CN102234132A - Method for preparing eight pointed star shaped lead sulphide material - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 title 1
- 239000004094 surface-active agent Substances 0.000 claims abstract description 41
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 32
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 32
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229940056932 lead sulfide Drugs 0.000 claims abstract description 27
- 229910052981 lead sulfide Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002159 nanocrystal Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明提供一种制备硫化铅材料的方法，包括以下步骤：按照1-2∶2-4∶0.01-0.10的摩尔比配制硝酸铅、硫脲、松香基表面活性剂的反应混合物，将该混合物加入到溶剂中，搅拌均匀，得到反应液；其中，反应混合物与溶剂的质量比为1∶15-40，所述溶剂选自乙醇和去离子水中的一种；将反应液放入密封的高压反应釜中，加热到140-200℃，保温9-36小时，然后经过冷却、洗涤、干燥得到颗粒形状为八角星形硫化铅材料。或者将反应液放入微波反应器中，控制微波功率为50-150W，反应温度为120-160℃，反应时间为30-60min。然后经过冷却、洗涤、干燥得到颗粒形状为八角星形的硫化铅材料。The invention provides a method for preparing a lead sulfide material, comprising the following steps: preparing a reaction mixture of lead nitrate, thiourea, and rosin-based surfactant according to a molar ratio of 1-2:2-4:0.01-0.10; Add it into the solvent, stir evenly to obtain a reaction solution; wherein, the mass ratio of the reaction mixture to the solvent is 1:15-40, and the solvent is selected from one of ethanol and deionized water; the reaction solution is put into a sealed high-pressure In the reaction kettle, heat to 140-200°C, keep the temperature for 9-36 hours, then cool, wash and dry to obtain the lead sulfide material whose particle shape is an octagonal star. Or put the reaction solution into a microwave reactor, control the microwave power to 50-150W, the reaction temperature to 120-160°C, and the reaction time to 30-60min. After cooling, washing and drying, the lead sulfide material whose particle shape is an octagonal star is obtained.
Description
技术领域 technical field
本发明涉及一种制备硫化铅材料的方法，具体涉及一种制备八角星形的硫化铅材料的方法。The invention relates to a method for preparing a lead sulfide material, in particular to a method for preparing an octagonal star-shaped lead sulfide material.
背景技术 Background technique
硫化铅是一种重要的半导体材料，在近红外通讯、光电器件和太阳能电池等方面有着重要应用价值。近年来，人们发现材料的形貌、尺寸和结构直接影响材料的性能，因此，对材料的特殊形貌控制制备也成为材料制备领域的研究热点。人们采用各种方法制备得到多种形貌的硫化铅材料，如人们采用添加表面活性剂高压釜水热法得到硫化铅纳米球(CN101402468A)、纳米棒(CN101049960A)、空心立方状纳米晶(CN101402467A)、单分散立方状纳米晶(CN101402467A)、六角星形纳米晶(CN101117237A)、金字塔方形管(CrystalGrowth&Design，2009，7，第3119页)；利用微波辅助法制备出六角形、树枝状和耳状(Materials Letters，2009，63，第667页)；利用微乳液辅助法合成出花状纳米晶(Solid State Sciences，2009，11，第976-981页)。在各文献报道的各种方法中，其中高压釜水热法工艺设备简单，容易控制和实现工业化生产，微波法反应时间短，通常在几分钟或者几十分钟即反应完全，节省能源；而表面活性剂辅助这些方法又是控制材料形貌的较佳方法，以上文献中使用的表面活性剂为十二烷基苯磺酸钠阴离子表面活性剂或十六烷基三甲基溴化胺阳离子表面活性剂或这两种混合的表面活性剂，这两种表面活性剂为石油化学合成产品，且为长链烷基结构，具有很强柔性，在控制制备材料形貌具有一定缺陷。因此，在石油资源日益枯竭的今天，以新型可再生资源衍生物表面活性剂代替这两种表面活性剂成为一种必然。Lead sulfide is an important semiconductor material, which has important application value in near-infrared communication, optoelectronic devices and solar cells. In recent years, it has been found that the shape, size and structure of materials directly affect the properties of materials. Therefore, the preparation of materials with special shape control has become a research hotspot in the field of material preparation. People adopt various methods to prepare lead sulfide materials with multiple shapes, such as people adopting adding surfactant autoclave hydrothermal method to obtain lead sulfide nanospheres (CN101402468A), nanorods (CN101049960A), hollow cubic nanocrystals (CN101402467A ), monodisperse cubic nanocrystals (CN101402467A), hexagonal star nanocrystals (CN101117237A), pyramidal square tubes (Crystal Growth & Design, 2009, 7, p. 3119); hexagonal, dendritic and ear-shaped (Materials Letters, 2009, 63, p. 667); Utilize microemulsion-assisted method to synthesize flower-like nanocrystals (Solid State Sciences, 2009, 11, p. 976-981). Among the various methods reported in the literature, the autoclave hydrothermal method has simple equipment, is easy to control and realizes industrial production, and the microwave method has a short reaction time, usually complete reaction in a few minutes or tens of minutes, saving energy; and the surface Active agent assists these methods and is the preferred method of controlling material morphology again, and the surfactant used in the above literature is sodium dodecylbenzenesulfonate anionic surfactant or hexadecyltrimethylammonium bromide cationic surface The active agent or these two mixed surfactants, these two surfactants are petrochemical synthetic products, and have a long-chain alkyl structure, which is very flexible and has certain defects in controlling the morphology of the prepared materials. Therefore, in today's increasingly depleted petroleum resources, it is inevitable to replace these two surfactants with new renewable resource derivative surfactants.
