CN110394193A - 一种3d打印骨架＠钨酸铋的光催器件的制备方法 - Google Patents
一种3d打印骨架＠钨酸铋的光催器件的制备方法 Download PDFInfo
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Abstract
本发明公开一种3D打印骨架@钨酸铋的光催器件的制备方法，由以下方法制得：(1)制备含生物质的耐热型线材，通过3D打印(FDM)获得不同结构骨架制件；(2)在3D打印骨架表面水热合成钨酸铋。本发明的光催器件，具有光催效率高，易于回收，成本较低，制备工艺简单等优点。可应用于污水、空气和土壤中有机污染物的光催化降解处理。
Description
技术领域
本发明属于废水、废气处理的环保领域，具体涉及一种3D打印骨架@钨酸铋的光催器件的制备方法。
背景技术
随着工业化进程快速推进，重经济轻环保的发展模式造成了大气、水体、土壤等环境污染问题。这些问题给人类社会的可持续发展带来重大挑战，解决环境问题已是刻不容缓。其中水体污染是极其重要的一个环节。水污染处理方法很多，其中光催化技术是一种利用新能源来解决环境污染问题的有效方法，它利用光催化降解有毒有害物质，提供了一种非常环保治理污染方法。但是目前大部分光催化剂为粉体，难回收成为限制其应用的一大难题，器件化则是解决这个难题的可行方法。
目前实现器件化方法很多，如将催化剂涂覆在各种材料表面，CN201510118618.2和CN201510118543.8公开了两种光催化涂覆剂的制备方法和涂覆方法，这种方法负载率较高，但较为复杂，且固载的催化剂易脱落。也有与高分子材料直接熔融共混制成各种光催化材料，此法较为简单，但催化剂大部分包覆在高分子内部，造成浪费。
3D打印是一种新型的智能增材制造技术，相比传统成型方式相比，具有快速制备、精细化制造、材料利用率高、制件结构可设计等优点。其中熔融沉积成型(FDM)最为普及的3D打印技术，它可将高分子材料打印成复杂结构的器件，以满足不同应用的不同需求。
水热反应一般在水热反应釜中进行，水热反应釜为受热自生压密封压力容器。水热合成技术是一种反应温和、易控、节能和少污染的新合成路线，具有价态稳定化作用与非氧嵌入特征等特点。
如果能将3D打印器件与光催化降解相结合，将会大大拓展3D打印应用范围。本发明通过3D打印技术与水热技术相结合，实现光催化剂在3D打印制件上的固定化。
发明内容
针对现有技术的不足，本发明的目的是提供一种3D打印骨架@钨酸铋的光催器件的制备方法。
本发明所选基体树脂是一种具有优良的机械性能、耐热性和可加工性的材料，也是3D打印(FDM)的主流材料。本发明引入一种体积微小的单细胞自养生物，富含功能性官能团能使3D打印器件表面更加易于负载Bi2WO6，通过双螺杆挤出工艺制造含生物质的3D打印线材，将耐热性好的树脂作为基体，使3D打印器件在光催化剂Bi2WO6合成过程中保持其原有形貌。
本发明光催化剂Bi2WO6通过水热的方法进行合成，在Bi2WO6水热法合成过程中加入3D打印制件，实现将其负载于3D制件的目的。Bi2WO6水热合成温度为100～200℃，反应温度较低，合成过程中不会造成3D打印制件内部树脂老化、降解。与熔融共混法相比，能够解决光催化剂与高分子材料直接熔融共混制成的光催化材料，大部分光催化助剂包覆在高分子内部，造成浪费等问题。与沉淀法直接负载相比，能够解决光催化剂与基体结合力差、易于脱落的问题。
为了实现本发明，具体技术方案如下：
一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，包括以下步骤：
