods, such as hydrothermal method and sol-gel method, limit the practical application because of the large particle size of the prepared product and the high reaction temperature. Therefore, it is of great significance to develop an easy-to-operate, low-cost, and environmentally friendly method to synthesize nanoscale transition metal oxide materials.

发明内容Contents of the invention

本发明的目的是针对上述存在问题,提供一种工艺简单、反应温度低、成本低廉和能耗低的纳米化的过渡金属氧化物和金属单质材料的制备方法。The object of the present invention is to address the above existing problems and provide a method for preparing nano-sized transition metal oxides and metal elemental materials with simple process, low reaction temperature, low cost and low energy consumption.

本发明的技术方案:Technical scheme of the present invention:

一种纳米化的过渡金属氧化物和金属单质材料的制备方法,所述纳米化的过渡金属氧化物和金属单质材料包括Cr2O3、TiO2、MnO、Fe3O4、CoO、NiO、ZnO、Cu、Au和Ag纳米颗粒,步骤如下:A method for preparing nano-sized transition metal oxides and simple metal materials, the nano-sized transition metal oxides and simple metal materials include Cr 2 O 3 , TiO 2 , MnO, Fe 3 O 4 , CoO, NiO, ZnO, Cu, Au and Ag nanoparticles, the steps are as follows:

1)将金属盐和长链氨基有机物溶液混合并剧烈搅拌后,在氮气或氩气气氛下进行冷凝回流,回流温度为100-200℃,回流时间1-12小时,冷却至室温后得到反应液;1) After mixing the metal salt and the long-chain amino organic solution and vigorously stirring, condense and reflux under nitrogen or argon atmosphere, the reflux temperature is 100-200°C, the reflux time is 1-12 hours, and the reaction solution is obtained after cooling to room temperature ;

2)将低沸点溶剂A加入上述反应液中搅拌均匀后静置沉降,将离心得到的颗粒产物用正己烷分散并保存在通风干燥处。2) Add the low-boiling point solvent A into the above reaction solution, stir evenly, and then let it settle down, and disperse the granular product obtained by centrifugation with n-hexane and store it in a ventilated and dry place.

所述金属盐为过渡金属的氯化物、硝酸盐、碳酸盐或硫酸盐,其中过渡金属为钛、铬、锰,铁、钴、镍、铜、锌、银或金;长链氨基有机物溶液为油酸溶液、十二胺溶液、十六胺溶液或十八烯胺溶液;金属盐与长链氨基有机物溶液的摩尔比为1:40。The metal salt is chloride, nitrate, carbonate or sulfate of a transition metal, wherein the transition metal is titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver or gold; long-chain amino organic solution It is oleic acid solution, dodecylamine solution, hexadecylamine solution or octadecylamine solution; the molar ratio of metal salt to long-chain amino organic solution is 1:40.

所述溶剂A为乙醇、丙酮或二氯甲烷,低沸点溶剂A与反应液的体积比为3:1。The solvent A is ethanol, acetone or methylene chloride, and the volume ratio of the low boiling point solvent A to the reaction solution is 3:1.

本发明的优点和有益效果是:Advantage and beneficial effect of the present invention are:

该制备方法工艺简单,成本低廉、易于操作且能耗低;制备的产物颗粒粒径小、粒径分布较窄、分散度好且易于控制,纳米化的过渡金属氧化物表现出更高的催化活性、更好的电化学性能和循环性能;制备过程中不会造成环境污染,绿色环保,适合大规模生产。The preparation method has the advantages of simple process, low cost, easy operation and low energy consumption; the prepared product has small particle size, narrow particle size distribution, good dispersion and easy control, and the nano-sized transition metal oxide exhibits higher catalytic activity. Activity, better electrochemical performance and cycle performance; the preparation process will not cause environmental pollution, green and environmentally friendly, and suitable for large-scale production.

附图说明Description of drawings

图1为Fe3O4纳米颗粒的XRD图。Figure 1 is the XRD pattern of Fe 3 O 4 nanoparticles.

图2为Fe3O4纳米颗粒的TEM图。Figure 2 is a TEM image of Fe 3 O 4 nanoparticles.

图3为CoO纳米颗粒的XRD图。Figure 3 is the XRD pattern of CoO nanoparticles.

图4为CoO纳米颗粒的TEM图。Figure 4 is a TEM image of CoO nanoparticles.

图5为NiO纳米颗粒的XRD图。Figure 5 is the XRD pattern of NiO nanoparticles.

图6为NiO纳米颗粒的TEM图。Fig. 6 is a TEM image of NiO nanoparticles.

图7为ZnO纳米颗粒的XRD图。FIG. 7 is an XRD pattern of ZnO nanoparticles.

图8为ZnO纳米颗粒的TEM图。Fig. 8 is a TEM image of ZnO nanoparticles.

具体实施方式Detailed ways

下面结合实施例对本发明做进一步描述。The present invention will be further described below in conjunction with the examples.