发明内容 Contents of the invention
本发明提供一种制备硫化铅材料的方法，其中采用松香基表面活性剂作为控制材料微观形貌的表面活性剂。其中松香基表面活性剂是以我国重要的可再生资源松香为原料合成的产品，具有原料易得，环保等特点。The invention provides a method for preparing a lead sulfide material, wherein a rosin-based surfactant is used as a surfactant for controlling the microscopic morphology of the material. Among them, the rosin-based surfactant is a product synthesized from rosin, an important renewable resource in my country, and has the characteristics of easy-to-obtain raw materials and environmental protection.
根据本发明的一个实施方案，制备八角星状的硫化铅材料的方法包括以下步骤：According to one embodiment of the present invention, the method for preparing the star-shaped lead sulfide material comprises the following steps:
按照1-2∶2-4∶0.01-0.10的摩尔比配制硝酸铅、硫脲、松香基表面活性剂的反应混合物，将该混合物加入到溶剂中，搅拌均匀，得到反应液；其中，反应混合物与溶剂的质量比为1∶15-40，所述溶剂选自乙醇和去离子水中的一种；Prepare the reaction mixture of lead nitrate, thiourea, and rosin-based surfactant according to the molar ratio of 1-2:2-4:0.01-0.10, add the mixture into the solvent, and stir evenly to obtain the reaction liquid; wherein, the reaction mixture The mass ratio to the solvent is 1:15-40, and the solvent is selected from one of ethanol and deionized water;
将反应液放入密封的高压反应釜中，加热到140-200℃，保温9-36小时，然后经过冷却、洗涤、干燥得到产品。The reaction solution is put into a sealed high-pressure reaction kettle, heated to 140-200°C, kept for 9-36 hours, then cooled, washed and dried to obtain the product.
其中，高压反应釜可以使用本领域技术人员熟知的反应釜而没有特殊要求。Wherein, the high-pressure reactor can use a reactor well-known to those skilled in the art without special requirements.
根据本发明的另一个实施方案，制备八角星状的硫化铅材料的方法包括如下步骤：According to another embodiment of the present invention, the method for preparing the star-shaped lead sulfide material comprises the steps:
按照1-2∶2-4∶0.01-0.10的摩尔比配制硝酸铅、硫脲、松香基表面活性剂的反应混合物，将该混合物加入到溶剂中，搅拌均匀，得到反应液；其中，反应混合物与溶剂的质量比为1∶15-40，所述溶剂选自乙醇和去离子水中的一种；Prepare the reaction mixture of lead nitrate, thiourea, and rosin-based surfactant according to the molar ratio of 1-2:2-4:0.01-0.10, add the mixture into the solvent, and stir evenly to obtain the reaction liquid; wherein, the reaction mixture The mass ratio to the solvent is 1:15-40, and the solvent is selected from one of ethanol and deionized water;
将反应液放入微波反应器中，控制微波功率为50-150W，反应温度为120-160℃，反应时间为30-60min。然后经过冷却、洗涤、干燥得到产品。Put the reaction solution into a microwave reactor, control the microwave power to 50-150W, the reaction temperature to 120-160°C, and the reaction time to 30-60min. Then the product is obtained through cooling, washing and drying.
本发明所用的微波反应器没有特殊要求，只要能够达到本发明方法的反应条件即可。The microwave reactor used in the present invention has no special requirements, as long as the reaction conditions of the method of the present invention can be achieved.