(1)将基体树脂59-91份、生物质8-40份、白油0.05-2份置于高速捏合机中，保持转速1000-6000rpm，高速搅拌5-20min后投入到螺杆挤出机，加工温度160-255℃，螺杆转速80-280rpm，挤出造粒，得到母粒经线材机挤出、牵引、收卷成线材，得到皮芯结构3D打印线材，再用3D打印得到形状可控的3D打印骨架；
(2)将钨酸盐溶解于去离子水为A液、铋盐溶解于有机酸为B液，将A液滴入B液，在10-80r/min速率搅拌下滴入碱溶液调节PH=2-4，搅拌下保持20-60min至反应完全；
(3)将步骤(1)中得到的3D打印骨架和步骤(2)中得到的悬浮液同时加入水热反应釜中，于100～200℃环境中密闭反应10～24h；反应结束后，进行冲洗、干燥，得到3D打印骨架@钨酸铋的光催器件。
所述步骤(1)中的基体树脂，选自ABS、ASA、PPS、POM、PC、PEEK、PA中的一种或几种。
所述步骤(1)中的生物质，选自小球藻、浒苔、螺旋藻、藻渣中的一种或几种。
所述步骤(1)中基体树脂和生物质分别真空干燥8-12h。
上述步骤(1)中3D打印条件为：打印温度为180-250℃、底板温度为50-100 ℃、打印速度为20-150mm/s、打印层厚为0.1-0.4mm。
上述步骤(2)中Bi2WO6的水热法合成中的钨酸盐、铋盐、有机酸、水的质量比为：0.5:1.5:4.5:25；所述步骤(2)中钨酸盐为：钨酸钠、钨酸钾中的一种；所述步骤(2)有机酸为：醋酸、草酸、柠檬酸中的一种；所述步骤(2)中碱溶液的滴入速率为：10-20mL/min以调节PH=2-4。
上述步骤(3)中步骤(1)中得到的3D打印骨架与步骤(2)中得到的悬浮液体积比为：0.01-0.05:1。
采用上述技术方案后，本发明有益效果为：1、制备方法简单高效，可制成复杂结构的光催化器件；2、生物质为器件表面提供活性位点，使大量光催化剂均匀地分布在器件表面；3、基体选用耐热型树脂，有利于在水热合成光催剂Bi2WO6过程中保护3D器件结构，提高光催器件使用寿命。
附图说明
图1是3D打印模型二十四面螺旋体；
图2是应用本发明实施例1所制备的3D打印骨架@钨酸铋的光催器件的表面形貌；
图3是应用本发明实施例1所制备的3D打印骨架@钨酸铋的光催器件，对罗丹明B的光降解和暗吸附活性谱图。
具体实施方式
实施例1
一种3D打印骨架@钨酸铋的光催器件的制备方法为按以下步骤进行：
（1）将ABS、小球藻真空干燥12h，称取干燥后的ABS(700g)、小球藻(299.5g)和白油(0.5g)，置于高速捏合机中，保持转速1000rpm，高速搅拌5min后投入到双螺杆挤出机，挤出温度设定为160℃、170℃、175℃、180℃、195℃、195℃、190℃、185℃、170℃、165℃，在双螺杆熔腔内熔融塑化并以转速为150rpm，挤出原料，将机头挤出的线条进入存有冷水的水槽，充分水冷冷却；线条进入牵引机收卷，得到3D打印线材。
（2）将上述线材，通过3D打印机（FDM）打印成体积为1cm3的二十四面螺旋体(见图1)，3D打印机参数为：打印温度为185℃、底板温度为60 ℃、打印速度为50mm/s、打印层厚为0.1mm。
（3）将钨酸钠0.7g溶解于25mL去离子水为A液、硝酸铋1.6g溶解于15mL 5mol/L的醋酸溶液为B液，在20mol/min速率下将A液滴入B液，在20r/min速率搅拌下滴入1mol/LNaOH溶液调节PH=2，搅拌下保持20min至反应完全。
（4）将步骤（2）得到的3D打印二十四面螺旋体小方块和步骤（3）中得到悬浮液的30mL同时加入50mL水热反应釜中，于120℃环境中密闭反应18h。反应后取出3D打印光催化器件，用去离子冲洗3次再用无水乙醇冲洗3次，最后在25℃下干燥24h。
