CN103922394B - The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O - Google Patents

The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O Download PDF

Info

Publication number
CN103922394B
CN103922394B CN201410147181.0A CN201410147181A CN103922394B CN 103922394 B CN103922394 B CN 103922394B CN 201410147181 A CN201410147181 A CN 201410147181A CN 103922394 B CN103922394 B CN 103922394B
Authority
CN
China
Prior art keywords
cacu
preparation
calcium titanate
nanoribbon
copper calcium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410147181.0A
Other languages
Chinese (zh)
Other versions
CN103922394A (en
Inventor
王传义
李英宣
何洪泉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN201410147181.0A priority Critical patent/CN103922394B/en
Publication of CN103922394A publication Critical patent/CN103922394A/en
Application granted granted Critical
Publication of CN103922394B publication Critical patent/CN103922394B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

本发明公开了一种超长纳米线结构和纳米带结构钛酸铜钙的可控制备方法,该方法中用于制备CaCu3Ti4O12的氧化物原料TiO2、CaO和CuO,在高温下溶于NaCl和KCl的共熔体系中,Ca2+、Cu2+、Ti4+离子以10?5-10?8cm2/s的迁移速度重组形成纳米线结构和纳米带结构的CaCu3Ti4O12一维材料。该方法具有原料种类少,操作方法简便,工艺简单,成本低廉,绿色环保等特点,所制备的超长纳米线结构和纳米带结构的CaCu3Ti4O12对于研究其可见光响应光催化机理以及对于其他化合物的一维纳米材料制备,具有重大意义。同时在制备四元纳米线和纳米带结构化合物方面有广泛的指导意义。

The invention discloses a controllable preparation method of ultralong nanowire structure and nanoribbon structure copper calcium titanate. In the method, the oxide raw materials TiO 2 , CaO and CuO used to prepare CaCu 3 Ti 4 O 12 are prepared at high temperature Dissolved in the eutectic system of NaCl and KCl, Ca 2+ , Cu 2+ , Ti 4+ ions recombine at a migration speed of 10 ?5 -10 ?8 cm 2 /s to form CaCu with nanowire structure and nanoribbon structure 3 Ti 4 O 12 one-dimensional material. The method has the characteristics of few types of raw materials, simple operation method, simple process, low cost, and environmental protection. The prepared CaCu 3 Ti 4 O 12 with ultra-long nanowire structure and nanoribbon structure is useful for studying its visible light response photocatalytic mechanism and It is of great significance for the preparation of one-dimensional nanomaterials of other compounds. At the same time, it has extensive guiding significance in the preparation of quaternary nanowire and nanobelt structure compounds.

Description

一种超长纳米线结构及纳米带结构钛酸铜钙的制备方法Preparation method of ultralong nanowire structure and nanoribbon structure copper calcium titanate

技术领域technical field

本发明涉及一种超长纳米线结构和纳米带结构钛酸铜钙的制备方法,属于光催化纳米材料领域。The invention relates to a preparation method of ultralong nanowire structure and nanoribbon structure copper calcium titanate, belonging to the field of photocatalytic nanomaterials.

背景技术Background technique

一维纳米材料在近几年甚至近几十年来受到了广泛的研究,是由它的尺寸依赖性质决定的,其相比于块状纳米材料而言有着独特的物理、化学性质,所以其往往在光电、光伏、电化学以及电动机械方面有着广泛的应用。故而,一维纳米材料的合成对于现今的科技应用有着重要的基础意义。One-dimensional nanomaterials have been widely studied in recent years or even decades, which is determined by their size-dependent properties. Compared with bulk nanomaterials, they have unique physical and chemical properties, so they are often It has a wide range of applications in optoelectronics, photovoltaics, electrochemistry, and electromechanics. Therefore, the synthesis of one-dimensional nanomaterials has important fundamental significance for today's scientific and technological applications.

近十年来,各种二元化合物一维纳米材料,如:TiO2、ZnO、SnO2、MnO2、Ga2O3都已经被成功合成;三元化合物一维纳米材料,如:K2Ti6O13、K2Ti8O17纳米线也被人们用水热方法成功制备。而对于四元化合物的一维合成仍然是一个挑战。In the past ten years, various binary compound one-dimensional nanomaterials, such as: TiO 2 , ZnO, SnO 2 , MnO 2 , Ga 2 O 3 have been successfully synthesized; ternary compound one-dimensional nanomaterials, such as: K 2 Ti 6 O 13 , K 2 Ti 8 O 17 nanowires have also been successfully prepared by hydrothermal method. However, the one-dimensional synthesis of quaternary compounds remains a challenge.