根据本发明的一个实施方案，其中所用的松香基表面活性剂选自以下表面活性剂中的一种或多种：According to one embodiment of the present invention, wherein the rosin-based surfactant used is selected from one or more of the following surfactants:
松香基表面活性剂(I)Rosin-based Surfactant (I)
其中，n的范围为：1≤n≤6，Among them, the range of n is: 1≤n≤6,
松香基表面活性剂(II)Rosin-based Surfactant (II)
其中，n的范围为：1≤n≤4，Among them, the range of n is: 1≤n≤4,
松香基表面活性剂(III)Rosin-based surfactant (III)
其中，n的范围为：1≤n≤10，Among them, the range of n is: 1≤n≤10,
松香基表面活性剂(IV)Rosin-based Surfactant (IV)
其中，
冷却可以为自然冷却，也可以是强制冷却。洗涤和干燥步骤可以采用本领域技术人员熟知的各种洗涤干燥方法，例如干燥可以包括但不限于直接在烘箱内干燥、经抽滤后在烘箱内干燥、红外干燥、微波干燥等等。Cooling can be natural cooling or forced cooling. The washing and drying steps can adopt various washing and drying methods well known to those skilled in the art. For example, drying can include but not limited to direct drying in an oven, drying in an oven after suction filtration, infrared drying, microwave drying, etc.
使用扫描电子显微镜分析根据本发明的实施方案制备的硫化铅材料。硫化铅材料的形状为八角星形颗粒。Lead sulfide materials prepared according to embodiments of the present invention were analyzed using scanning electron microscopy. The shape of the lead sulfide material is an octagonal star grain.
附图说明 Description of drawings
参照附图以及以下的实施例，可以更好地理解本发明的制备硫化铅材料的方法。The method for preparing lead sulfide material of the present invention can be better understood with reference to the accompanying drawings and the following examples.
图1是根据本发明的一个实施例制备的硫化铅颗粒的扫描电镜(SEM)照片；Fig. 1 is the scanning electron microscope (SEM) photograph of the lead sulfide particle prepared according to one embodiment of the present invention;
图2是根据本发明的另一个实施例制备的硫化铅颗粒的扫描电镜(SEM)照片；Fig. 2 is the scanning electron microscope (SEM) photo of the lead sulfide particle prepared according to another embodiment of the present invention;
图3是根据本发明的另一个实施例制备的硫化铅颗粒的扫描电镜(SEM)照片；Fig. 3 is the scanning electron microscope (SEM) photograph of the lead sulfide particle prepared according to another embodiment of the present invention;
图4是根据本发明的另一个实施例制备的硫化铅颗粒的扫描电镜(SEM)照片；Fig. 4 is the scanning electron microscope (SEM) photograph of the lead sulfide particle that prepares according to another embodiment of the present invention;
图5是根据本发明的另一个实施例制备的硫化铅颗粒的扫描电镜(SEM)照片。Fig. 5 is a scanning electron microscope (SEM) photograph of lead sulfide particles prepared according to another embodiment of the present invention.
具体实施方式 Detailed ways
实施例1Example 1
取0.4mol/L的硝酸铅2mL、0.4mol/L的硫脲3mL、10g/mL松香基表面活性剂A乙醇溶液1mL加入到反应釜中，混合均匀后放入10mL密封试管中，放入美国CEM discover单模微波反应仪，控制微波功率80W，温度150℃下反应50min，冷却至室温，去离子水和乙醇洗涤黑色沉淀3次，离心分离得到黑色沉淀，在80℃下干燥8h得到形貌如图1的八角星形硫化铅产品。Take 2mL of 0.4mol/L lead nitrate, 3mL of 0.4mol/L thiourea, and 1mL of 10g/mL rosin-based surfactant A ethanol solution into the reaction kettle, mix well, put them into a 10mL sealed test tube, and put them in the U.S. CEM discover single-mode microwave reactor, controlled microwave power 80W, reacted at 150°C for 50min, cooled to room temperature, washed the black precipitate with deionized water and ethanol for 3 times, centrifuged to obtain the black precipitate, dried at 80°C for 8h to obtain the morphology An octagonal star-shaped lead sulfide product as shown in Figure 1.
