Preparation of 3D graphene by 3D printing and its application in water treatment

doi:10.16085/j.issn.1000-6613.2021-1277

Abstract

Abstract:

Graphene, as a new type of nano materials, has good adsorption and removal performance for various pollutants in water. However, the final state of graphene nanopowder makes it difficult to separate from the solution after use, resulting in secondary pollution. Therefore, the construction of large volume three-dimensional graphene structure can effectively remedy the problem of difficult separation of nano materials in water treatment. This paper introduced the three-dimensional structure preparation methods commonly used nowadays, such as template method, self-assembly method and so on, but these methods were usually cumbersome steps, many influencing factors and required conditions and other shortcomings, which were easy to produce structural defects in the process, and thus affecting the mechanical properties of the three-dimensional structure. The 3D printing method had the advantages of simple operation, accurate structure design and batch preparation through computer data control. It can prepare excellent three-dimensional structure and modify or increase its mechanical properties through flexible control of slurry components. To sum up, the key to make 3D printing graphene suitable for water treatment was to configure the slurry that met the viscosity requirements of 3D printing and to make the 3D structure havng certain required mechanical.

Key words: graphene, 3D printing, preparation, sewage treatment

摘要：

石墨烯作为一类新型纳米材料，具有对水中各类污染物良好的吸附去除性能，但石墨烯纳米粉末态的性状使其在使用后难以从溶液中分离出来而造成二次污染。因此构建大体积的三维石墨烯结构，可以有效弥补水处理中纳米材料难以分离的问题。本文介绍了如今常用的三维结构制备方法，如模板法、自组装法等，但这些方法通常步骤烦琐、影响因素及所需条件较多等，在过程中易产生结构缺陷，从而影响制得的三维结构的力学性能。文中指出，3D打印法通过计算机数据调控，具有操作简便、结构设计精准、批量制备的优点，可制备出优良的三维结构体，并可通过对浆料组分的灵活调控进行改性或增加其力学性能。综上所述，配置满足3D打印黏度要求的浆料，并使制得的三维结构具备一定要求的力学性能，充分利用其精密的规模化生产，是使3D打印三维石墨烯适用于水处理的关键所在。

关键词: 石墨烯, 3D打印, 制备, 污水处理

CLC Number:

ZHANG Huining, SHI Zhongyu, XIAO Yankui, ZHANG Xiaoqin, YIN Xin, TIAN Lihong. Preparation of 3D graphene by 3D printing and its application in water treatment[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2231-2242.

张惠宁, 石中玉, 肖彦奎, 张晓琴, 尹鑫, 田丽红. 3D打印制备三维石墨烯及其在水处理中的应用[J]. 化工进展, 2022, 41(5): 2231-2242.

Figures/Tables 12

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项目	模板法	化学交联法	自组装法	3D打印法
优点	方法简便、成本较低、制备的三维石墨烯力学性能较差	使三维结构具有高强度的化学交联	工艺简便、能耗较低	快速制备、结构精密、较好的力学性能，且无须后处理工程
缺点	模板通常无法去除干净，并且去除模板时可能损坏结构，导致表面的缺陷较多	交联剂会降低导电性，反应所需温度也会增加能源消耗	影响因素较多，无法控制结构形貌的精度，力学性能较差	通常对材料及浆料具有一定要求。且部分3D打印技术成本较高
孔隙率	孔隙率高	孔隙率受pH影响^［74］	可一步成型获得比表面积较大的三维石墨烯凝胶	孔隙率高

项目	模板法	化学交联法	自组装法	3D打印法
优点	方法简便、成本较低、制备的三维石墨烯力学性能较差	使三维结构具有高强度的化学交联	工艺简便、能耗较低	快速制备、结构精密、较好的力学性能，且无须后处理工程
缺点	模板通常无法去除干净，并且去除模板时可能损坏结构，导致表面的缺陷较多	交联剂会降低导电性，反应所需温度也会增加能源消耗	影响因素较多，无法控制结构形貌的精度，力学性能较差	通常对材料及浆料具有一定要求。且部分3D打印技术成本较高
孔隙率	孔隙率高	孔隙率受pH影响^［74］	可一步成型获得比表面积较大的三维石墨烯凝胶	孔隙率高

项目	喷墨打印法	熔融沉积成型	直写成型法
打印材料	工程塑料、粉末、尼龙、光敏树脂，甚至是金属、陶瓷等^［36］	丙烯腈-丁二烯-苯乙烯共聚物（ABS）、聚乳酸（PLA）、聚碳酸酯（PC）、耐冲击性聚苯乙烯（HIPS）、热塑性聚氨酯（TPU）、聚醚醚酮（PEEK）等^［43］	一定流变性能的碳浆、聚酰亚胺、低温油墨、导电材料（金、银、铜等导电浆料）、环氧树脂、可消散有机物等
墨水要求	墨水具备较快的干燥速度、良好的黏附性、优异的稳定性、易生产加工	墨水具备良好的热塑加工性能，具备合适的模量和黏度，较低的热收缩率，较低的结晶度，较高的稳定性	墨水具备一定的黏度，同时具备“剪切稀化”的性能
优点	无须制作模板，固化过程无溶剂挥发，灵活设定打印效果	设备投入低、操作简单	打印材料的选择广泛，结构便于设计，无过多影响参数
缺点	干燥时间较长，墨水回收利用易变质	材料限制较大，打印结构表面粗糙，可能具备细胞毒性	设备成本高
应用	3D 制作和增值产品（喷边、手机壳等）、装饰建材、印刷电子、纺织、图像展示、陶瓷、木材、墙面装饰	零件制造、汽车、航天等领域广泛应用	生物医学、微电子器件、高性能材料等方面的应用

项目	喷墨打印法	熔融沉积成型	直写成型法
打印材料	工程塑料、粉末、尼龙、光敏树脂，甚至是金属、陶瓷等^［36］	丙烯腈-丁二烯-苯乙烯共聚物（ABS）、聚乳酸（PLA）、聚碳酸酯（PC）、耐冲击性聚苯乙烯（HIPS）、热塑性聚氨酯（TPU）、聚醚醚酮（PEEK）等^［43］	一定流变性能的碳浆、聚酰亚胺、低温油墨、导电材料（金、银、铜等导电浆料）、环氧树脂、可消散有机物等
墨水要求	墨水具备较快的干燥速度、良好的黏附性、优异的稳定性、易生产加工	墨水具备良好的热塑加工性能，具备合适的模量和黏度，较低的热收缩率，较低的结晶度，较高的稳定性	墨水具备一定的黏度，同时具备“剪切稀化”的性能
优点	无须制作模板，固化过程无溶剂挥发，灵活设定打印效果	设备投入低、操作简单	打印材料的选择广泛，结构便于设计，无过多影响参数
缺点	干燥时间较长，墨水回收利用易变质	材料限制较大，打印结构表面粗糙，可能具备细胞毒性	设备成本高
应用	3D 制作和增值产品（喷边、手机壳等）、装饰建材、印刷电子、纺织、图像展示、陶瓷、木材、墙面装饰	零件制造、汽车、航天等领域广泛应用	生物医学、微电子器件、高性能材料等方面的应用

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[13]	YU Jie, ZHANG Wenlong. Development status and progress of lithium ion battery separator [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1760-1768.
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