CN101898749B - Method for preparing metal oxide hollow particles or fibers - Google Patents
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- Inorganic Fibers (AREA)
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Abstract
本发明涉及一种金属氧化物空心粒子、金属氧化物空心纤维、金属空心粒子或金属空心纤维的制备方法。一种金属氧化物空心粒子或纤维的制备方法，其特征在于它包括如下步骤：将含有金属化合物和聚合物的复合粒子或复合纤维置炉中，以5-400℃/min的升温速率在300-1000℃下对其进行处理10min-48h，随炉冷却后得到金属氧化物空心粒子或金属氧化物空心纤维。该方法简易，通过调节升温速率可以得到具有不同内部空心结构的空心粒子或空心纤维。
The invention relates to a method for preparing metal oxide hollow particles, metal oxide hollow fibers, metal hollow particles or metal hollow fibers. A method for preparing metal oxide hollow particles or fibers is characterized in that it comprises the following steps: placing composite particles or composite fibers containing metal compounds and polymers in a furnace, and heating at a rate of 5-400°C/min at 300- It is treated at 1000° C. for 10 minutes to 48 hours, and the metal oxide hollow particles or metal oxide hollow fibers are obtained after cooling in a furnace. The method is simple, and hollow particles or hollow fibers with different internal hollow structures can be obtained by adjusting the heating rate.
Description
技术领域 technical field
本发明涉及一种金属氧化物空心粒子、金属氧化物空心纤维、金属空心粒子或金属空心纤维的制备方法。The invention relates to a method for preparing metal oxide hollow particles, metal oxide hollow fibers, metal hollow particles or metal hollow fibers.
背景技术 Background technique
具有空心结构的微纳米粒子和纤维，由于其低密度，高比表面积和低的热膨胀系数，被广泛应用于药物输送，催化，传感，储氢，锂电池和微反应器等领域(Lou，X.W.；Archer，L.A.；Yang Z.C.Adv.Mater.2008，20，3987)。特别地，被誉为第三代纳米材料的具有多级内部结构的多级空心纳米粒子和纤维(Multilevel Hollow Nanoparticles andnanofibers，MHNPs and MHNFs，包括核壳空心，多层空心及多腔室空心纳米粒子和纤维)引起了各国科研工作者的广泛关注(Zhao，Y.；Jiang，L.Adv.Mater.2009，21，1)。相对于第一代(如纳米粒子，纳米棒等)和第二代纳米材料(如空心球，纳米管等)，多级空心纳米粒子和纤维具有以下特点：(1)具有多层微纳空心结构和多重界面，有可能引起新的物理化学性质；(2)其复杂的内部结构有利于更好地控制粒子各部位的物理和化学环境；(3)具有多重内表面和高比表面积，比相同尺寸的实心和单层空心材料具有更高的活性，在药物输送，催化，传感，储氢，锂电池和微反应器等方面表现出新的更好的性能。如Q.S.Zhu课题组(Zhang，H.G.；Zhu，Q.S.；Zhang，Y.；Wang，Y.；Zhao，L.；Yu，B.Adv.Funct.Mater.2007，17，2766)研究发现Cu2O多层空心微粒子的对乙醇蒸气探测的灵敏度(8.2)远高于Cu2O纳米晶(2.7)和相同尺寸的实心微粒子(1.5)；Ikeda等(Ikeda，S.；Ishino，S.；Harada，T.；N.Okamoto，N.；Sakata，T.；Mori，H.；Kuwabata，S.；Torimoto，T.；Matsumura，M.Angew.Chem.Int.Ed.2006，45，7063)发现PtC核壳型空心纳米粒子在催化加氢反应上有着比其他形式的Pt催化剂更高的产率和更好的循环使用特性。Micro-nanoparticles and fibers with hollow structures are widely used in drug delivery, catalysis, sensing, hydrogen storage, lithium batteries, and microreactors due to their low density, high specific surface area, and low thermal expansion coefficient (Lou, XW; Archer, LA; Yang ZCAdv. Mater. 2008, 20, 3987). In particular, Multilevel Hollow Nanoparticles and nanofibers (MHNPs and MHNFs, including core-shell hollow, multilayer hollow and multi-chamber hollow nanoparticles) and fiber) has aroused extensive attention of scientific researchers in various countries (Zhao, Y.; Jiang, L. Adv. Mater. 2009, 21, 1). Compared with the first generation (such as nanoparticles, nanorods, etc.) and the second generation of nanomaterials (such as hollow spheres, nanotubes, etc.), the multi-level hollow nanoparticles and fibers have the following characteristics: structure and multiple interfaces, which may lead to new physical and chemical properties; (2) its complex internal structure is conducive to better control of the physical and chemical environment of each part of the particle; (3) with multiple internal surfaces and high specific surface area, the ratio Solid and single-layer hollow materials with the same size have higher activity and exhibit new and better performances in drug delivery, catalysis, sensing, hydrogen storage, lithium batteries, and microreactors. For example, the QSZhu research group (Zhang, HG; Zhu, QS; Zhang, Y.; Wang, Y.; Zhao, L.; Yu, B. Adv. Funct. Mater. 2007, 17, 2766) found that Cu 2 O The sensitivity (8.2) of layered hollow microparticles to ethanol vapor detection is much higher than that of Cu 2 O nanocrystals (2.7) and solid microparticles of the same size (1.5); Ikeda et al. (Ikeda, S.; Ishino, S.; Harada, T. .; N. Okamoto, N.; Sakata, T.; Mori, H.; Kuwabata, S.; Torimoto, T.; Matsumura, M. Angew. Chem. Int. Ed. Shell-shaped hollow nanoparticles have higher yields and better recycling characteristics than other forms of Pt catalysts in catalytic hydrogenation reactions.