实施例2Example 2
取0.4mol/L的硝酸铅4mL、0.4mol/L的硫脲8mL、10g/mL松香基表面活性剂B乙醇溶液0.8mL加入到反应釜中，混合均匀后将反应釜放入160℃的烘箱中反应16h，冷却至室温，去离子水和乙醇洗涤黑色沉淀3次，离心分离得到黑色沉淀，在80℃下干燥8h得到形貌如图2的硫化铅产品。Take 4mL of 0.4mol/L lead nitrate, 8mL of 0.4mol/L thiourea, and 0.8mL of 10g/mL rosin-based surfactant B ethanol solution into the reaction kettle, mix well and put the reaction kettle into an oven at 160°C React in medium for 16 hours, cool to room temperature, wash the black precipitate with deionized water and ethanol three times, centrifuge to obtain the black precipitate, and dry at 80°C for 8 hours to obtain the lead sulfide product with the morphology shown in Figure 2.
实施例3Example 3
取0.4mol/L的硝酸铅4mL、0.4mol/L的硫脲8mL、10g/mL松香基表面活性剂C乙醇溶液0.6mL加入到反应釜中，混合均匀后将反应釜放入170℃的烘箱中反应12h，冷却至室温，去离子水和乙醇洗涤黑色沉淀3次，离心分离得到黑色沉淀，在80℃下干燥8h得到形貌如图3、4的硫化铅产品。Take 4mL of 0.4mol/L lead nitrate, 8mL of 0.4mol/L thiourea, and 0.6mL of 10g/mL rosin-based surfactant C ethanol solution into the reaction kettle, mix well and put the reaction kettle into an oven at 170°C React in medium for 12 hours, cool to room temperature, wash the black precipitate with deionized water and ethanol three times, centrifuge to obtain the black precipitate, and dry it at 80°C for 8 hours to obtain the lead sulfide products with the morphology shown in Figures 3 and 4.
实施例4Example 4
取0.4mol/L的硝酸铅4mL、0.4mol/L的硫脲8mL、10g/mL松香基表面活性剂D 乙醇溶液0.2mL加入到反应釜中，混合均匀后将反应釜放入150℃的烘箱中反应20h，冷却至室温，去离子水和乙醇洗涤黑色沉淀3次，离心分离得到黑色沉淀，在80℃下干燥8h得到形貌如图5的硫化铅产品。Take 4mL of 0.4mol/L lead nitrate, 8mL of 0.4mol/L thiourea, and 0.2mL of 10g/mL rosin-based surfactant D ethanol solution into the reaction kettle, mix well and put the reaction kettle into an oven at 150°C React in medium for 20 hours, cool to room temperature, wash the black precipitate with deionized water and ethanol three times, centrifuge to obtain the black precipitate, and dry it at 80°C for 8 hours to obtain the lead sulfide product with the morphology shown in Figure 5.
松香基表面活性剂A 松香基表面活性剂BRosin-based Surfactant A Rosin-based Surfactant B
松香基表面活性剂CRosin-based Surfactant C
松香基表面活性剂DRosin-based Surfactant D
其中，
虽然以上实施例举例说明了本发明的具体实施方案，但是，应当理解的是，这些实施例仅用于举例说明本发明的实施方案而不对本发明的范围有任何限定意义。所附权利要求及其任何变化形式都应包括在本发明要求保护的范围内。Although the above examples illustrate specific embodiments of the present invention, it should be understood that these examples are only used to illustrate the embodiments of the present invention and do not have any limiting meaning to the scope of the present invention. The appended claims and any variations thereof should be included within the scope of the present invention.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101452A (en) * | 1952-09-27 | 1978-07-18 | Electronics Corporation Of America | Lead sulfide activation process |
| CN101117237A (en) * | 2007-07-17 | 2008-02-06 | 浙江大学 | A method for preparing hexagonal star-shaped lead sulfide nanocrystals |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4101452A (en) * | 1952-09-27 | 1978-07-18 | Electronics Corporation Of America | Lead sulfide activation process |
| CN101117237A (en) * | 2007-07-17 | 2008-02-06 | 浙江大学 | A method for preparing hexagonal star-shaped lead sulfide nanocrystals |
Non-Patent Citations (2)
| Title |
|---|
| BO DING ET AL.: "Shape-controlledsynthesesofPbSsubmicro-/nano-crystals via hydrothermal method", 《JOURNAL OF CRYSTAL GROWTH》 * |
| GUANGJUN ZHOU ET AL.: "Controlled Synthesis of High-Quality PbS Star-Shaped Dendrites, Multipods, Truncated Nanocubes, and Nanocubes and Their Shape Evolution Process", 《J. PHYS. CHEM. B》 * |
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