CN103318954B - Method for preparing sodium trititanate nanorods through solid-phase chemical reaction - Google Patents
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- 239000011734 sodium Substances 0.000 title claims abstract description 31
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 30
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002073 nanorod Substances 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 13
- 239000007790 solid phase Substances 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明的目的在于提供一种三钛酸钠纳米棒的制备方法，该方法通过使用廉价的原料，采用简单的操作方法，经固相化学反应可以合成出三钛酸钠纳米棒。本发明用硫酸氧钛和氢氧化钠或钠盐作为反应物，在室温下通过研磨合成前驱体，进而热处理，产物经过洗涤干燥后制得三钛酸钠纳米棒。本发明以固相化学反应为基础，采用廉价易得的原料，通过简单的研磨，再经过适当的热处理，洗涤干燥后可制得三钛酸钠纳米棒。制备方法简单，产品产率高，环境友好，易于实现大批量生产等特点都使本发明具有极为广阔的应用前景。The object of the present invention is to provide a preparation method of sodium trititanate nanorods, which can synthesize sodium trititanate nanorods through solid-phase chemical reaction by using cheap raw materials and adopting a simple operation method. The invention uses titanyl sulfate and sodium hydroxide or sodium salt as reactants, and synthesizes a precursor by grinding at room temperature, and then heat-treats, and the product is washed and dried to prepare sodium trititanate nanorods. The invention is based on solid-phase chemical reaction, adopts cheap and easy-to-obtain raw materials, and can prepare sodium trititanate nanorods after simple grinding, proper heat treatment, washing and drying. The preparation method is simple, the product yield is high, the environment is friendly, and the characteristics such as easy realization of mass production all make the present invention have extremely broad application prospects.
Description
技术领域 technical field
本发明涉及一种通过固相化学反应制备三钛酸钠纳米棒的方法。 The invention relates to a method for preparing sodium trititanate nanorods through solid phase chemical reaction.
背景技术 Background technique
三钛酸钠属单斜晶系。在三钛酸钠中，(Ti3O7)2-层被碱金属离子Na+结合到一起，为层状结构，这种层状结构使其具有非常强的阳离子交换和吸附性能，尤其是对重金属离子的交换和吸附，显示其独特的性能，目前已用于用于痕量重金属离子的分离和富集。三钛酸钠的晶体结构为隧道状结构，钠离子被包覆在隧道中间，具有高的化学稳定性。 Sodium trititanate belongs to the monoclinic crystal system. In sodium trititanate, (Ti 3 O 7 ) 2- layers are combined by alkali metal ions Na + into a layered structure. This layered structure makes it have very strong cation exchange and adsorption properties, especially The exchange and adsorption of heavy metal ions shows its unique performance and has been used for the separation and enrichment of trace heavy metal ions. The crystal structure of sodium trititanate is a tunnel-like structure, and sodium ions are coated in the middle of the tunnel, which has high chemical stability.
三钛酸钠具有特殊的结构和性质，在微电子、电致发光、蓄电池电极、吸附、离子交换、复合材料、涂料与颜料，以及催化领域有着广泛用途。三钛酸钠可用于离子交换、陶瓷电容器、微波振荡器等的绝缘谐振器的传送带、塑料增强剂、绝缘材料、电位计传感器的氧电极等。三钛酸钠为n型半导体，显示极好的光催化活性。三钛酸钠常被用作二氧化钛基材料的诱导体，以提高离子交换反应速率或向其中搀入过渡金属后的性能独特的材料。通过熔融法合成的三钛酸钠的化学稳定性和热稳定性高于沉积法合成的，而且更方便用于核技术领域，可以直接使用到核废料领域的处理。一些文献都有相关的报道：Journal of Materials Chemistry A. 1(2013).2653-2662报道了水热法合成三钛酸钠作为钠离子电池电极材料；Materials Research Bulletin. 47(2012).3770-3773报道了合成三钛酸钠及其光学性能的研究等等。 Sodium trititanate has a special structure and properties, and is widely used in the fields of microelectronics, electroluminescence, battery electrodes, adsorption, ion exchange, composite materials, coatings and pigments, and catalysis. Sodium trititanate can be used for ion exchange, ceramic capacitors, conveyor belts for insulating resonators such as microwave oscillators, plastic reinforcements, insulating materials, oxygen electrodes for potentiometer sensors, etc. Sodium trititanate is an n-type semiconductor and exhibits excellent photocatalytic activity. Sodium trititanate is often used as an inducer for titanium dioxide-based materials to increase the rate of ion exchange reactions or to make materials with unique properties after doping transition metals into them. The chemical stability and thermal stability of the sodium trititanate synthesized by the melting method are higher than those synthesized by the deposition method, and it is more convenient to be used in the field of nuclear technology, and can be directly used in the field of nuclear waste treatment. Some documents have relevant reports: Journal of Materials Chemistry A. 1 (2013). 2653-2662 reported the hydrothermal synthesis of sodium trititanate as an electrode material for sodium ion batteries; Materials Research Bulletin. 47 (2012). 3770- 3773 reported the synthesis of sodium trititanate and its optical properties and so on.