目前，模板法作为一种具有高可控性的方法，被广泛用于单层空心及多级空心微纳米粒子和纤维的制备(Xu，H.L.；Wang，W.Z.Angew.Chem.Int.Ed.2007，46，1489)。模板法是利用预先合成的微纳米结构作为框架(如SiO2或PS球等)，采用逐层包覆的方法在其表面沉积多层第二相物质及过渡层，并随后除去模板和过渡层而得到第二相物质的单层空心及多级空心结构。但在制备单层空心及多级空心微纳米粒子时有几个问题尚需解决：1)沉积速度慢且不能大面积生长，难以满足大规模工业化的需要；2)制备工序繁琐，模板的处理工序较多，要求模板质量近乎完美，沉积时容易受外界条件干扰，导致沉积质量下降，沉积层强度低；3)所用模板必须加以去除，这给单层空心及多级空心微纳米粒子后续应用带来了麻烦，空心结构容易塌陷和变形。因此，利用非模板法制备单层空心及多级空心微纳米粒子近年来成为了科技工者探索的新方向。其中具有代表性的方法是基于Kirkendall效应和Ostwald熟化机制制备空心粒子的方法。Kirkendall效应是指原子在两种物质界面扩散的一种现象，如果原子扩散及空腔聚集的方向得到控制即可得到空心纳米粒子。Ostwald熟化机制是指较大晶粒的生长过程中不断消耗小晶粒的一种机制，如果粒子聚集体的晶粒尺寸分布得到控制，那么在晶粒在后续生长时空心纳米粒子即可形成。但基于Kirkendall效应和Ostwald熟化机制制备得到的空心粒子常为较为简单的单层空心或单层核壳空心粒子，还无法对产物的结构实现***的控制(Yin，Y.D.；Rioux，R.M.；Erdonmez，C.K.；Hughes，S.；Somorjai，G.A.；Alivisatos，A.P.Science 2004，304，711；Liu，B.；Zeng，H.C.Small2005，1，566)。专利CN101293192A利用表面活性剂囊泡作为模板制备了单层及多层金属氧化物空心粒子，专利CN101318710A采用溶剂热条件下的Ostwald熟化机制制备出了氧化铁核壳空心粒子，但利用含有金属化合物和聚合物的复合前驱体粒子或纤维在快速加热条件下的非均匀收缩机制制备各种金属或多金属氧化物空心粒子和纤维的方法尚未见有报道。Currently, the template method, as a method with high controllability, is widely used in the preparation of single-layer hollow and multi-level hollow micro-nano particles and fibers (Xu, HL; Wang, WZAngew.Chem.Int.Ed.2007, 46, 1489). The template method is to use the pre-synthesized micro-nano structure as a framework (such as SiO 2 or PS spheres, etc.), and use a layer-by-layer coating method to deposit multiple layers of second-phase substances and transition layers on its surface, and then remove the template and transition layer. The single-layer hollow and multi-level hollow structures of the second phase material are obtained. However, there are several problems to be solved in the preparation of single-layer hollow and multi-level hollow micro-nano particles: 1) the deposition rate is slow and cannot grow in a large area, which is difficult to meet the needs of large-scale industrialization; 2) the preparation process is cumbersome, and the template processing There are many processes, and the quality of the template is required to be nearly perfect. The deposition is easily disturbed by external conditions, resulting in a decrease in the deposition quality and low strength of the deposited layer; 3) The template used must be removed, which hinders the subsequent application of single-layer hollow and multi-level hollow micro-nano particles. Bringing trouble, the hollow structure is prone to collapse and deformation. Therefore, the use of non-template methods to prepare single-layer hollow and multi-level hollow micro-nano particles has become a new direction for scientific and technological workers to explore in recent years. The representative method is the method of preparing hollow particles based on Kirkendall effect and Ostwald ripening mechanism. The Kirkendall effect refers to a phenomenon in which atoms diffuse at the interface of two substances. If the direction of atom diffusion and cavity aggregation is controlled, hollow nanoparticles can be obtained. The Ostwald ripening mechanism refers to a mechanism in which small grains are continuously consumed during the growth of larger grains. If the grain size distribution of particle aggregates is controlled, then hollow nanoparticles can be formed during the subsequent growth of grains. However, the hollow particles prepared based on the Kirkendall effect and the Ostwald ripening mechanism are usually relatively simple single-layer hollow or single-layer core-shell hollow particles, and the structure of the product cannot be systematically controlled (Yin, YD; Rioux, RM; Erdonmez, CK; Hughes, S.; Somorjai, GA; Alivisatos, AP Science 2004, 304, 711; Liu, B.; Zeng, HCSmall 2005, 1, 566). Patent CN101293192A uses surfactant vesicles as templates to prepare single-layer and multi-layer metal oxide hollow particles. Patent CN101318710A uses the Ostwald aging mechanism under solvothermal conditions to prepare iron oxide core-shell hollow particles, but uses metal compounds and The non-uniform shrinkage mechanism of polymer composite precursor particles or fibers under rapid heating conditions has not yet been reported.
发明内容 Contents of the invention
本发明的目的是提供一种金属氧化物空心粒子或纤维的制备方法，该方法简易，通过调节升温速率可以得到具有不同内部空心结构的空心粒子或空心纤维。The purpose of the present invention is to provide a method for preparing metal oxide hollow particles or fibers, which is simple and convenient, and hollow particles or fibers with different internal hollow structures can be obtained by adjusting the heating rate.
为了实现上述目的，本发明所采取的技术方案是：一种金属氧化物空心粒子或纤维的制备方法，其特征在于它包括如下步骤：将含有金属化合物和聚合物的复合粒子或复合纤维置炉中，以5-400℃/min的升温速率在300-1000℃下对其进行处理10min-48h，随炉冷却后得到金属氧化物空心粒子或金属氧化物空心纤维。In order to achieve the above object, the technical solution adopted by the present invention is: a method for preparing metal oxide hollow particles or fibers, which is characterized in that it includes the following steps: placing composite particles or composite fibers containing metal compounds and polymers in a furnace , treat it at 300-1000°C for 10min-48h at a heating rate of 5-400°C/min, and obtain metal oxide hollow particles or metal oxide hollow fibers after cooling in a furnace.