钛酸铜钙(CaCu3Ti4O12)作为一种层状钙钛矿结构,其价带顶是Cu(3d)-O(2p)σ反键轨道,所以相对于TiO2的单纯O2p轨道,CaCu3Ti4O12具有更窄的禁带宽度,约为2.21eV。故而,CaCu3Ti4O12能够响应太阳光中的可见光部分,大大拓宽了光催化技术对于太阳光的利用率,受到了人们的广泛研究。目前,合成的CaCu3Ti4O12主要为6面的立方体结构,对于其一维纳米线和纳米带结构未见著于公开文献。而制备出不同结构的光催化材料对于研究材料的光催化机理和寻找更高效的光催化剂具有重要意义。Copper calcium titanate (CaCu 3 Ti 4 O 12 ), as a layered perovskite structure, has a Cu(3d)-O(2p)σ antibonding orbital at the top of its valence band, so compared to the pure O2p orbital of TiO 2 , CaCu 3 Ti 4 O 12 has a narrower band gap of about 2.21eV. Therefore, CaCu 3 Ti 4 O 12 can respond to the visible part of sunlight, which greatly broadens the utilization rate of sunlight for photocatalytic technology, and has been extensively studied by people. At present, the synthesized CaCu 3 Ti 4 O 12 is mainly a 6-sided cubic structure, and its one-dimensional nanowire and nanoribbon structures have not been found in the open literature. The preparation of photocatalytic materials with different structures is of great significance for studying the photocatalytic mechanism of materials and finding more efficient photocatalysts.

对于一维纳米材料的制备,目前见著于文献中的方法主要是:(1)、气-液-固生长技术(VLS),如:Si单质纳米线的生长;(2)、热蒸发生长技术,如:ZnO、SnO2、In2O3、VO等一维纳米线的制备;(3)、金属催化-分子束外延生长技术,如:ZnSe一维纳米线的制备;(4)、溶液生长技术。然而,作为一种非常简单的一维纳米材料生长方法:熔盐法,却非常少见于公开文献。故而,本发明采用简单易行的熔盐生长方法制备四元化合物对于其他化合物的一维纳米材料制备有很重要的指导意义。For the preparation of one-dimensional nanomaterials, the methods currently seen in the literature are mainly: (1), gas-liquid-solid growth technology (VLS), such as: the growth of Si elemental nanowires; (2), thermal evaporation growth Technology, such as: preparation of one-dimensional nanowires such as ZnO, SnO 2 , In 2 O 3 , VO; (3), metal catalysis-molecular beam epitaxy growth technology, such as: preparation of one-dimensional nanowires of ZnSe; (4), Solution growth technique. However, as a very simple one-dimensional nanomaterial growth method: molten salt method, it is very rare in the open literature. Therefore, the preparation of quaternary compounds by the simple and feasible molten salt growth method in the present invention has very important guiding significance for the preparation of one-dimensional nanomaterials of other compounds.

综上,通过本发明所述方法获得的超长纳米线结构和纳米带结构钛酸铜钙,对于研究其可见光响应光催化机理以及对于其他化合物的一维纳米材料制备具有重大意义。In summary, the superlong nanowire structure and nanoribbon structure copper calcium titanate obtained by the method of the present invention are of great significance for the study of its visible light-responsive photocatalytic mechanism and for the preparation of one-dimensional nanomaterials of other compounds.

发明内容Contents of the invention

本发明的目的在于,提供一种超长纳米线结构和纳米带结构钛酸铜钙的制备方法,是工艺简单、成本低廉的制备方法,该方法基于熔盐法合成化合物的原理,包括作为合成钛酸铜钙所需的氧化物原料与盐的混合,再在高温条件下灼烧数小时,最后生成超长纳米线结构和纳米带结构钛酸铜钙。该方法具有操作简便,工艺简单,绿色环保等特点,在制备四元纳米线和纳米带结构化合物方面有广泛的指导意义。The object of the present invention is to provide a method for preparing ultra-long nanowire structure and nanoribbon structure copper calcium titanate, which is a preparation method with simple process and low cost. The method is based on the principle of compound synthesis by molten salt method, including Copper calcium titanate required oxide raw materials are mixed with salt, and then burned for several hours under high temperature conditions, and finally ultra-long nanowire structure and nanoribbon structure copper calcium titanate are produced. The method has the characteristics of simple operation, simple process, environmental protection, etc., and has extensive guiding significance in the preparation of quaternary nanowire and nanobelt structure compounds.

