A method for preparing antimony oxide / tin oxide composite nanowires

Abstract

The present invention discloses a method for preparing antimony oxide / tin oxide composite nanowires, belonging to the field of nanomaterial technology. The preparation method comprises heating sodium stannate, antimony acetate, citric acid, and deionized water in a water bath to obtain a uniform sol; then reacting the sol in a sealed reaction vessel to obtain a precursor for the antimony oxide / tin oxide composite nanowires; and finally reacting the precursor and nano-indium in the high-temperature and low-temperature zones of a two-stage tubular furnace to obtain the antimony oxide / tin oxide composite nanowires. The composite nanowires are composed of tetragonal SnO2 and orthorhombic Sb2O3 crystal phases, with a diameter of 50 to 150 nm and a length greater than 5 μm. The present invention utilizes a multi-step preparation process that is easy to control. The resulting composite nanowires have broad application prospects in semiconductor devices, electrochemical sensors, catalysts, supercapacitors, batteries, and other fields.

Description

Technical Field

[0001] The invention belongs to the technical field of nanomaterials, and particularly relates to a method for preparing antimony oxide / tin oxide composite nanowires. Background Art

[0002] Antimony- and tin-based oxide nanomaterials have a wide range of applications in semiconductor devices, electrochemical sensors, catalysts, supercapacitors, batteries, and other fields due to their large active surface area, excellent electron transport properties, interfacial properties, catalytic characteristics, and high chemical and thermal stability. As important rare metal oxide nanomaterials, nanoantimony oxide and nanotin oxide have attracted widespread research interest.

[0003] The national invention patent "Method for Preparing Nano-Antimony Oxide" (National Invention Patent No.: ZL201110407345.5) reports a method for preparing nano-antimony oxide. This method uses antimony powder as the raw material and deionized water, alkylphenol polyoxyethylene ether, polyoxyethylene sorbitan monooleate, and ethanol as liquid additives. The antimony powder and liquid additives are ball-milled for 10 to 60 hours. The resulting ball-milled powder is filtered and dried to obtain nano-antimony oxide. The national invention patent "Silicon dioxide / tin oxide nanocomposite particles with a core-shell structure and preparation method thereof" (National Invention Patent No.: ZL200910041763.X) discloses silicon dioxide / tin oxide nanocomposite particles with a core-shell structure. The core is nano-silicon dioxide and the surface is coated with a tin oxide shell. The preparation method uses nano-silicon dioxide, a soluble tin salt, and an amine precipitant as raw materials, followed by dispersion, precursor preparation, drying, and calcination. The national invention patent "Carbon Nanotube / Tin Dioxide Nanocomposite Material, Preparation Method, and Application thereof" (National Invention Patent Application No.: 202210777530.1) discloses a carbon nanotube / tin dioxide nanocomposite material. The preparation method involves electrospinning and heat treating a precursor solution of polyacrylonitrile, stannous chloride, and selenium dioxide. This composite material can be used as an electrode in lithium-ion batteries. Antimony oxide and tin oxide are combined to form an antimony oxide / tin oxide composite nanomaterial, which increases catalytically active sites and has broad application prospects in semiconductor devices, electrochemical sensors, catalysts, supercapacitors, and batteries. A national invention patent (Patent No.: ZL200710304877.X) also describes the preparation of antimony-doped tin dioxide (ATO) conductive powder from nano-antimony oxide and tin oxide powders. The preparation method involves ball milling the nano-tin oxide and nano-antimony oxide in a ball mill for 1-8 hours. The milled powder is then calcined in air at 800-1200°C for 2-8 hours. Summary of the Invention

[0004] The object of the present invention is to provide a method for preparing antimony oxide / tin oxide composite nanowires, the specific steps of which are:

[0005] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, heated to 80-100°C in a water bath, and kept warm for 2-4 hours to obtain a uniform sol;

[0006] (2) placing the sol obtained in step (1) in a sealed reaction vessel, keeping the temperature at 150-200° C. for 10-20 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0007] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, and a corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1400-1600°C, and the low temperature zone was heated to 200-400°C and kept warm for 5-10 hours. Ar gas was used as the carrier gas with a flow rate of 50-150 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0008] The molar ratio of sodium stannate to antimony acetate is 1:1;

[0009] The weight of the citric acid accounts for 5 to 10% of the total weight of the sodium stannate and antimony acetate;

[0010] The total weight of the sodium stannate, antimony acetate and citric acid accounts for 5 to 15% of the weight of deionized water;

[0011] The total weight of the sodium stannate, antimony acetate, citric acid and deionized water accounts for 50-80% of the filling degree of the sealed reaction container;

[0012] The weight of the nano-indium accounts for 3-8% of the total weight of the sodium stannate and antimony acetate.

[0013] Furthermore, the antimony oxide / tin oxide composite nanowires are composed of tetragonal SnO2 and orthorhombic Sb2O3 crystal phases.

[0014] Furthermore, the antimony oxide / tin oxide composite nanowires have a diameter of 50 to 150 nm and a length greater than 5 μm.

