CN103788369B - Aqueous phase prepares the method for poly-o-phenylenediamine fluorescence nano band - Google Patents
Aqueous phase prepares the method for poly-o-phenylenediamine fluorescence nano band Download PDFInfo
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 39
- 239000002127 nanobelt Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 3
- 239000002074 nanoribbon Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 2
- -1 Poly(o-phenylenediamine) Polymers 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- LYVWMIHLNQLWAC-UHFFFAOYSA-N [Cl].[Cu] Chemical compound [Cl].[Cu] LYVWMIHLNQLWAC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Abstract
水相法制备聚邻苯二胺荧光纳米带的方法，涉及一种制备具有良好荧光性能的聚邻苯二胺纳米带的方法。所述方法为：将0.5mL0.001～0.15mol/L的邻苯二胺溶液加入到1mL去离子水中，加入0.8～1.2mL饱和的NaCl溶液或KCl溶液，搅拌均匀，加入0.5mL0.25～1.0mol/L氯化铜溶液，反应进行0.5～3小时后将溶液离心分离，沉淀物水洗后室温条件下自然干燥，将干燥后的聚邻苯二胺纳米带用碱性溶液进行超声处理，即可得到聚邻苯二胺荧光纳米带。该工艺在室温条件下进行，得到的产物形貌均一且荧光强度强；通过本发明的方法得到的聚邻苯二胺纳米带可用于光电和重金属离子提取等领域。
The invention discloses a method for preparing poly-o-phenylenediamine fluorescent nanobelts by an aqueous phase method, relating to a method for preparing poly-o-phenylenediamine nanoribbons with good fluorescent properties. The method is as follows: add 0.5mL of 0.001-0.15mol/L o-phenylenediamine solution into 1mL of deionized water, add 0.8-1.2mL of saturated NaCl solution or KCl solution, stir evenly, add 0.5mL of 0.25- 1.0mol/L copper chloride solution, the solution was centrifuged after the reaction was carried out for 0.5 to 3 hours, the precipitate was washed with water and dried naturally at room temperature, and the dried poly-o-phenylenediamine nanobelt was ultrasonically treated with an alkaline solution. The poly-o-phenylenediamine fluorescent nanobelt can be obtained. The process is carried out at room temperature, and the obtained product has uniform appearance and strong fluorescence intensity; the poly-o-phenylenediamine nanobelt obtained by the method of the invention can be used in the fields of optoelectronics, heavy metal ion extraction and the like.
Description
技术领域 technical field
本发明涉及一种制备具有良好荧光性能的聚邻苯二胺纳米带的方法，具体涉及一种在水相环境中制备聚邻苯二胺荧光纳米带的方法。 The invention relates to a method for preparing poly-o-phenylenediamine nanobelts with good fluorescent properties, in particular to a method for preparing poly-o-phenylenediamine fluorescent nanobelts in an aqueous phase environment.
背景技术 Background technique
聚邻苯二胺作为导电聚合物的重要组成部分，与聚苯胺相比具有更多的氨基和亚氨基结构，能够提供更多的可供修饰的官能团，从而其在电催化、传感器等方面都具有巨大的应用潜力。聚邻苯二胺纳米带作为一类具有较大长径比的一维纳米材料，具有较长的共轭结构，从而在聚合物导电方面具有独特的优势。纳米带的荧光性能进一步拓展了其应用领域，而聚邻苯二胺的结构对其光电性能影响显著，因此，发明一种合成具有良好荧光性能的聚邻苯二胺纳米带的工艺具有重要的理论价值和现实意义。 As an important part of conductive polymers, poly-ortho-phenylenediamine has more amino and imino structures than polyaniline, which can provide more functional groups for modification, so that it can be used in electrocatalysis, sensors, etc. It has great application potential. Poly-o-phenylenediamine nanoribbons, as a class of one-dimensional nanomaterials with a large aspect ratio, have a longer conjugated structure, which has unique advantages in polymer conductivity. The fluorescent properties of nanobelts further expand its application fields, and the structure of poly-o-phenylenediamine has a significant impact on its photoelectric properties. Therefore, it is important to invent a process for synthesizing poly-o-phenylenediamine nanoribbons with good fluorescence properties. Theoretical value and practical significance.