本发明所述的一种超长纳米线结构或纳米带结构钛酸铜钙的制备方法,其特征在于按下列步骤进行:A kind of preparation method of superlong nanowire structure or nanoribbon structure copper calcium titanate of the present invention is characterized in that following steps are carried out:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO20.39-3.90g、CaO0.07-0.70g、CuO0.29-2.90g,再称取盐质量为NaCl7.60-50.50g,KCl7.00-49.50g置入玛瑙研钵中在球磨机上球磨1-12h,使其混合均匀;a. According to the chemical formula of copper calcium titanate CaCu 3 Ti 4 O 12 , weigh the quality of the oxide raw material as TiO 2 0.39-3.90g, CaO0.07-0.70g, CuO0.29-2.90g, and then weigh the quality of the salt as NaCl7. Put 60-50.50g, KCl7.00-49.50g into an agate mortar and mill on a ball mill for 1-12h to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为650-1000℃,反应时间为4-15h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 650-1000°C, and the reaction time is 4-15h;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在10-100kHz超声作用下清洗1-10次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构或纳米带结构钛酸铜钙。c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 1-10 times under the action of 10-100kHz ultrasonic to remove impurities, and then place the sample in a drying oven Drying at a temperature of 60° C. for 5 hours to obtain the target product copper calcium titanate with ultra-long nanowire structure or nanoribbon structure.

步骤b中的反应温度650-850℃为纳米线结构钛酸铜钙,反应温度850-1000℃为纳米带结构钛酸铜钙。The reaction temperature in step b is 650-850°C for copper calcium titanate with nanowire structure, and the reaction temperature for 850-1000°C is copper calcium titanate with nanobelt structure.

本发明所描述的一种超长纳米线结构和纳米带结构钛酸铜钙的制备方法,该方法中用于制备CaCu3Ti4O12的氧化物原料TiO2:0.39-3.90g、CaO:0.07-0.70g、CuO:0.29-2.90g,在高温下溶于NaCl和KCl的共熔体系中,Ca2+、Cu2+、Ti4+离子以10-5-10-8cm2/s的迁移速度重组形成纳米线结构和纳米带结构的CaCu3Ti4O12。反应过程控制反应温度为650℃-1000℃以保证盐能熔化,反应时间控制为4-15h,最后样品在管式炉中自然冷却到室温。将反应得到的产物加入去离子水洗涤、过滤、除去NaCl和KCl,再在10-100kHz超声作用下清洗1-10次以除去杂质,最后在温度60℃的烘箱中干燥5小时,得到CaCu3Ti4O12一维材料。该方法具有原料种类少,操作方法简便,工艺简单,成本低廉等特点,所制备的超长纳米线结构和纳米带结构的CaCu3Ti4O12对于研究其可见光响应光催化机理以及对于其他化合物的一维纳米材料制备具有重大意义。The preparation method of a superlong nanowire structure and nanoribbon structure copper calcium titanate described in the present invention, the oxide raw material TiO 2 used to prepare CaCu 3 Ti 4 O 12 in the method: 0.39-3.90g, CaO: 0.07-0.70g, CuO: 0.29-2.90g, dissolved in the eutectic system of NaCl and KCl at high temperature, Ca 2+ , Cu 2+ , Ti 4+ ions at 10 -5 -10 -8 cm 2 /s The migration velocity recombined to form the CaCu 3 Ti 4 O 12 nanowire structure and nanoribbon structure. During the reaction process, the reaction temperature is controlled at 650°C-1000°C to ensure that the salt can be melted, the reaction time is controlled at 4-15h, and finally the sample is naturally cooled to room temperature in a tube furnace. The product obtained by the reaction was washed with deionized water, filtered to remove NaCl and KCl, and then washed 1-10 times under the action of 10-100kHz ultrasound to remove impurities, and finally dried in an oven at a temperature of 60°C for 5 hours to obtain CaCu 3 Ti4O12 one -dimensional material. This method has the characteristics of few types of raw materials, simple operation method, simple process, and low cost. The prepared CaCu 3 Ti 4 O 12 with ultra-long nanowire structure and nanoribbon structure is very useful for studying its visible light response photocatalytic mechanism and for other compounds. The preparation of one-dimensional nanomaterials is of great significance.