[0015] Furthermore, the weight of the citric acid accounts for 7% of the total weight of the sodium stannate and antimony acetate; the total weight of the sodium stannate, antimony acetate and citric acid accounts for 10% of the weight of deionized water; the total weight of the sodium stannate, antimony acetate, citric acid and deionized water accounts for 60% of the filling degree of the sealed reaction container; and the weight of the nano-indium accounts for 5% of the total weight of the sodium stannate and antimony acetate.

[0016] The innovation of the present invention:

[0017] The present invention first heats sodium stannate, antimony acetate, citric acid, and deionized water at 80-100°C for 2-4 hours to obtain a uniform sol. The uniform sol is then heated at 150-200°C for 10-20 hours to obtain a precursor for antimony oxide / tin oxide composite nanowires. The precursor for the antimony oxide / tin oxide composite nanowires and nano-indium are heated at 1400-1600°C for 5-10 hours. Under the influence of Ar carrier gas, the metal catalysis of the nano-indium and the synergistic effects of antimony oxide and tin oxide, in a low-temperature range of 200-400°C, the antimony oxide / tin oxide composite nanowires composed of tetragonal SnO2 and orthorhombic Sb2O3 crystal phases are formed on the surface of a corundum substrate through a metal catalytic and oxide-assisted growth process.

[0018] Compared with the prior art, the present invention has the following technical effects:

[0019] 1. The present invention adopts a multi-step preparation process, which is easy to control and has good repeatability. The obtained antimony oxide / tin oxide composite nanowires have low cost, which provides conditions for the practical application of antimony oxide / tin oxide composite nanowires.

[0020] 2. The raw materials used in the present invention are sodium stannate, antimony acetate, citric acid, nano-indium and deionized water, which do not produce any toxic or harmful gases and are environmentally friendly.

[0021] 3. Antimony oxide / tin oxide composite nanowires have a large number of catalytic active sites and have broad application prospects in semiconductor devices, electrochemical sensors, catalysts, supercapacitors, batteries and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the X-ray diffraction (XRD) pattern of the antimony oxide / tin oxide composite nanowires prepared in Example 1;

[0023] According to the JCPDS PDF card, it can be retrieved that the obtained antimony oxide / tin oxide composite nanowires are composed of tetragonal SnO2 (JCPDS card, card number: 41-1445) and orthorhombic Sb2O3 (JCPDS card, card number: 65-2426) crystal phases.

[0024] Figure 2 This is a scanning electron microscope (SEM) image of the antimony oxide / tin oxide composite nanowires prepared in Example 1;

[0025] It can be seen from the figure that the product is composed of antimony oxide / tin oxide composite nanowires, the diameter of the nanowires is 50 to 150 nm and the length is greater than 5 μm.

[0026] Figure 3 Transmission electron microscope (TEM) image of antimony oxide / tin oxide composite nanowires prepared in Example 1 ( Figure 3 (a)) and high-resolution TEM (HRTEM) images ( Figure 3 (b));

[0027] It can be seen from the figure that the product is composed of antimony oxide / tin oxide composite nanowires. The nanowires have a polycrystalline structure with interplanar spacings of 0.33nm and 0.35nm, which correspond to the interplanar spacings of the (110) crystal plane of the tetragonal SnO2 crystal phase and the (111) crystal plane of the orthorhombic Sb2O3 crystal phase, respectively. DETAILED DESCRIPTION

[0028] The present invention is described in detail below with reference to specific embodiments, but the present invention is not limited to the following embodiments.

[0029] Example 1

[0030] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 10% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 15% of the weight of deionized water, and the mixture is heated to 100° C. in a water bath and kept warm for 4 hours to obtain a uniform sol;

[0031] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 80% of the filling degree of the sealed reaction vessel, heating at 200° C. for 20 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0032] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 8% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1600°C, and the low temperature zone was heated to 400°C and kept warm for 10 hours. Ar gas was used as the carrier gas at a flow rate of 150 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0033] Example 2

[0034] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 5% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 5% of the weight of deionized water, and the mixture is heated to 80°C in a water bath and kept warm for 2 hours to obtain a uniform sol;

[0035] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 50% of the filling degree of the sealed reaction vessel, heating at 150° C. for 10 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0036] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 3% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1400°C, and the low temperature zone was heated to 200°C and kept warm for 5 hours. Ar gas was used as the carrier gas at a flow rate of 50 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0037] Example 3

[0038] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 6% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 6% of the weight of deionized water, and the mixture is heated to 85°C in a water bath and kept warm for 2.5 hours to obtain a uniform sol;

[0039] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 55% of the filling degree of the sealed reaction vessel, heating at 160° C. for 12 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0040] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 4% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1450°C, and the low temperature zone was heated to 250°C and kept warm for 6 hours. Ar gas was used as the carrier gas at a flow rate of 70 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0041] Example 4

[0042] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 7% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 8% of the weight of deionized water, and the mixture is heated to 90° C. in a water bath and kept warm for 3 hours to obtain a uniform sol;

[0043] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 60% of the filling degree of the sealed reaction vessel, heating at 170° C. for 14 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0044] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 5% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1500°C, and the low temperature zone was heated to 300°C and kept warm for 7 hours. Ar gas was used as the carrier gas at a flow rate of 80 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0045] Example 5