（5）将所得3D打印骨架@钨酸铋的光催器件（见图2是3D打印骨架@钨酸铋的光催器件的表面形貌）加入到 80mL浓度为30mg/L的罗丹明B溶液中，避光搅拌120min 使达到吸附脱附平衡后，以紫外光（500W）为光源进行光照，每隔一定时间取样，用紫外分光光度计分别测定吸光度。得应用本发明实施例1所制备的3D打印骨架@钨酸铋的光催器件对罗丹明B的光降解和暗吸附活性谱图（见图3）。
实施例2
一种3D打印骨架@钨酸铋的光催器件的制备方法为按以下步骤进行：
（1）将ASA、浒苔真空干燥12h，称取干燥后的ASA(780g)、浒苔(218g)和白油(2g)，置于高速捏合机中，保持转速1000rpm，高速搅拌5min后投入到双螺杆挤出机，挤出温度设定为160℃、170℃、175℃、180℃、195℃、195℃、190℃、185℃、170℃、165℃，在双螺杆熔腔内熔融塑化并以转速为150rpm，挤出原料，将机头挤出的线条进入存有冷水的水槽，充分水冷冷却；线条进入牵引机收卷，得到3D打印线材。
（2）将上述线材，通过3D打印机（FDM）打印成体积为1cm3的二十四面螺旋体(图1)，3D打印机参数为：打印温度为190℃、底板温度为60 ℃、打印速度为50mm/s、打印层厚为0.2mm。
（3）将钨酸钠0.7g溶解于25mL去离子水为A液、硝酸铋1.6g溶解于15mL 5mol/L的醋酸溶液为B液，在20mol/min速率下将A液滴入B液，在20r/min速率搅拌下滴入NaOH溶液调节PH=2，搅拌下保持20min至反应完全。
（4）将步骤（2）得到的3D打印二十四面螺旋体小方块和步骤（3）中得到悬浮液的30mL同时加入50mL水热反应釜中，于120℃环境中密闭反应18h。反应后取出3D打印光催化器件，用去离子冲洗3次再用无水乙醇冲洗3次，最后在25℃下干燥24h。
实施例3
一种3D打印骨架@钨酸铋的光催器件的制备方法为按以下步骤进行：
（1）将PA、藻渣真空干燥12h，称取干燥后的PA(650g)、藻渣(347g)和白油(3g)，置于高速捏合机中，保持转速1000rpm，高速搅拌5min后投入到双螺杆挤出机，挤出温度设定为170℃、180℃、185℃、190℃、205℃、205℃、195℃、185℃、170℃、165℃，在双螺杆熔腔内熔融塑化并以转速为150rpm，挤出原料，将机头挤出的线条进入存有冷水的水槽，充分水冷冷却；线条进入牵引机收卷，得到3D打印线材。
（2）将上述线材，通过3D打印机（FDM）打印成体积为1cm3的二十四面螺旋体(图1)，3D打印机参数为：打印温度为195℃、底板温度为60 ℃、打印速度为50mm/s、打印层厚为0.1mm。
（3）将钨酸钠0.7g溶解于25mL去离子水为A液、硝酸铋1.6g溶解于15mL 5mol/L的醋酸溶液为B液，在20mol/min速率下将A液滴入B液，在20r/min速率搅拌下滴入NaOH溶液调节PH=2，搅拌下保持20min至反应完全。
（4）将步骤（2）得到的3D打印二十四面螺旋体小方块和步骤（3）中得到悬浮液的30mL同时加入50mL水热反应釜中，于120℃环境中密闭反应18h。反应后取出3D打印光催化器件，用去离子冲洗3次再用无水乙醇冲洗3次，最后在25℃下干燥24h。
实施例4
一种3D打印骨架@钨酸铋的光催器件的制备方法为按以下步骤进行：
（1）将PA、小球藻真空干燥12h，称取干燥后的PA(650g)、小球藻(347g)和白油(3g)，置于高速捏合机中，保持转速1000rpm，高速搅拌5min后投入到双螺杆挤出机，挤出温度设定为170℃、180℃、185℃、190℃、205℃、205℃、195℃、185℃、170℃、165℃，在双螺杆熔腔内熔融塑化并以转速为150rpm，挤出原料，将机头挤出的线条进入存有冷水的水槽，充分水冷冷却；线条进入牵引机收卷，得到3D打印线材。