附图说明Description of drawings

图1为本发明熔盐法制备的超长纳米线结构钛酸铜钙的X射线衍射图;Fig. 1 is the X-ray diffraction pattern of the superlong nanowire structure copper calcium titanate prepared by molten salt method of the present invention;

图2为本发明熔盐法制备的超长纳米带结构钛酸铜钙的X射线衍射图;Fig. 2 is the X-ray diffraction figure of the superlong nanoribbon structure copper calcium titanate prepared by the molten salt method of the present invention;

图3为本发明熔盐法制备的超长纳米线结构钛酸铜钙的扫描电子显微镜照片,其中标尺长度为2μm;Fig. 3 is the scanning electron micrograph of the superlong nanowire structure copper calcium titanate prepared by the molten salt method of the present invention, wherein the scale length is 2 μm;

图4为本发明熔盐法制备的超长纳米带结构钛酸铜钙的扫描电子显微镜照片,其中标尺长度为2μm;Fig. 4 is the scanning electron micrograph of the superlong nanoribbon structure copper calcium titanate prepared by the molten salt method of the present invention, wherein the scale length is 2 μm;

图5为本发明熔盐法制备的超长纳米线结构钛酸铜钙的投射电子显微镜照片,其中标尺长度为1μm;Fig. 5 is the projection electron micrograph of the superlong nanowire structure copper calcium titanate prepared by the molten salt method of the present invention, wherein the length of the scale is 1 μm;

图6为本发明熔盐法制备的超长纳米带结构钛酸铜钙的投射电子显微镜照片,其中标尺长度为1μm。Fig. 6 is a transmission electron micrograph of ultra-long nanoribbon calcium copper titanate prepared by the molten salt method of the present invention, where the length of the scale is 1 μm.

具体实施方式detailed description

为了更好地理解本发明,通过以下实例进一步说明;In order to better understand the present invention, further illustrate by following example;

实施例1Example 1

制备超长纳米线结构钛酸铜钙:Preparation of ultra-long nanowire structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO20.39g、CaO0.07g、CuO0.29g,再称取盐质量为NaCl7.60g和KCl7.00g置入玛瑙球磨罐中在球磨机上球磨1h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the oxide raw materials as TiO 2 0.39g, CaO 0.07g, CuO 0.29g, then weigh the salt as NaCl 7.60g and KCl 7.00g and put them into agate Mill in a ball mill for 1 hour on a ball mill to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为650℃,反应时间为4h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 650° C., and the reaction time is 4 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤,过滤,除去熔盐,再在10kHz超声作用下清洗1次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter to remove molten salt, and then wash once under the action of 10kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product calcium copper titanate CaCu 3 Ti 4 O 12 with ultra-long nanowire structure was obtained.

实施例2Example 2

制备超长纳米带结构钛酸铜钙:Preparation of ultra-long nanoribbon structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO20.39g、CaO0.07g、CuO0.29g,再称取盐质量为NaCl7.60g和KCl7.00g置入玛瑙球磨罐中在球磨机上球磨1h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the oxide raw materials as TiO 2 0.39g, CaO 0.07g, CuO 0.29g, then weigh the salt as NaCl 7.60g and KCl 7.00g and put them into agate Mill in a ball mill for 1 hour on a ball mill to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为850℃,反应时间为4h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 850° C., and the reaction time is 4 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤,过滤,除去熔盐,再在10kHz超声作用下清洗1次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米带结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter to remove molten salt, and then wash once under the action of 10kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product CaCu 3 Ti 4 O 12 is obtained.

实施例3Example 3

制备超长纳米线结构钛酸铜钙:Preparation of ultra-long nanowire structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO20.78-3.90g、CaO0.14g、CuO0.58g,再称取盐质量为NaCl14.05g,KCl13.25g置入玛瑙研钵中在球磨机上球磨3h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 0.78-3.90g, CaO0.14g, CuO0.58g, and then weigh the quality of salt as NaCl14.05g, KCl13.25g and set Put it into an agate mortar and mill it on a ball mill for 3 hours to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为700℃,反应时间为5h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 700°C, and the reaction time is 5h;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在30kHz超声作用下清洗2次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, and remove molten salt, and then wash it twice under the action of 30kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product calcium copper titanate CaCu 3 Ti 4 O 12 with ultra-long nanowire structure was obtained.