目前，目前合成钛酸钠纳米材料的主要方法有：气-液-固生长机制和气-固生长机制；水(溶剂)热法；溶液-液体-固体生长法；模板合成法；自组装法、水热法等。这些方法合成过程复杂，成本高，材料热稳定性差。因此，选择一种简单易行的制备方法，制备出三钛酸钠具有十分重要的意义。固相化学合成法不使用溶剂，具有高选择性、高产率、工艺过程简单等优点，已经成为合成纳米材料的一种重要方法。 At present, the main methods for synthesizing sodium titanate nanomaterials are: gas-liquid-solid growth mechanism and gas-solid growth mechanism; water (solvent) thermal method; solution-liquid-solid growth method; template synthesis method; self-assembly method, Hydrothermal method, etc. The synthesis process of these methods is complicated, the cost is high, and the thermal stability of the material is poor. Therefore, it is of great significance to choose a simple and feasible preparation method to prepare sodium trititanate. The solid-phase chemical synthesis method does not use solvents, has the advantages of high selectivity, high yield, and simple process, and has become an important method for synthesizing nanomaterials.
发明内容 Contents of the invention
本发明的目的在于提供一种三钛酸钠纳米棒的制备方法，该方法通过使用廉价的原料，采用简单的操作方法，经固相化学反应可以合成出三钛酸钠纳米棒。 The object of the present invention is to provide a preparation method of sodium trititanate nanorods, which can synthesize sodium trititanate nanorods through solid-phase chemical reaction by using cheap raw materials and adopting a simple operation method.
本发明的技术方案如下： Technical scheme of the present invention is as follows:
一种固相化学反应制备钛酸钠纳米棒的方法，其包括以下步骤：硫酸氧钛与氢氧化钠或钠盐的比例为 1:1.2~5 ；研磨反应的时间为 20~60 分钟 ；前驱体在空气气氛中以每分钟5~10℃·min-1速度升至900~1000℃，进行热处理2小时；产物用蒸馏水洗涤后室温干燥，得到三钛酸钠纳米棒。 A method for preparing sodium titanate nanorods by solid phase chemical reaction, comprising the following steps: the ratio of titanyl sulfate to sodium hydroxide or sodium salt is 1:1.2~5; the grinding reaction time is 20~60 minutes; The body was raised to 900-1000°C at a rate of 5-10°C·min -1 per minute in an air atmosphere, and heat-treated for 2 hours; the product was washed with distilled water and dried at room temperature to obtain sodium trititanate nanorods.
本发明所述的钠盐为草酸钠、碳酸钠、碳酸氢钠中的一种或多种。 The sodium salt of the present invention is one or more of sodium oxalate, sodium carbonate, sodium bicarbonate.
与现有技术相比，本发明具有以下优点：以固相化学反应为基础，采用廉价易得的原料，通过简单的研磨，再经过适当的热处理，洗涤干燥后可制得三钛酸钠纳米棒。制备方法简单，产品产率高，环境友好，易于实现大批量生产等特点都使本发明具有极为广阔的应用前景。 Compared with the prior art, the present invention has the following advantages: based on solid-phase chemical reaction, using cheap and easy-to-obtain raw materials, through simple grinding, and then through appropriate heat treatment, sodium trititanate nanometer can be prepared after washing and drying Great. The preparation method is simple, the product yield is high, the environment is friendly, and the characteristics such as easy realization of mass production all make the present invention have extremely broad application prospects.