以上述金属氧化物空心粒子或金属氧化物空心纤维为原料，进行还原反应(经H2或CO等还原)，即可得到金属空心粒子或金属空心纤维。The above-mentioned metal oxide hollow particles or metal oxide hollow fibers are used as raw materials, and the reduction reaction (reduction by H 2 or CO, etc.) can be performed to obtain metal hollow particles or metal hollow fibers.
所述的含有金属化合物和聚合物的复合粒子的制备(喷雾方法)：按金属化合物与聚合物的质量比为(0.1-10)∶1，选取金属化合物和聚合物并溶解配制成浓度(金属化合物和聚合物的质量之和与溶液质量之比)为20-40wt.％的静电喷雾前驱体溶液；将静电喷雾前驱体溶液置于装有直径为0.6mm针头的静电喷雾给料装置中，溶液的供料速为0.02-0.2mL/h，采用7-30kV的工作电压于25℃室温下进行静电喷雾，在距离针头4-15cm处，以铝片收集静电喷雾产物，得到含有金属化合物和聚合物的复合粒子。The preparation (spray method) of the composite particle that contains metal compound and polymer: according to the mass ratio of metal compound and polymer is (0.1-10): 1, select metal compound and polymer and dissolve and prepare to concentration (metal The mass sum of compound and polymer and the ratio of solution mass) is the electrostatic spray precursor solution of 20-40wt.%; The electrostatic spray precursor solution is placed in the electrostatic spray feeding device that diameter is 0.6mm needle, The feeding rate of the solution is 0.02-0.2mL/h, and the working voltage of 7-30kV is used for electrostatic spraying at room temperature of 25°C. At a distance of 4-15cm from the needle, the electrostatic spray product is collected with an aluminum sheet to obtain a solution containing metal compounds and Composite particles of polymers.
所述的含有金属化合物和聚合物的复合粒子的制备也可采用乳液聚合方法制备。The preparation of the composite particles containing metal compounds and polymers can also be prepared by emulsion polymerization.
所述的含有金属化合物和聚合物的复合纤维的制备(利用纺丝方法)：按金属化合物与聚合物的质量比为(0.1-10)∶1，选取金属化合物和聚合物并溶解配制成浓度(金属化合物和聚合物的质量之和与溶液质量之比)为45-60wt.％的静电纺丝前驱体溶液；将静电纺丝前驱体溶液置于装有直径为0.6mm针头的静电纺丝给料装置中，溶液的供料速为0.1-1mL/h，采用10-30kV的工作电压于25℃室温下进行静电纺丝，在距离针头4-20cm处，以铜网收集静电纺丝产物，得到含有金属化合物和聚合物的复合纤维。The preparation of the composite fiber containing metal compound and polymer (using spinning method): according to the mass ratio of metal compound and polymer (0.1-10): 1, the metal compound and polymer are selected and dissolved to form a concentration (The ratio of the sum of the mass of the metal compound and the polymer to the mass of the solution) is 45-60wt.% electrospinning precursor solution; the electrospinning precursor solution is placed in an electrospinning needle with a diameter of 0.6mm In the feeding device, the feeding rate of the solution is 0.1-1mL/h, and the electrospinning is carried out at a room temperature of 25°C with a working voltage of 10-30kV, and the electrospinning product is collected with a copper net at a distance of 4-20cm from the needle. , to obtain composite fibers containing metal compounds and polymers.
所述的金属化合物为金属有机酸盐、金属无机盐、有机金属络合物等中的任意一种或任意二种以上(含任意二种)的混合物，任意二种以上(含任意二种)混合时为任意配比。The metal compound is any one or a mixture of any two or more (including any two) of metal organic acid salts, metal inorganic salts, organic metal complexes, etc., any two or more (including any two) It can be mixed in any ratio.
所述的金属有机酸盐为乙酸盐、柠檬酸盐等中的任意一种或二种的混合，二种混合时为任意配比；所述的金属无机盐为卤盐、硝酸盐、硫酸盐等中的任意一种或任意二种以上(含任意二种)的混合，任意二种以上(含任意二种)混合时为任意配比。The metal organic acid salt is any one of acetate, citrate, etc. or a mixture of the two, and the two are mixed in any ratio; the metal inorganic salt is halogen salt, nitrate, sulfuric acid A mixture of any one or two or more (including any two) of salts, etc., when any two or more (including any two) are mixed, it is an arbitrary proportion.
所述的有机金属络合物为金属Fe、Co或Ni的羰基化合物，或者为钛酸丁酯、异丙醇铝或乙醇钽等。The organometallic complex is a carbonyl compound of metal Fe, Co or Ni, or butyl titanate, aluminum isopropoxide or tantalum ethoxide.
乙酸盐为Fe、Co、Ni、Zn、Cu、Ba或Sr等的金属离子的乙酸盐；柠檬酸盐为Fe、Co、Ni、Zn、Cu、Ba或Sr等的金属离子的柠檬酸盐；卤盐为Fe、Co、Ni、Zn、Cu、Ba或Sr等的金属离子的卤盐，硝酸盐为Fe、Co、Ni、Zn、Cu、Ba或Sr等的金属离子的硝酸盐，碳酸盐为Fe、Co、Ni、Zn、Cu、Ba或Sr等的金属离子的碳酸盐。Acetate is acetate of metal ions such as Fe, Co, Ni, Zn, Cu, Ba or Sr; citrate is citric acid of metal ions such as Fe, Co, Ni, Zn, Cu, Ba or Sr Salt; halide salts are halide salts of metal ions such as Fe, Co, Ni, Zn, Cu, Ba or Sr, etc., nitrates are nitrates of metal ions such as Fe, Co, Ni, Zn, Cu, Ba or Sr, etc. Carbonates are carbonates of metal ions such as Fe, Co, Ni, Zn, Cu, Ba, or Sr.