实施例4Example 4

制备超长纳米带结构钛酸铜钙:Preparation of ultra-long nanoribbon structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO20.78-3.90g、CaO0.14g、CuO0.58g,再称取盐质量为NaCl14.05g,KCl13.25g置入玛瑙研钵中在球磨机上球磨3h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 0.78-3.90g, CaO0.14g, CuO0.58g, and then weigh the quality of salt as NaCl14.05g, KCl13.25g and set Put it into an agate mortar and mill it on a ball mill for 3 hours to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为900℃,反应时间为5h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 900°C, and the reaction time is 5h;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在30kHz超声作用下清洗2次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米带结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, and remove molten salt, and then wash it twice under the action of 30kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product CaCu 3 Ti 4 O 12 is obtained.

实施例5Example 5

制备超长纳米线结构钛酸铜钙:Preparation of ultra-long nanowire structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO21.56g、CaO0.28g、CuO1.16g,再称取盐质量为NaCl20.20g,KCl19.50g置入玛瑙研钵中在球磨机上球磨5h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 1.56g, CaO0.28g, CuO1.16g, then weigh the quality of salt as NaCl20.20g, KCl19.50g and put it into agate Ball mill on a ball mill for 5 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为750℃,反应时间为8h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 750°C, and the reaction time is 8h;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在50kHz超声作用下清洗5次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 5 times under the action of 50kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product calcium copper titanate CaCu 3 Ti 4 O 12 with ultra-long nanowire structure was obtained.

实施例6Example 6

制备超长纳米带结构钛酸铜钙:Preparation of ultra-long nanoribbon structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO21.56g、CaO0.28g、CuO1.16g,再称取盐质量为NaCl20.20g,KCl19.50g置入玛瑙研钵中在球磨机上球磨5h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 1.56g, CaO0.28g, CuO1.16g, then weigh the quality of salt as NaCl20.20g, KCl19.50g and put it into agate Ball mill on a ball mill for 5 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为950℃,反应时间为8h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 950° C., and the reaction time is 8 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在50kHz超声作用下清洗5次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米带结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 5 times under the action of 50kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product CaCu 3 Ti 4 O 12 is obtained.

实施例7Example 7

制备超长纳米线结构钛酸铜钙:Preparation of ultra-long nanowire structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO22.34g、CaO0.42g、CuO1.74g,再称取盐质量为NaCl30.56g,KCl29.50g置入玛瑙研钵中在球磨机上球磨6h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 2.34g, CaO0.42g, CuO1.74g, then weigh the quality of salt as NaCl30.56g, KCl29.50g and put it into agate Ball mill on a ball mill for 6 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为800℃,反应时间为9h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 800° C., and the reaction time is 9 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在60kHz超声作用下清洗6次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 6 times under the action of 60kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product calcium copper titanate CaCu 3 Ti 4 O 12 with ultra-long nanowire structure was obtained.

实施例8Example 8

制备超长纳米带结构钛酸铜钙:Preparation of ultra-long nanoribbon structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO22.34g、CaO0.42g、CuO1.74g,再称取盐质量为NaCl30.56g,KCl29.50g置入玛瑙研钵中在球磨机上球磨6h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 2.34g, CaO0.42g, CuO1.74g, then weigh the quality of salt as NaCl30.56g, KCl29.50g and put it into agate Ball mill on a ball mill for 6 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为950℃,反应时间为9h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 950° C., and the reaction time is 9 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在60kHz超声作用下清洗6次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米带结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 6 times under the action of 60kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product CaCu 3 Ti 4 O 12 is obtained.

实施例9Example 9

制备超长纳米线结构钛酸铜钙:Preparation of ultra-long nanowire structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO23.12g、CaO0.56g、CuO2.32g,再称取盐质量为NaCl40.56g,KCl39.50g置入玛瑙研钵中在球磨机上球磨8h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 3.12g, CaO0.56g, CuO2.32g, then weigh the quality of salt as NaCl40.56g, KCl39.50g and put it into agate Ball mill on a ball mill for 8 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为850℃,反应时间为10h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 850°C, and the reaction time is 10h;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在80kHz超声作用下清洗8次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 8 times under the action of 80kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product calcium copper titanate CaCu 3 Ti 4 O 12 with ultra-long nanowire structure was obtained.