发明内容 Contents of the invention
本发明的目的是提供一种在水相环境中制备聚邻苯二胺荧光纳米带的方法。该工艺在室温条件下进行，得到的产物形貌均一且荧光强度强；设备简单，操作方便，容易控制；通过本发明的方法得到的聚邻苯二胺纳米带可用于光电和重金属离子提取等领域。 The purpose of the present invention is to provide a method for preparing poly-o-phenylenediamine fluorescent nanobelts in an aqueous environment. The process is carried out at room temperature, and the obtained product has uniform appearance and strong fluorescence intensity; the equipment is simple, the operation is convenient, and it is easy to control; the poly-o-phenylenediamine nanobelt obtained by the method of the present invention can be used for photoelectricity and heavy metal ion extraction, etc. field.
本发明的目的是通过以下技术方案实现的： The purpose of the present invention is achieved through the following technical solutions:
将0.5ml0.001～0.15mol/L的邻苯二胺溶液加入到1ml去离子水中，加入0.8～1.2ml饱和的NaCl溶液或KCl溶液，搅拌均匀，加入0.5ml0.25～1.0mol/L氯化铜溶液，反应进行0.5～3小时后将溶液离心分离，沉淀物水洗后室温条件下自然干燥，将干燥后的聚邻苯二胺纳米带用碱性溶液进行超声处理10～25分钟，即可得到聚邻苯二胺荧光纳米带。 Add 0.5ml of 0.001～0.15mol/L o-phenylenediamine solution to 1ml of deionized water, add 0.8～1.2ml of saturated NaCl solution or KCl solution, stir well, add 0.5ml of 0.25～1.0mol/L chlorine Copper solution, the solution is centrifuged after the reaction is carried out for 0.5 to 3 hours, the precipitate is washed with water and then dried naturally at room temperature, and the dried poly-o-phenylenediamine nanobelt is ultrasonically treated with an alkaline solution for 10 to 25 minutes, namely The poly-o-phenylenediamine fluorescent nanobelt can be obtained.
本发明在水相环境中，通过氧化剂与邻苯二胺单体发生氧化还原反应，在高浓度氯化钠或氯化钾存在的条件下，低聚体发生自组装过程，形成一维的纳米带结构；通过对氧化剂和单体浓度和摩尔比以及反应的离子环境的控制，可以对产物的形貌进行调控；纳米带合成后，用碱性溶液对纳米带进行超声处理，即可得到具有良好荧光性能的聚邻苯二胺纳米带。 In the present invention, in the aqueous phase environment, the oxidation-reduction reaction occurs between the oxidant and the o-phenylenediamine monomer, and under the condition of the presence of high-concentration sodium chloride or potassium chloride, the oligomer undergoes a self-assembly process to form a one-dimensional nanometer Band structure; by controlling the concentration and molar ratio of the oxidant and monomer and the reaction ion environment, the morphology of the product can be regulated; after the nanobelt is synthesized, the nanobelt is ultrasonically treated with an alkaline solution to obtain a Poly(o-phenylenediamine) nanobelts with good fluorescence properties.
相比于现有技术，本方法具有以下优点： Compared with the prior art, this method has the following advantages:
1、该工艺采用水相环境，避免了有机相的高毒性和高成本问题； 1. The process adopts a water phase environment, which avoids the high toxicity and high cost of the organic phase;
2、以氯化铜为氧化剂合成聚邻苯二胺纳米带； 2. Synthesis of poly-o-phenylenediamine nanobelts with copper chloride as oxidant;
3、该工艺能有效的合成聚邻苯二胺纳米带且合成的纳米带荧光强度强； 3. This process can effectively synthesize poly-o-phenylenediamine nanobelts and the synthesized nanobelts have strong fluorescence intensity;
4、实验中采用氯化钠或氯化钾溶液作为纳米带生成的离子环境； 4. In the experiment, sodium chloride or potassium chloride solution was used as the ion environment generated by the nanobelt;
5、采用超声处理加快了去质子化过程，在10分钟之内即可使纳米带发光； 5. Ultrasonic treatment is used to speed up the deprotonation process, and the nanobelt can emit light within 10 minutes;
6、通过该工艺合成的纳米带形貌均一，缺陷少，可重复性好，荧光强度强，产物的提取方便； 6. The nanoribbons synthesized by this process have uniform morphology, few defects, good repeatability, strong fluorescence intensity, and easy extraction of products;
7、该工艺的所有步骤均在室温条件下进行，无需加热； 7. All steps of the process are carried out at room temperature without heating;
8、该方法操作简单，反应时间短，可重复性好，制备的聚邻苯二胺荧光纳米带可作为导电聚合物应用于光电技术领域或者作为吸附载体应用于重金属离子提取。 8. The method is simple in operation, short in reaction time and good in repeatability. The prepared poly-o-phenylenediamine fluorescent nanobelt can be used as a conductive polymer in the field of photoelectric technology or as an adsorption carrier in the extraction of heavy metal ions.