所述的聚合物为聚乙烯吡咯烷酮(PVP)、聚苯乙烯(PS)、聚乙烯(PE)、聚氧化乙烯(PEO)、聚丙烯腈(PANI)等中的任意一种或任意二种以上(含任意二种)的混合，任意二种以上(含任意二种)混合时为任意配比。The polymer is any one or two or more of polyvinylpyrrolidone (PVP), polystyrene (PS), polyethylene (PE), polyethylene oxide (PEO), polyacrylonitrile (PANI), etc. (including any two kinds) mixing, any two or more kinds (including any two kinds) are mixed in any proportion.
所述金属氧化物空心粒子为：单层空心、核壳空心、多层空心或多层核壳空心的金属氧化物空心粒子。The metal oxide hollow particles are: single-layer hollow, core-shell hollow, multi-layer hollow or multi-layer core-shell hollow metal oxide hollow particles.
所述金属氧化物空心纤维为：单层空心、核壳空心、多层空心或多层核壳空心的金属氧化物空心纤维。The metal oxide hollow fiber is: single-layer hollow, core-shell hollow, multi-layer hollow or multi-layer core-shell hollow metal oxide hollow fiber.
用本发明方法制备的金属氧化物空心粒子或纤维包括：MxFeyOz、MxOy(M＝Fe，Co，Ni，Zn，Cu，Ba，Sr，Ti等金属离子)。The metal oxide hollow particles or fibers prepared by the method of the present invention include: M x Fe y O z , M x O y (M=Fe, Co, Ni, Zn, Cu, Ba, Sr, Ti and other metal ions).
本发明的有益效果是：本发明利用金属化合物和聚合物的复合粒子或纤维在快速加热条件下的非均匀收缩制备各种内部空心结构的金属氧化物空心粒子和纤维，通过调节升温速率可以得到具有不同内部空心结构的空心粒子或纤维[升温速率为5-400℃/min，从低至高，依次可得到单层空心、核壳空心、多层(核壳)空心粒子或纤维]。The beneficial effects of the present invention are: the present invention utilizes the non-uniform shrinkage of composite particles or fibers of metal compounds and polymers under rapid heating conditions to prepare metal oxide hollow particles and fibers with various internal hollow structures, which can be obtained by adjusting the heating rate Hollow particles or fibers with different internal hollow structures [The heating rate is 5-400°C/min, from low to high, in order to obtain single-layer hollow, core-shell hollow, multi-layer (core-shell) hollow particles or fibers].
本方法与模板法比较具有工艺简单，时间短，容易控制，便于规模化生产；与基于Kirkendall效应和Ostwald熟化机制的空心粒子(纤维)制备方法比较，本方法可简单地通过对升温速率的调节即可实现对产物结构由单层空心至核壳空心，再至多层(核壳)空心粒子或纤维。Compared with the template method, this method has simple process, short time, easy control, and is convenient for large-scale production; compared with the hollow particle (fiber) preparation method based on the Kirkendall effect and Ostwald ripening mechanism, this method can simply adjust the heating rate The product structure can be realized from single-layer hollow to core-shell hollow, and then to multi-layer (core-shell) hollow particles or fibers.
附图说明 Description of drawings
图1是所制备的γ-Fe2O3(A)单层空心，(B)核壳空心，(C)双层空心，(D)双层核壳空心粒子的透射电子显微镜图。Fig. 1 is a transmission electron microscope image of prepared γ-Fe 2 O 3 (A) single-layer hollow, (B) core-shell hollow, (C) double-layer hollow, (D) double-layer core-shell hollow particles.
图2是所制备的γ-Fe2O3(A)核壳空心，(B)双层空心纤维的扫描电子显微镜图。Fig. 2 is a scanning electron microscope image of the prepared γ-Fe 2 O 3 (A) core-shell hollow, (B) double-layer hollow fiber.
图3是所制备的α-Fe2O3(A)核壳空心，(B)双层空心纤维的扫描电子显微镜图。Fig. 3 is a scanning electron microscope image of the prepared α-Fe 2 O 3 (A) core-shell hollow, (B) double-layer hollow fiber.
图4是所制备的CoFe2O4(A)核壳空心，(B)双层空心粒子的透射电子显微镜图。Fig. 4 is a transmission electron microscope image of the prepared CoFe 2 O 4 (A) core-shell hollow, (B) double-layer hollow particles.
图5是所制备的NiFe2O4(A)核壳空心，(B)双层空心粒子的透射电子显微镜图。Fig. 5 is a transmission electron microscope image of the prepared NiFe 2 O 4 (A) core-shell hollow, (B) double-layer hollow particles.
图6是所制备的BaFe12O19双层空心纤维的扫描电子显微镜图。Fig. 6 is a scanning electron microscope image of the prepared BaFe 12 O 19 double-layer hollow fiber.
图7是制备的γ-Fe2O3，α-Fe2O3，CoFe2O4，NiFe2O4，和BaFe12O19空心结构材料的XRD图。Fig. 7 is the XRD patterns of prepared γ-Fe 2 O 3 , α-Fe 2 O 3 , CoFe 2 O 4 , NiFe 2 O 4 , and BaFe 12 O 19 hollow structure materials.
具体实施方式 Detailed ways
下面结合具体实施例对本发明作进一步说明，但不限定本发明。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited.