实施例10Example 10

制备超长纳米带结构钛酸铜钙:Preparation of ultra-long nanoribbon structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO23.12g、CaO0.56g、CuO2.32g,再称取盐质量为NaCl40.56g,KCl39.50g置入玛瑙研钵中在球磨机上球磨8h,使其混合均匀;a. According to the chemical formula of calcium copper titanate CaCu 3 Ti 4 O 12 , weigh the quality of oxide raw materials as TiO 2 3.12g, CaO0.56g, CuO2.32g, then weigh the quality of salt as NaCl40.56g, KCl39.50g and put it into agate Ball mill on a ball mill for 8 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为1000℃,反应时间为12h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 1000° C., and the reaction time is 12 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在80kHz超声作用下清洗8次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米带结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 8 times under the action of 80kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product CaCu 3 Ti 4 O 12 is obtained.

实施例11Example 11

制备超长纳米线结构钛酸铜钙:Preparation of ultra-long nanowire structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO23.90g、CaO0.70g、CuO2.90g,再称取盐质量为NaCl50.50g,KCl49.50g置入玛瑙研钵中在球磨机上球磨12h,使其混合均匀;a. According to the chemical formula of copper calcium titanate CaCu 3 Ti 4 O 12 , weigh the oxide raw materials as TiO 2 3.90g, CaO0.70g, CuO2.90g, then weigh the salt as NaCl50.50g, KCl49.50g and put them into agate Mill it on a ball mill for 12 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为800℃,反应时间为15h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 800°C, and the reaction time is 15h;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在100kHz超声作用下清洗10次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 10 times under the action of 100kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product calcium copper titanate CaCu 3 Ti 4 O 12 with ultra-long nanowire structure was obtained.

实施例12Example 12

制备超长纳米带结构钛酸铜钙:Preparation of ultra-long nanoribbon structure copper calcium titanate:

a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO23.90g、CaO0.70g、CuO2.90g,再称取盐质量为NaCl50.50g,KCl49.50g置入玛瑙研钵中在球磨机上球磨12h,使其混合均匀;a. According to the chemical formula of copper calcium titanate CaCu 3 Ti 4 O 12 , weigh the oxide raw materials as TiO 2 3.90g, CaO0.70g, CuO2.90g, then weigh the salt as NaCl50.50g, KCl49.50g and put them into agate Mill it on a ball mill for 12 hours in a mortar to make it evenly mixed;

b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应温度为900℃,反应时间为15h;b. The raw material mixture in step a is placed in a corundum crucible and reacted at high temperature in a tube furnace, the reaction temperature is 900° C., and the reaction time is 15 hours;

c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在100kHz超声作用下清洗10次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米带结构钛酸铜钙CaCu3Ti4O12c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 10 times under the action of 100kHz ultrasound to remove impurities, and then place the sample in a drying oven at a temperature of 60 After drying at ℃ for 5 hours, the target product CaCu 3 Ti 4 O 12 is obtained.

实施例13Example 13

对钛酸铜钙进行X射线衍射分析(XRD):X-ray diffraction analysis (XRD) of calcium copper titanate:

取实施例1-12获得的目标产物各150-400mg,将目标产物平整地压片于XRD样品槽里,再将样品槽放入BrukerD8粉末衍射仪进行衍射分析,衍射射线为:CuKɑX射线,衍射角度为:20°-80°,将分析测试结果与CaCu3Ti4O12的XRD标准卡片(JCPDS75-1149)进行比对,以上12个实施例得到的目标产物的X射线衍射分析结果见表1-13。Take 150-400 mg of the target products obtained in Examples 1-12, press the target products flatly into the XRD sample tank, and then put the sample tank into the Bruker D8 powder diffractometer for diffraction analysis. The diffracted rays are: CuK ɑ X-ray , the diffraction angle is: 20°-80°, compare the analytical test results with the CaCu 3 Ti 4 O 12 XRD standard card (JCPDS75-1149), the X-ray diffraction analysis results of the target product obtained in the above 12 examples See Table 1-13.