附图说明 Description of drawings
图1为本发明实施例1所制备聚邻苯二胺纳米带荧光显微镜形貌图。 Fig. 1 is a fluorescence microscope topography of poly-o-phenylenediamine nanoribbons prepared in Example 1 of the present invention.
图2为本发明实施例2所制备聚邻苯二胺纳米带荧光显微镜形貌图。 Fig. 2 is a fluorescence microscope topography of poly-o-phenylenediamine nanoribbons prepared in Example 2 of the present invention.
具体实施方式 detailed description
下面结合实施例对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。 The technical solution of the present invention will be further described below in conjunction with the examples, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention within the scope of protection.
实施例1：Example 1:
将0.5ml现配的0.1mol/L的邻苯二胺溶液加入到1ml去离子水中，加入1ml饱和的NaCl溶液，搅拌均匀，加入0.5ml0.5mol/L的氯化铜溶液，静置，溶液中出现大量肉眼可见的絮状沉淀，反应进行1小时后将溶液离心并用去离子水洗三次，室温条件下自然干燥。将干燥后的聚邻苯二胺纳米带用0.8mol/L的NaOH溶液超声处理10分钟，即可得到聚邻苯二胺绿色荧光纳米带（图1）。 Add 0.5ml of the prepared 0.1mol/L o-phenylenediamine solution to 1ml of deionized water, add 1ml of saturated NaCl solution, stir evenly, add 0.5ml of 0.5mol/L copper chloride solution, let it stand, and the solution A large number of flocculent precipitates visible to the naked eye appeared in the solution. After the reaction was carried out for 1 hour, the solution was centrifuged and washed three times with deionized water, and dried naturally at room temperature. The dried poly-o-phenylenediamine nanoribbons were ultrasonically treated with 0.8 mol/L NaOH solution for 10 minutes to obtain poly-o-phenylenediamine green fluorescent nanoribbons (Figure 1).
实施例2:Example 2:
将0.5ml现配的0.01mol/L的邻苯二胺溶液加入到1ml去离子水中，加入1ml饱和的KCl溶液，搅拌均匀，加入0.5ml0.25mol/L的氯化铜溶液，静置，溶液中出现大量肉眼可见的絮状沉淀，反应进行1小时后将溶液离心并用去离子水洗三次，室温条件下自然干燥。将干燥后的聚邻苯二胺纳米带用1.0mol/L的NaOH溶液超声处理10分钟，即可得到聚邻苯二胺绿色荧光纳米带（图2）。 Add 0.5ml of the prepared 0.01mol/L o-phenylenediamine solution to 1ml of deionized water, add 1ml of saturated KCl solution, stir evenly, add 0.5ml of 0.25mol/L copper chloride solution, let it stand, and the solution A large number of flocculent precipitates visible to the naked eye appeared in the solution. After the reaction was carried out for 1 hour, the solution was centrifuged and washed three times with deionized water, and dried naturally at room temperature. The dried poly-o-phenylenediamine nanoribbons were ultrasonically treated with 1.0 mol/L NaOH solution for 10 minutes to obtain poly-o-phenylenediamine green fluorescent nanoribbons (Figure 2).
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| CN1363418A (en) * | 2001-12-07 | 2002-08-14 | 华南理工大学 | Process for preparing colloid crystal with ordered 3D structure |
| CN102634015A (en) * | 2012-05-04 | 2012-08-15 | 中南大学 | Synthesis method of poly(m-phenylenediamine) nanoparticles |
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| CN1363418A (en) * | 2001-12-07 | 2002-08-14 | 华南理工大学 | Process for preparing colloid crystal with ordered 3D structure |
| CN102634015A (en) * | 2012-05-04 | 2012-08-15 | 中南大学 | Synthesis method of poly(m-phenylenediamine) nanoparticles |
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