实施例1：γ-Fe2O3单层空心、核壳空心、双层空心、双层核壳空心粒子制备：Example 1: Preparation of γ-Fe 2 O 3 single-layer hollow, core-shell hollow, double-layer hollow, and double-layer core-shell hollow particles:
1)将聚乙烯吡咯烷酮(PVP)溶解于30mL预先配制的浓度为0.1g/mL的柠檬酸铁溶液中，柠檬酸铁与聚乙烯吡咯烷酮(PVP)的质量比为5∶4，在60℃下加热磁力搅拌脱水使溶质(柠檬酸铁和PVP)的浓度达到40wt.％形成静电喷雾前驱体溶液；将静电喷雾前驱体溶液置于装有直径为0.6mm针头的静电喷雾给料装置中，溶液的供料速为0.1mL/h，采用25kV的工作电压于25℃室温下进行静电喷雾，在距离针头15cm处，以铝片收集静电喷雾产物——PVP/柠檬酸铁复合粒子。1) Dissolve polyvinylpyrrolidone (PVP) in 30 mL of ferric citrate solution with a concentration of 0.1 g/mL prepared in advance, the mass ratio of ferric citrate to polyvinylpyrrolidone (PVP) is 5:4, at 60 °C Heating magnetic stirring dehydration makes the concentration of solute (ferric citrate and PVP) reach 40wt.% to form electrostatic spray precursor solution; Electrostatic spray precursor solution is placed in the electrostatic spray feeding device that diameter is equipped with 0.6mm needle, solution The feed rate is 0.1mL/h, and electrostatic spraying is carried out at room temperature of 25°C with a working voltage of 25kV. At a distance of 15cm from the needle, the electrostatic spray product—PVP/ferric citrate composite particles—is collected with an aluminum sheet.
2)将上述PVP/柠檬酸铁复合粒子连同铝片一起置于程序控温的管式炉中，以10℃/min的升温速率升至500℃，然后在该温度下持续煅烧2h，使PVP和柠檬酸铁分解，随炉冷却即可制备得到γ-Fe2O3单层空心粒子；2) Put the above-mentioned PVP/ferric citrate composite particles together with the aluminum sheet in a temperature-programmed tube furnace, raise the temperature to 500°C at a rate of 10°C/min, and then continue to calcinate at this temperature for 2 hours to make the PVP Decompose with ferric citrate and cool down in the furnace to prepare γ-Fe 2 O 3 single-layer hollow particles;
将升温速率调高至20℃/min，重复上述热处理工艺即可得到γ-Fe2O3核壳空心粒子；Increase the heating rate to 20°C/min, and repeat the above heat treatment process to obtain γ-Fe 2 O 3 core-shell hollow particles;
将升温速率调高至50℃/min，重复上述热处理工艺即可得到γ-Fe2O3双层空心粒子；Increase the heating rate to 50°C/min, and repeat the above heat treatment process to obtain γ-Fe 2 O 3 double-layer hollow particles;
将升温速率调高至250℃/min，重复上述热处理工艺即可得到γ-Fe2O3双层核壳空心粒子；γ-Fe2O3双层核壳空心粒子产物的XRD图如图4中的A所示。Increase the heating rate to 250°C/min, and repeat the above heat treatment process to obtain γ-Fe 2 O 3 double-layer core-shell hollow particles; the XRD pattern of γ-Fe 2 O 3 double-layer core-shell hollow particles is shown in Figure 4 Shown in A.
利用透射电镜(TEM，JEM-2100F，JEOL Co.，Ltd.，Japan)和场发射扫描电镜(SEM，S-4800，Hitachi Co.，Ltd.，Japan)对产物的结构和形貌进行表征，制备得到的单层空心粒子、核壳空心粒子、双层空心粒子和双层核壳空心粒子的结构和形貌如图1中的A、B、C和D所示，图1中的A、B、C和D说明了得到的产物为单层空心粒子、核壳空心粒子、双层空心粒子和双层核壳空心粒子。利用X射线衍射(XRD，D/max-ⅢA，Rigaku Co.，Ltd.，Japan)对γ-Fe2O3双层核壳空心粒子产物的物相进行表征，表明制备得到产物为γ-Fe2O3，如图7中的A所示。The structure and morphology of the product were characterized by transmission electron microscope (TEM, JEM-2100F, JEOL Co., Ltd., Japan) and field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan), The structures and appearances of the prepared single-layer hollow particles, core-shell hollow particles, double-layer hollow particles and double-layer core-shell hollow particles are shown in A, B, C and D in Fig. 1, A, B and D in Fig. 1 B, C and D illustrate that the obtained products are single-layer hollow particles, core-shell hollow particles, double-layer hollow particles and double-layer core-shell hollow particles. X-ray diffraction (XRD, D/max-ⅢA, Rigaku Co., Ltd., Japan) was used to characterize the phase of the γ-Fe 2 O 3 double-layer core-shell hollow particle product, indicating that the prepared product was γ-Fe 2 O 3 , as shown in A in Fig. 7 .
实施例2：γ-Fe2O3核壳空心，双层空心纤维制备：Example 2: Preparation of γ-Fe 2 O 3 core-shell hollow, double-layer hollow fiber:
1)：将聚乙烯吡咯烷酮(PVP)溶解于30mL预先配制的浓度为0.1g/mL的柠檬酸铁溶液中，柠檬酸铁与PVP的质量比为4∶1，在60℃下加热磁力搅拌脱水使溶质(柠檬酸铁和PVP)的浓度达到50wt.％形成静电纺丝前驱体溶液；将前驱体溶液置于装有直径为0.6mm针头的静电纺丝给料装置中，溶液的供料速为0.3mL/h，采用25kV的工作电压于25℃室温下进行静电纺丝，在距离针头15cm处，以铜网收集静电喷雾产物PVP/柠檬酸铁复合纤维。1): Dissolve polyvinylpyrrolidone (PVP) in 30 mL of pre-prepared ferric citrate solution with a concentration of 0.1 g/mL, the mass ratio of ferric citrate to PVP is 4:1, heat at 60 °C with magnetic stirring for dehydration Make the concentration of solute (ferric citrate and PVP) reach 50wt.% and form electrospinning precursor solution; Precursor solution is placed in the electrospinning feeding device that diameter is equipped with 0.6mm needle, the feeding speed of solution Electrospinning was carried out at room temperature of 25°C with a working voltage of 25kV at 0.3mL/h. At a distance of 15cm from the needle, the electrostatically sprayed PVP/iron citrate composite fiber was collected with a copper net.