实施例1:Example 1:

一种过渡金属氧化物Fe3O4纳米颗粒的制备方法,步骤如下:A preparation method of transition metal oxide Fe 3 O 4 nanoparticles, the steps are as follows:

1)将0.2gFe(NO3)3·9H2O和10mL油酸溶液分别加入三口瓶内剧烈搅拌后,在氩气气氛下进行冷凝回流,回流温度为200℃,回流时间4小时,冷却至室温后得到反应液;1) Add 0.2g Fe(NO 3 ) 3 ·9H 2 O and 10mL oleic acid solution into a three-necked flask and stir vigorously, then condense and reflux under an argon atmosphere. The reflux temperature is 200°C, and the reflux time is 4 hours. Cool to Obtain reaction solution after room temperature;

2)将30mL乙醇加入上述反应液中搅拌均匀后静置沉降,将离心得到的颗粒产物用正己烷分散,保存在通风干燥处。2) Add 30mL of ethanol to the above reaction solution, stir evenly, and then let it settle down, disperse the granular product obtained by centrifugation with n-hexane, and store it in a ventilated and dry place.

图1为制得的Fe3O4纳米颗粒的XRD图,图中显示:产物的所有衍射峰都可归属为立方相的Fe3O4Figure 1 is the XRD pattern of the prepared Fe 3 O 4 nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the cubic phase Fe 3 O 4 .

图2为制得的Fe3O4纳米颗粒的TEM图,图中显示:Fe3O4纳米颗粒的形貌为量子点,且粒径为3-7nm。Fig. 2 is a TEM image of the prepared Fe 3 O 4 nanoparticles, which shows that the appearance of the Fe 3 O 4 nanoparticles is quantum dots, and the particle size is 3-7nm.

实施例2:Example 2:

一种过渡金属氧化物CoO纳米颗粒的制备方法,步骤如下:A preparation method of transition metal oxide CoO nanoparticles, the steps are as follows:

1)将0.2gCoCO3、10mL油酸溶液分别加入三口瓶内剧烈搅拌后,在氩气气氛下进行冷凝回流,回流温度为180℃,回流时间8小时,冷却至室温后得到反应液;1) Add 0.2g CoCO 3 and 10mL oleic acid solution into the three-necked flask and stir vigorously, then condense and reflux under an argon atmosphere. The reflux temperature is 180°C, the reflux time is 8 hours, and the reaction solution is obtained after cooling to room temperature;

2)将30mL丙酮加入上述反应液中搅拌均匀后静置沉降,将离心得到的颗粒产物用正己烷分散,保存在通风干燥处。2) Add 30 mL of acetone into the above reaction solution, stir evenly, and then let it settle down. The granular product obtained by centrifugation is dispersed with n-hexane, and stored in a ventilated and dry place.

图3为制得的CoO纳米颗粒的XRD图,图中显示:产物的所有衍射峰都可归属为立方相的CoO。Figure 3 is the XRD pattern of the prepared CoO nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the cubic phase of CoO.

图4为制得的CoO纳米颗粒的TEM图,图中显示:CoO纳米颗粒的形貌为纳米立方,且粒径为20-25nm。FIG. 4 is a TEM image of the prepared CoO nanoparticles, which shows that the shape of the CoO nanoparticles is nanocubic, and the particle size is 20-25nm.

实施例3:Example 3:

一种过渡金属氧化物NiO纳米颗粒的制备方法,步骤如下:A preparation method of transition metal oxide NiO nanoparticles, the steps are as follows:

1)将0.5gNiSO4·6H2O、8mL十二胺溶液分别加入三口瓶内剧烈搅拌后,在氩气气氛下进行冷凝回流,回流温度为100℃,回流时间12小时,冷却至室温后得到反应液;1) Add 0.5gNiSO 4 ·6H 2 O and 8mL dodecylamine solution into a three-necked flask and stir vigorously, then condense and reflux under an argon atmosphere, the reflux temperature is 100°C, the reflux time is 12 hours, and after cooling to room temperature, The reaction solution;

2)将30mL丙酮加入上述反应液中搅拌均匀后静置沉降,将离心得到的颗粒产物用正己烷分散,保存在通风干燥处。2) Add 30 mL of acetone into the above reaction solution, stir evenly, and then let it settle down. The granular product obtained by centrifugation is dispersed with n-hexane, and stored in a ventilated and dry place.

图5为制得的NiO纳米颗粒的XRD图,图中显示:产物的所有衍射峰都可归属为立方相的NiO。Figure 5 is the XRD pattern of the prepared NiO nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the cubic NiO.

图6为制得的NiO纳米颗粒的TEM图,图中显示:NiO纳米颗粒的形貌为纳米花,且粒径为30-40nm。Fig. 6 is a TEM image of the prepared NiO nanoparticles, which shows that the appearance of the NiO nanoparticles is nanoflowers, and the particle size is 30-40nm.