表1XRD标准卡片JCPDS75-1149的衍射角、衍射强度及钛酸铜钙晶面数据Table 1 Diffraction angle, diffraction intensity and copper calcium titanate crystal plane data of XRD standard card JCPDS75-1149

表2实施例1获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 2 Example 1 obtains the XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表3实施例2获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 3 Example 2 obtains the XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表4实施例3获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 4 Example 3 obtains the XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表5实施例4获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 5 Example 4 Obtains the XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表6实施例5获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 6 Example 5 obtains the XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表7实施例6获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 7 Example 6 Obtained XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表8实施例7获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 8 Example 7 Obtained XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表9实施例8获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 9 Example 8 Obtained XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表10实施例9获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 10 Example 9 Obtains the XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表11实施例10获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 11 The XRD diffraction angle, diffraction intensity and crystal plane data of the target product obtained in Example 10

表12实施例11获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 12 Example 11 Obtained XRD diffraction angle, diffraction intensity and crystal plane data of the target product

表13实施例12获得目标产物的XRD衍射角、衍射强度及其晶面数据Table 13 Example 12 Obtained XRD diffraction angle, diffraction intensity and crystal plane data of the target product

从表中结果可以看出:通过实施例1-12获得的目标产物均是钛酸铜钙(CaCu3Ti4O12)。以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此。It can be seen from the results in the table that the target products obtained in Examples 1-12 are copper calcium titanate (CaCu 3 Ti 4 O 12 ). The above descriptions are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto.

Claims (1)

1.一种超长纳米线结构或纳米带结构钛酸铜钙的制备方法,其特征在于按下列步骤进行: 1. a preparation method of superlong nanowire structure or nanoribbon structure copper calcium titanate, is characterized in that carrying out according to the following steps: a、按钛酸铜钙化学式CaCu3Ti4O12称取氧化物原料质量为TiO20.39-3.90g、CaO0.07-0.70g、CuO0.29-2.90g,再称取盐质量为NaCl7.60-50.50g,KCl7.00-49.50g置入玛瑙研钵中在球磨机上球磨1-12h,使其混合均匀; a. According to the chemical formula of copper calcium titanate CaCu 3 Ti 4 O 12 , weigh the quality of the oxide raw material as TiO 2 0.39-3.90g, CaO0.07-0.70g, CuO0.29-2.90g, and then weigh the quality of the salt as NaCl7. Put 60-50.50g, KCl7.00-49.50g into an agate mortar and mill on a ball mill for 1-12h to make it evenly mixed; b、将步骤a中的原料混合物置于刚玉坩埚中在管式炉中高温反应,反应时间为4-15h,反应温度650-850℃为纳米线结构钛酸铜钙,反应温度900-1000℃为纳米带结构钛酸铜钙; b. Put the raw material mixture in step a into a corundum crucible and react at a high temperature in a tube furnace. The reaction time is 4-15h, and the reaction temperature is 650-850°C. It is copper calcium titanate with nanowire structure, and the reaction temperature is 900-1000°C. It is copper calcium titanate with nanoribbon structure; c、将步骤b得到的样品随炉冷却至室温,加入去离子水洗涤、过滤、除去熔盐,再在10-100kHz超声作用下清洗1-10次以除去杂质,再将样品置于干燥箱中于温度60℃干燥5小时,即得目标产物超长纳米线结构或纳米带结构钛酸铜钙。 c. Cool the sample obtained in step b to room temperature with the furnace, add deionized water to wash, filter, remove molten salt, and then wash 1-10 times under the action of 10-100kHz ultrasonic to remove impurities, and then place the sample in a drying oven Drying at a temperature of 60° C. for 5 hours to obtain the target product copper calcium titanate with ultra-long nanowire structure or nanoribbon structure.
CN201410147181.0A 2014-04-12 2014-04-12 The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O Expired - Fee Related CN103922394B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410147181.0A CN103922394B (en) 2014-04-12 2014-04-12 The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410147181.0A CN103922394B (en) 2014-04-12 2014-04-12 The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O

Publications (2)

Publication Number Publication Date
CN103922394A CN103922394A (en) 2014-07-16
CN103922394B true CN103922394B (en) 2016-03-02

Family

ID=51140829

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410147181.0A Expired - Fee Related CN103922394B (en) 2014-04-12 2014-04-12 The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O

Country Status (1)