2)将上述PVP/柠檬酸铁复合纤维从铜网转移到瓷舟中并将其一起置于程序控温的管式炉中，以100℃/min的升温速率升至500℃，然后在该温度下持续煅烧2h，使PVP和柠檬酸铁分解，随炉冷却即可制备得到γ-Fe2O3核壳空心纤维，如图2中的A所示；2) Transfer the above-mentioned PVP/ferric citrate composite fiber from the copper mesh to a porcelain boat and place them together in a temperature-programmed tube furnace, raise the temperature to 500 °C at a rate of 100 °C/min, and then Continuous calcination at high temperature for 2 hours to decompose PVP and ferric citrate, and then cool down in the furnace to prepare γ-Fe 2 O 3 core-shell hollow fibers, as shown in A in Figure 2;
将升温速率调高至250℃/min，重复上述热处理工艺即可得到γ-Fe2O3双层空心纤维，如图1中的B所示。Increase the heating rate to 250°C/min, and repeat the above heat treatment process to obtain a γ-Fe 2 O 3 double-layer hollow fiber, as shown in B in Figure 1 .
利用场发射扫描电镜(SEM，S-4800，Hitachi Co.，Ltd.，Japan)对产物的结构和形貌进行表征，制备得到的核壳空心纤维、双层空心纤维的结构和形貌如图2中的A和B所示，图2中的A说明了得到的产物为核壳空心纤维，图2中的B说明了得到的产物为双层空心纤维。The structure and morphology of the product were characterized by a field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan). The structure and morphology of the prepared core-shell hollow fiber and double-layer hollow fiber are shown in the figure As shown in A and B in Figure 2, A in Figure 2 shows that the obtained product is a core-shell hollow fiber, and B in Figure 2 shows that the obtained product is a double-layer hollow fiber.
实施例3α-Fe2O3核壳空心，双层空心纤维制备：Example 3 α-Fe 2 O 3 core-shell hollow, double-layer hollow fiber preparation:
1)将聚乙烯吡咯烷酮(PVP)溶解于30mL预先配制的浓度为0.1g/mL的柠檬酸铁溶液中，柠檬酸铁与PVP的质量比为4∶1，在60℃下加热磁力搅拌脱水使溶质(柠檬酸铁和PVP)的浓度达到55wt.％形成静电喷纺丝前驱体溶液；将前驱体溶液置于装有直径为0.6mm针头的静电纺丝给料装置中，溶液的供料速为0.3mL/h，采用25kV的工作电压于25℃室温下进行静电纺丝，在距离针头15cm处，以铜网收集静电喷雾产物——PVP/柠檬酸铁复合纤维。1) Dissolve polyvinylpyrrolidone (PVP) in 30 mL of pre-prepared ferric citrate solution with a concentration of 0.1 g/mL. The mass ratio of ferric citrate to PVP is 4:1. The concentration of solute (ferric citrate and PVP) reaches 55wt.% to form the electrospinning precursor solution; The precursor solution is placed in the electrospinning feeding device that diameter is equipped with 0.6mm needle, and the feeding speed of solution Electrospinning was carried out at room temperature of 25°C with a working voltage of 25kV at 0.3mL/h. At a distance of 15cm from the needle, the electrostatic spray product—PVP/iron citrate composite fiber—was collected with a copper mesh.
2)将上述PVP/柠檬酸铁复合纤维从铜网转移到瓷舟中并将其一起置于程序控温的管式炉中，以100℃/min的升温速率升至400℃预处理30min后，以10℃/min的升温速率升至800℃，然后在该温度下持续煅烧2h，使PVP和柠檬酸铁完全分解，随炉冷却即可制备得到α-Fe2O3核壳空心纤维。2) Transfer the above-mentioned PVP/ferric citrate composite fiber from the copper mesh to a porcelain boat and place them together in a temperature-programmed tube furnace, and raise the temperature to 400°C at a rate of 100°C/min for 30 minutes of pretreatment , at a rate of 10°C/min to 800°C, and then continue to calcine at this temperature for 2 hours to completely decompose PVP and ferric citrate, and then cool down in the furnace to prepare α-Fe 2 O 3 core-shell hollow fibers.
将预处理升温速率调高至200℃/min，重复上述热处理工艺即可得到α-Fe2O3双层空心纤维。Increase the pretreatment heating rate to 200°C/min, and repeat the above heat treatment process to obtain α-Fe 2 O 3 double-layer hollow fibers.
利用场发射扫描电镜(SEM，S-4800，Hitachi Co.，Ltd.，Japan)对产物的结构和形貌进行表征，制备得到的核壳空心纤维和双层空心纤维的结构形貌如图3中的A和B所示。利用X射线衍射(XRD，D/max-ⅢA，Rigaku Co.，Ltd.，Japan)对产物的物相进行表征，表明制备得到双层空心纤维产物为α-Fe2O3，如图7中的B所示。The structure and morphology of the product were characterized by field emission scanning electron microscopy (SEM, S-4800, Hitachi Co., Ltd., Japan). The structure and morphology of the prepared core-shell hollow fiber and double-layer hollow fiber are shown in Figure 3 shown in A and B. The phase of the product was characterized by X-ray diffraction (XRD, D/max-ⅢA, Rigaku Co., Ltd., Japan), which showed that the double-layer hollow fiber product was α-Fe 2 O 3 , as shown in Figure 7 shown in B.