实施例4:Example 4:

一种过渡金属氧化物ZnO纳米颗粒的制备方法,步骤如下:A preparation method of transition metal oxide ZnO nanoparticles, the steps are as follows:

1)将0.3gZnCl2·6H2O、10mL十八烯胺溶液分别加入三口瓶内剧烈搅拌后,在氮气气氛下进行冷凝回流,回流温度为200℃,回流时间8小时,冷却至室温后得到反应液;1) Add 0.3g of ZnCl 2 ·6H 2 O and 10mL of octadecylamine solution into a three-necked flask and stir vigorously, then condense and reflux under a nitrogen atmosphere, the reflux temperature is 200°C, the reflux time is 8 hours, and after cooling to room temperature, The reaction solution;

2)将20mL二氯甲烷加入上述反应液中搅拌均匀后静置沉降,将离心得到的颗粒产物用环己烷分散,保存在通风干燥处。2) Add 20mL of dichloromethane into the above reaction solution and stir evenly, then let it settle down, disperse the granular product obtained by centrifugation with cyclohexane, and store it in a ventilated and dry place.

图7为制得的ZnO纳米颗粒的XRD图,图中显示:产物的所有衍射峰都可归属为六方相的ZnO。Figure 7 is the XRD pattern of the prepared ZnO nanoparticles, which shows that all the diffraction peaks of the product can be attributed to the hexagonal ZnO.

图8为制得的ZnO纳米颗粒的TEM图,图中显示:ZnO纳米颗粒的形貌为纳米片,且粒径为30-40nm。FIG. 8 is a TEM image of the prepared ZnO nanoparticles, which shows that the morphology of the ZnO nanoparticles is nanosheets, and the particle size is 30-40nm.

Claims (3)

1. the transition metal oxide of nanometer and a preparation method for metal simple-substance material, is characterized in that: transition metal oxide and the metal simple-substance material of described nanometer comprise Cr 2o 3, TiO 2, MnO, Fe 3o 4, CoO, NiO, ZnO, Cu, Au and Ag nano particle, step is as follows:
1) by metal-salt and long chain amino organic solution mixing and vigorous stirring after, under nitrogen or argon gas atmosphere, carry out condensing reflux, reflux temperature is 100-200 DEG C, and return time 1-12 hour obtains reaction solution after being cooled to room temperature;
2) low boiling point solvent A is added stir in above-mentioned reaction solution after standing sedimentation, the centrifugal granular product normal hexane obtained is disperseed and is kept at air seasoning place.
2. the transition metal oxide of nanometer and the preparation method of metal simple-substance material according to claim 1, it is characterized in that: described metal-salt is the muriate of transition metal, nitrate, carbonate or vitriol, wherein transition metal is titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver or golden; Long chain amino organic solution is oleic acid solutions, amino dodecane solution, cetylamine solution or octadecenyl amine solution; The mol ratio of metal-salt and long chain amino organic solution is 1:40.
3. the transition metal oxide of nanometer and the preparation method of metal simple-substance material according to claim 1, it is characterized in that: described solvent orange 2 A is ethanol, acetone or methylene dichloride, the volume ratio of low boiling point solvent A and reaction solution is 3:1.
CN201510404102.4A 2015-07-10 2015-07-10 Preparation method of nanometer transition metal oxide and metal elementary substance material Pending CN105152225A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105562033A (en) * 2016-03-09 2016-05-11 扬州大学 A kind of preparation method of hydrophilic Fe3O4-Au double-sided particle catalyst
CN107399767A (en) * 2017-08-28 2017-11-28 四川理工学院 A kind of Fe doping NiO composites and semiconductor gas sensor
CN108080035A (en) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 A kind of method of hydrocarbon catalytic selective oxidation
CN109876176A (en) * 2019-02-22 2019-06-14 泉州市洛江区汇丰妇幼用品有限公司 A kind of Traditional Chinese medicine bacteriostatic sanitary napkin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XUEMIN HE ET AL.: "Phase- and Size-Dependent Optical and Magnetic Properties of CoO Nanoparticles", 《J. PHYS. CHEM. C》 *
窦永华 等: "单分散Fe3O4纳米粒子的合成、表征及其自组装", 《功能材料》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105562033A (en) * 2016-03-09 2016-05-11 扬州大学 A kind of preparation method of hydrophilic Fe3O4-Au double-sided particle catalyst
CN108080035A (en) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 A kind of method of hydrocarbon catalytic selective oxidation
CN108080035B (en) * 2016-11-22 2021-01-22 中国科学院大连化学物理研究所 Method for catalytic selective oxidation of hydrocarbon
CN107399767A (en) * 2017-08-28 2017-11-28 四川理工学院 A kind of Fe doping NiO composites and semiconductor gas sensor
CN107399767B (en) * 2017-08-28 2019-05-03 四川理工学院 A Fe-doped NiO composite material and semiconductor gas sensor
CN109876176A (en) * 2019-02-22 2019-06-14 泉州市洛江区汇丰妇幼用品有限公司 A kind of Traditional Chinese medicine bacteriostatic sanitary napkin

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Application publication date: 20151216