Country Link
CN (1) CN103922394B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105110375B (en) * 2015-07-20 2017-06-23 常州市武进晨光金属涂料有限公司 Infrared and chromic oxide-based pigment of visual camouflage and preparation method thereof
CN105198405B (en) * 2015-10-13 2017-06-06 福州大学 A kind of pressure-sensitive double functional ceramics of electric capacity and preparation method thereof
CN107029728A (en) * 2017-05-11 2017-08-11 中国科学院新疆理化技术研究所 A kind of Preparation method and use of the photochemical catalyst CaCu 3 Ti 4 O of the Lacking oxygen containing high density
CN111646497B (en) * 2019-03-04 2021-05-25 中国科学院物理研究所 Multi-order ordered perovskite PbHg3Ti4O12 crystal and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747051A (en) * 2009-10-21 2010-06-23 南昌大学 Low-temperature sintering method of CaCu3Ti4O12 ceramic material
CN101880160A (en) * 2010-07-08 2010-11-10 桂林理工大学 A kind of method for preparing CaCu3Ti4O12 powder
CN102173781A (en) * 2011-02-24 2011-09-07 西北工业大学 Preparation method of CaCu3Ti4O12 ceramics

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747051A (en) * 2009-10-21 2010-06-23 南昌大学 Low-temperature sintering method of CaCu3Ti4O12 ceramic material
CN101880160A (en) * 2010-07-08 2010-11-10 桂林理工大学 A kind of method for preparing CaCu3Ti4O12 powder
CN102173781A (en) * 2011-02-24 2011-09-07 西北工业大学 Preparation method of CaCu3Ti4O12 ceramics

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis of calcium copper titanate ceramics via the molten salts method;Ke-pi Chen et al.;《Ceramics International》;20100309;第36卷;1523-1527 *

Also Published As

Publication number Publication date
CN103922394A (en) 2014-07-16

Similar Documents

Publication Publication Date Title
Shandilya et al. Hydrothermal technology for smart materials
CN103395826B (en) Preparation method of aluminum doped zinc oxide nano powder
CN103922394B (en) The preparation method of a kind of overlong nanowire structure and nano belt structure CaCu 3 Ti 4 O
Samanta et al. Synthesis of mixed calcite–calcium oxide nanojasmine flowers
Márquez-Herrera et al. A novel synthesis of SrCO3–SrTiO3 nanocomposites with high photocatalytic activity
Rahman et al. Comprehensive review of micro/nanostructured ZnSnO 3: characteristics, synthesis, and diverse applications
Ullah et al. ZnO/TiO2 nanocomposite synthesized by sol gel from highly soluble single source molecular precursor
CN101857430B (en) Method for synthesizing titanate series electronic ceramic nano-crystalline materials
Huang et al. Preparation and characterization of the biomineralized zinc oxide particles in spider silk peptides
CN103274425B (en) Method for preparing globular nanometer nickel borate
CN103933990B (en) A kind of preparation method of 26 body structure CaCu 3 Ti 4 Os
CN104192914B (en) A kind of preparation method of manganese tungstate monocrystal nanowire
CN103318954B (en) Method for preparing sodium trititanate nanorods through solid-phase chemical reaction
CN108609652B (en) Method for preparing zirconium dioxide nano powder by using molten salt
Jose et al. Formation and optical characterization of unique zinc hydroxy stannate nanostructures by a simple hydrothermal method
CN103466703A (en) Bismuth titanate nanoneedle and preparation method thereof
CN109205662B (en) Two-step molten salt method for preparing flaky BaTiO3 microcrystals
Zhang et al. Hydrothermal synthesis of γ-MnOOH nanowires and α-MnO2 sea urchin-like clusters
CN107628641A (en) A kind of titanium dioxide nano thread and preparation method thereof
JP6758685B2 (en) Manufacturing method of nickel oxide nanoparticles
CN108163820B (en) Method for preparing tin diselenide nanowire at low temperature
Tian et al. Nano-sized coupled photocatalyst (Sn0. 25, Ti0. 75) O2 powders synthesized by a low temperature molten salt method
CN104386750B (en) A kind of scandium barium tantalate raw powder's production technology
Ma Green synthesis: properties and potential applications in nanomaterials and biomass nanocomposites
CN104671285A (en) Method for preparing cadmium molybdate nanorod

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160302

Termination date: 20190412