附图说明 Description of drawings
图 1为所制备三钛酸钠纳米棒的粉末衍射图。 Figure 1 is the powder diffraction pattern of the prepared sodium trititanate nanorods.
图 2为所制备三钛酸钠纳米棒的投射电镜图。 Figure 2 is the transmission electron microscope image of the prepared sodium trititanate nanorods.
图 3为所制备三钛酸钠纳米棒的扫描电镜图。 Figure 3 is a scanning electron microscope image of the prepared sodium trititanate nanorods.
具体实施方式 Detailed ways
下面结合具体的实施例对本发明作进一步阐述。这些实施例应理解为仅用于说明本发明而不用于限制本发明的保护范围。在阅读了本发明记载的内容之后，基于本发明的原理对本发明所做出的各种改动或修改同样落入本发明权利要求书所限定的范围。 The present invention will be further elaborated below in conjunction with specific examples. These examples should be understood as only for illustrating the present invention but not for limiting the protection scope of the present invention. After reading the contents of the present invention, various changes or modifications made to the present invention based on the principles of the present invention also fall within the scope defined by the claims of the present invention.
实施例一： Embodiment one:
准确称量0.01 mol 硫酸氧钛和0.015 mol 氢氧化钠于不同研钵中，分别研细并混合均匀，混合后快速研磨，随着研磨的进行，混合物变为白色细状的粉末，继续研磨30 min确保反应的充分进行。将前驱体置于马弗炉中，以5℃/min 的升温速率升至900℃，在此温度煅烧2h，产物用蒸馏水洗涤后室温干燥，即可得到三钛酸钠纳米棒。 Accurately weigh 0.01 mol titanyl sulfate and 0.015 mol sodium hydroxide in different mortars, grind them separately and mix them evenly. After mixing, grind them quickly. As the grinding progresses, the mixture becomes a white fine powder. Continue grinding for 30 min to ensure the full progress of the reaction. The precursor was placed in a muffle furnace, and the temperature was raised to 900°C at a rate of 5°C/min, and calcined at this temperature for 2 hours. The product was washed with distilled water and dried at room temperature to obtain sodium trititanate nanorods.
实施例二： Embodiment two:
准确称量0.01 mol 硫酸氧钛和0.02 mol 草酸钠于不同研钵中，分别研细并混合均匀，混合后快速研磨，随着研磨的进行，混合物变为白色细状的粉末，继续研磨30 min确保反应的充分进行。将前驱体置于马弗炉中，以8℃/min 的升温速率升至900℃，在此温度煅烧2h，产物用蒸馏水洗涤后室温干燥，即可得到三钛酸钠纳米棒。 Accurately weigh 0.01 mol titanyl sulfate and 0.02 mol sodium oxalate in different mortars, grind them separately and mix them evenly. After mixing, grind quickly. As the grinding progresses, the mixture becomes a white fine powder. Continue grinding for 30 min Ensure that the reaction is fully carried out. The precursor was placed in a muffle furnace, and the temperature was raised to 900°C at a rate of 8°C/min, and calcined at this temperature for 2 hours. The product was washed with distilled water and dried at room temperature to obtain sodium trititanate nanorods.
实施例三： Embodiment three:
准确称量0.01 mol 硫酸氧钛和0.03 mol碳酸钠于不同研钵中，分别研细并混合均匀，混合后快速研磨，随着研磨的进行，混合物变为白色细状的粉末，继续研磨30 min确保反应的充分进行。将前驱体置于马弗炉中，以10℃/min 的升温速率升至1000℃，在此温度煅烧2h，产物用蒸馏水洗涤后室温干燥，即可得到三钛酸钠纳米棒。 Accurately weigh 0.01 mol titanyl sulfate and 0.03 mol sodium carbonate in different mortars, grind them separately and mix them evenly, grind them quickly after mixing, as the grinding progresses, the mixture becomes a white fine powder, continue grinding for 30 min Ensure that the reaction is fully carried out. The precursor was placed in a muffle furnace, and the temperature was raised to 1000°C at a rate of 10°C/min, and calcined at this temperature for 2 hours. The product was washed with distilled water and dried at room temperature to obtain sodium trititanate nanorods.
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