[0046] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 8% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 10% of the weight of deionized water, and the mixture is heated to 95°C in a water bath and kept warm for 3.5 hours to obtain a uniform sol;

[0047] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 65% of the filling degree of the sealed reaction vessel, heating at 180° C. for 15 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0048] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 6% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1550°C, and the low temperature zone was heated to 350°C and kept warm for 8 hours. Ar gas was used as the carrier gas at a flow rate of 100 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0049] Example 6

[0050] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 9.5% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 11% of the weight of deionized water, and the mixture is heated to 90° C. in a water bath and kept warm for 3 hours to obtain a uniform sol;

[0051] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 70% of the filling degree of the sealed reaction vessel, heating at 190° C. for 16 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0052] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 7% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1500°C, and the low temperature zone was heated to 300°C and kept warm for 9 hours. Ar gas was used as the carrier gas at a flow rate of 120 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0053] Example 7

[0054] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 9% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 12% of the weight of deionized water, and the mixture is heated to 85°C in a water bath and kept warm for 2.5 hours to obtain a uniform sol;

[0055] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 75% of the filling degree of the sealed reaction vessel, heating at 195° C. for 18 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0056] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 7.5% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1450°C, and the low temperature zone was heated to 350°C and kept warm for 9.5 hours. Ar gas was used as the carrier gas at a flow rate of 130 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

[0057] Example 8

[0058] (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed, wherein the molar ratio of sodium stannate to antimony acetate is 1:1, the weight of citric acid accounts for 5% of the total weight of sodium stannate and antimony acetate, and the total weight of sodium stannate, antimony acetate and citric acid accounts for 14% of the weight of deionized water, and the mixture is heated to 90° C. in a water bath and kept warm for 3 hours to obtain a uniform sol;

[0059] (2) placing the sol obtained in step (1) in a sealed reaction vessel, wherein the total weight of sodium stannate, antimony acetate, citric acid and deionized water accounts for 70% of the filling degree of the sealed reaction vessel, heating at 180° C. for 19 hours, and drying to obtain a precursor of antimony oxide / tin oxide composite nanowires;

[0060] (3) The precursor of antimony oxide / tin oxide composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, wherein the weight of nano-indium accounted for 7% of the total weight of sodium stannate and antimony acetate. A corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1500°C, and the low temperature zone was heated to 300°C and kept warm for 8.5 hours. Ar gas was used as the carrier gas at a flow rate of 140 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain antimony oxide / tin oxide composite nanowires.

Claims

1. A method for preparing Sb2O3 / SnO2 composite nanowires, characterized in that The steps include: (1) Sodium stannate, antimony acetate, citric acid and deionized water are mixed and heated to 80-100°C in a water bath for 2-4 hours to obtain a uniform sol; (2) placing the sol obtained in step (1) in a sealed reaction vessel, keeping the temperature at 150-200° C. for 10-20 h, and drying to obtain a precursor of Sb2O3 / SnO2 composite nanowires; (3) The precursor of Sb2O3 / SnO2 composite nanowires and nano-indium were placed in the high temperature zone of a two-stage high temperature tube furnace, and a corundum substrate was placed in the low temperature zone of the tube furnace. The high temperature zone was heated to 1400-1600°C, and the low temperature zone was heated to 200-400°C and kept warm for 5-10 hours. Ar gas was used as the carrier gas at a flow rate of 50-150 mL / min. A deposit was obtained on the corundum substrate in the low temperature zone. The deposit was washed with deionized water to obtain Sb2O3 / SnO2 composite nanowires. The molar ratio of sodium stannate to antimony acetate is 1:1; The weight of the citric acid accounts for 5-10% of the total weight of the sodium stannate and antimony acetate; The total weight of the sodium stannate, antimony acetate and citric acid accounts for 5 to 15% of the weight of deionized water; The total weight of the sodium stannate, antimony acetate, citric acid and deionized water accounts for 50-80% of the filling degree of the sealed reaction container; The weight of the nano-indium accounts for 3-8% of the total weight of the sodium stannate and antimony acetate.

2. The method for preparing Sb2O3 / SnO2 composite nanowires according to claim 1, wherein: The Sb2O3 / SnO2 composite nanowires are composed of tetragonal SnO2 and orthorhombic Sb2O3 crystal phases.

3. The method for preparing Sb2O3 / SnO2 composite nanowires according to claim 1, wherein: The diameter of the Sb2O3 / SnO2 composite nanowire is 50-150nm and the length is greater than 5μm.

4. The method for preparing Sb2O3 / SnO2 composite nanowires according to claim 1, wherein At, The weight of the citric acid accounts for 7% of the total weight of the sodium stannate and antimony acetate; The total weight of the sodium stannate, antimony acetate and citric acid accounts for 10% of the weight of deionized water; The total weight of the sodium stannate, antimony acetate, citric acid and deionized water accounts for 60% of the filling degree of the sealed reaction container; The weight of the nano-indium accounts for 5% of the total weight of the sodium stannate and antimony acetate.

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