实施例4：CoFe2O4核壳空心，双层空心粒子制备：Example 4: Preparation of CoFe 2 O 4 core-shell hollow, double-layer hollow particles:
1)将聚乙烯吡咯烷酮(PVP)和乙酸钴溶解于30mL预先配制的浓度为0.1g/mL的柠檬酸铁溶液中，柠檬酸铁与PVP的质量比为5∶4，柠檬酸铁与乙酸钴的摩尔比为2∶1，在60℃下加热磁力搅拌脱水使溶质(柠檬酸铁，乙酸钴和PVP)的浓度达到40wt.％形成静电喷雾前驱体溶液；将前驱体溶液置于装有直径为0.6mm针头的静电喷雾给料装置中，溶液的供料速为0.1mL/h，采用25kV的工作电压于25℃室温下进行静电喷雾，在距离针头15cm处，以铝片收集静电喷雾产物——金属化合物复合粒子。1) Dissolve polyvinylpyrrolidone (PVP) and cobalt acetate in 30 mL of ferric citrate solution with a concentration of 0.1 g/mL prepared in advance, the mass ratio of ferric citrate to PVP is 5:4, ferric citrate and cobalt acetate The molar ratio is 2: 1, heating magnetic stirring dehydration at 60 ℃ makes the concentration of solute (ferric citrate, cobalt acetate and PVP) reach 40wt.% to form electrostatic spray precursor solution; In the electrostatic spray feeding device with a 0.6mm needle, the feeding rate of the solution is 0.1mL/h, and the electrostatic spray is carried out at a room temperature of 25°C with a working voltage of 25kV, and the electrostatic spray product is collected with an aluminum sheet at a distance of 15cm from the needle. - metal compound composite particles.
2)将上述静电喷雾产物连同铝片一起置于程序控温的管式炉中，以50℃/min的升温速率升至500℃，然后在该温度下持续煅烧2h，使PVP和柠檬酸铁分解，随炉冷却即可制备得到CoFe2O4核壳空心粒子；2) Put the above-mentioned electrostatic spray product together with the aluminum sheet in a temperature-programmed tube furnace, raise the temperature to 500°C at a rate of 50°C/min, and then continue calcining at this temperature for 2h to make PVP and ferric citrate Decompose and cool down in the furnace to prepare CoFe 2 O 4 core-shell hollow particles;
将升温速率调高至100℃/min，重复上述热处理工艺即可得到CoFe2O4双层空心粒子。The heating rate is increased to 100° C./min, and the above heat treatment process is repeated to obtain CoFe 2 O 4 double-layer hollow particles.
利用透射电镜(TEM，JEM-2100F，JEOL Co.，Ltd.，Japan)对产物的结构和形貌进行表征，制备得到的核壳空心粒子和双层空心粒子的结构和形貌如图4中的A和B所示。利用X射线衍射(XRD，D/max-ⅢA，Rigaku Co.，Ltd.，Japan)对产物的物相进行表征，表明制备得到产物为CoFe2O4如图7中的C所示。The structure and morphology of the product were characterized by transmission electron microscopy (TEM, JEM-2100F, JEOL Co., Ltd., Japan), and the structure and morphology of the prepared core-shell hollow particles and double-layer hollow particles are shown in Figure 4 A and B are shown. The phase of the product was characterized by X-ray diffraction (XRD, D/max-ⅢA, Rigaku Co., Ltd., Japan), which showed that the prepared product was CoFe 2 O 4 , as shown in C in FIG. 7 .
实施例5NiFe2O4核壳空心，双层空心粒子制备：Example 5 Preparation of NiFe 2 O 4 core-shell hollow, double-layer hollow particles:
1)将聚乙烯吡咯烷酮(PVP)和乙酸镍溶解于30mL预先配制的浓度为0.1g/mL的柠檬酸铁溶液中，柠檬酸铁与PVP的质量比为5∶4，柠檬酸铁与乙酸镍的摩尔比为2∶1，在60℃下加热磁力搅拌脱水使溶质(柠檬酸铁，乙酸镍和PVP)的浓度达到40wt.％形成静电喷雾前驱体溶液；将前驱体溶液置于装有直径为0.6mm针头的静电喷雾给料装置中，溶液的供料速为0.1mL/h，采用25kV的工作电压于25℃室温下进行静电喷雾，在距离针头15cm处，以铝片收集静电喷雾产物。1) Dissolve polyvinylpyrrolidone (PVP) and nickel acetate in 30 mL of ferric citrate solution with a concentration of 0.1 g/mL prepared in advance, the mass ratio of ferric citrate to PVP is 5:4, ferric citrate and nickel acetate The molar ratio is 2: 1, heating magnetic stirring dehydration at 60 ℃ makes the concentration of solute (iron citrate, nickel acetate and PVP) reach 40wt.% to form electrostatic spray precursor solution; In the electrostatic spray feeding device with a 0.6mm needle, the feeding rate of the solution is 0.1mL/h, and the electrostatic spray is carried out at a room temperature of 25°C with a working voltage of 25kV, and the electrostatic spray product is collected with an aluminum sheet at a distance of 15cm from the needle. .
2)将上述静电喷雾产物连同铝片基底一起置于程序控温的管式炉中，以50℃/min的升温速率升至500℃，然后在该温度下持续煅烧2h，使PVP和柠檬酸铁分解，随炉冷却即可制备得到CoFe2O4核壳空心粒子。2) Put the above-mentioned electrostatic spray product together with the aluminum sheet substrate in a temperature-programmed tube furnace, raise the temperature to 500°C at a rate of 50°C/min, and then continue calcining at this temperature for 2 hours to make PVP and citric acid CoFe 2 O 4 core-shell hollow particles can be prepared by decomposing iron and cooling in the furnace.
将升温速率调高至100℃/min，重复上述热处理工艺即可得到CoFe2O4双层空心粒子。The heating rate is increased to 100° C./min, and the above heat treatment process is repeated to obtain CoFe 2 O 4 double-layer hollow particles.
利用透射电镜(TEM，JEM-2100F，JEOL Co.，Ltd.，Japan)对产物的结构和形貌进行表征，制备得到的核壳空心粒子和双层空心粒子的结构和形貌如图5中的A和B所示。利用X射线衍射(XRD，D/max-ⅢA，Rigaku Co.，Ltd.，Japan)对产物的物相进行表征，表明制备得到产物的物相为NiFe2O4，如图7中的D所示。The structure and morphology of the product were characterized by transmission electron microscopy (TEM, JEM-2100F, JEOL Co., Ltd., Japan), and the structure and morphology of the prepared core-shell hollow particles and double-layer hollow particles are shown in Figure 5 A and B are shown. The phase of the product was characterized by X-ray diffraction (XRD, D/max-ⅢA, Rigaku Co., Ltd., Japan), which showed that the phase of the prepared product was NiFe 2 O 4 , as shown in D in Figure 7 Show.
实施例6BaFe12O19双层空心纤维制备Embodiment 6 BaFe 12 O 19 double-layer hollow fiber preparation
1)将聚乙烯吡咯烷酮(PVP)和乙酸钡溶解于30mL预先配制的浓度为0.1g/mL的柠檬酸铁溶液中，柠檬酸铁与PVP的质量比为4∶1，柠檬酸铁与乙酸镍的摩尔比为12∶1，在60℃下加热磁力搅拌脱水使溶质(柠檬酸铁，乙酸钡和PVP)的浓度达到50wt.％形成静电纺丝前驱体溶液；将前驱体溶液置于装有直径为0.6mm针头的静电纺丝给料装置中，溶液的供料速为0.3mL/h，采用25kV的工作电压于25℃室温下进行静电纺丝，在距离针头15cm处，以铜网收集静电纺丝复合纤维。1) Dissolve polyvinylpyrrolidone (PVP) and barium acetate in 30 mL of ferric citrate solution with a concentration of 0.1 g/mL prepared in advance, the mass ratio of ferric citrate to PVP is 4:1, ferric citrate and nickel acetate The molar ratio is 12: 1, heating magnetic stirring dehydration makes the concentration of solute (ferric citrate, barium acetate and PVP) reach 50wt.% to form electrospinning precursor solution at 60 ℃; In the electrospinning feeding device with a needle with a diameter of 0.6mm, the feeding rate of the solution is 0.3mL/h, and the electrospinning is carried out at a room temperature of 25°C with a working voltage of 25kV. Electrospun composite fibers.
2)将上述静电纺丝复合纤维从铜网转移到瓷舟中并将其一起置于程序控温的管式炉中，以200℃/min的升温速率升至400℃预处理30min后，以10℃/min的升温速率升至800℃，然后在该温度下持续煅烧2h，使PVP和柠檬酸铁完全分解，随炉冷却即可制备得到BaFe12O19双层空心纤维。2) Transfer the above-mentioned electrospun composite fibers from the copper mesh to the porcelain boat and place them together in a temperature-programmed tube furnace. After pretreatment for 30 min at a heating rate of 200 °C/min to 400 °C, The heating rate was increased to 800°C at a rate of 10°C/min, and then continued to be calcined at this temperature for 2 hours to completely decompose PVP and ferric citrate, and BaFe 12 O 19 double-layer hollow fibers could be prepared by cooling in the furnace.
利用场发射扫描电镜(SEM，S-4800，Hitachi Co.，Ltd.，Japan)对产物的结构和形貌进行表征，制备得到双层空心纤维的结构形貌如图6所示。利用X射线衍射(XRD，D/max-ⅢA，Rigaku Co.，Ltd.，Japan)对产物的物相进行表征，表明制备得到产物的物相为BaFe12O19，如图7中的E所示。The structure and morphology of the product were characterized by a field emission scanning electron microscope (SEM, S-4800, Hitachi Co., Ltd., Japan), and the structure and morphology of the prepared double-layer hollow fiber are shown in FIG. 6 . The phase of the product was characterized by X-ray diffraction (XRD, D/max-ⅢA, Rigaku Co., Ltd., Japan), which showed that the phase of the prepared product was BaFe 12 O 19 , as shown in E in Figure 7 Show.
本发明所列举的各原料，以及本发明各原料的上下限、区间取值，以及工艺参数(如温度、时间等)的上下限、区间取值都能实现本发明(都能达到实施例1-6的效果)，在此不一一列举实施例。Each raw material that the present invention enumerates, and the upper and lower limits of each raw material of the present invention, the interval value, and the upper and lower limits of process parameters (such as temperature, time, etc.), the interval value can realize the present invention (all can reach embodiment 1 -6 effect), do not enumerate embodiment one by one at this.
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| CN106395913B (en) * | 2016-08-26 | 2018-01-09 | 天津大学 | A kind of ferromagnetic nano α Fe with iron defect2O3And preparation method thereof |
| CN107098405B (en) * | 2017-04-01 | 2019-07-16 | 中南大学 | A method for one-step preparation of multi-layer core-shell structure transition metal oxides |
| CN107253737B (en) * | 2017-07-24 | 2018-10-19 | 海南省环境科学研究院 | A kind of environment protecting nano material and preparation method thereof can be used for nitrogen oxide in automobile exhaust catalytic purification |
| CN109128138B (en) * | 2018-09-13 | 2020-08-25 | 浙江师范大学 | A kind of core-shell heterostructure magnetic fiber and its preparation and application method |
| CN111039329A (en) * | 2019-01-16 | 2020-04-21 | 中国科学院过程工程研究所 | Hollow multi-shell metal oxide composite material and preparation method thereof |
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