（2）将上述线材，通过3D打印机（FDM）打印成体积为1cm3的二十四面螺旋体(图1)，3D打印机参数为：打印温度为195℃、底板温度为60 ℃、打印速度为50mm/s、打印层厚为0.1mm。
（3）将钨酸钾0.8g溶解于24mL去离子水为A液、硫酸铋2.0g溶解于15mL 5mol/L的醋酸溶液为B液，在20mol/min速率下将A液滴入B液，在25r/min速率搅拌下滴入NaOH溶液调节PH=3，搅拌下保持20min至反应完全。
（4）将步骤（2）得到的3D打印二十四面螺旋体小方块和步骤（3）中得到悬浮液的30mL同时加入50mL水热反应釜中，于120℃环境中密闭反应18h。反应后取出3D打印光催化器件，用去离子冲洗3次再用无水乙醇冲洗3次，最后在25℃下干燥24h。
实施例5
一种3D打印骨架@钨酸铋的光催器件的制备方法为按以下步骤进行：
（1）将POM、浒苔真空干燥12h，称取干燥后的ABS(700g)、浒苔(299.5g)和白油(0.5g)，置于高速捏合机中，保持转速1000rpm，高速搅拌5min后投入到双螺杆挤出机，挤出温度设定为160℃、170℃、1705℃、175℃、185℃、185℃、180℃、180℃、170℃、165℃，在双螺杆熔腔内熔融塑化并以转速为150rpm，挤出原料，将机头挤出的线条进入存有冷水的水槽，充分水冷冷却；线条进入牵引机收卷，得到3D打印线材。
（2）将上述线材，通过3D打印机（FDM）打印成体积为1cm3的二十四面螺旋体(图1)，3D打印机参数为：打印温度为185℃、底板温度为60 ℃、打印速度为50mm/s、打印层厚为0.1mm。
（3）将钨酸钠0.7g溶解于25mL去离子水为A液、硫酸铋2.0g溶解于15mL 5mol/L的草酸溶液为B液，在20mol/min速率下将A液滴入B液，在10-80r/min速率搅拌下滴入NaOH溶液调节PH=2，搅拌下保持20min至反应完全。
（4）将步骤（2）得到的3D打印二十四面螺旋体小方块和步骤（3）中得到悬浮液的30mL同时加入50mL水热反应釜中，于120℃环境中密闭反应18h。反应后取出3D打印光催化器件，用去离子冲洗3次再用无水乙醇冲洗3次，最后在25℃下干燥24h。
Claims (7)
1.一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，包括以下步骤：
(1)将基体树脂59-91份、生物质8-40份、白油0.05-2份置于高速捏合机中，保持转速1000-6000rpm，高速搅拌5-20min后投入到螺杆挤出机，加工温度160-255℃，螺杆转速80-280rpm，挤出造粒，得到母粒经线材机挤出、牵引、收卷成线材，得到皮芯结构3D打印线材，再用3D打印得到形状可控的3D打印骨架；
(2)将钨酸盐溶解于去离子水为A液、铋盐溶解于有机酸为B液，将A液滴入B液，在10-80r/min速率搅拌下滴入碱溶液调节PH=2-4，搅拌下保持20-60min至反应完全；
(3)将步骤(1)中得到的3D打印骨架和步骤(2)中得到的悬浮液同时加入水热反应釜中，于100～200℃环境中密闭反应10～24h；反应结束后，进行冲洗、干燥，得到3D打印骨架@钨酸铋的光催器件。
2.根据权利要求1所述的一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，所述步骤(1)中的基体树脂，选自ABS、ASA、PPS、POM、PC、PEEK、PA中的一种或几种。
3.根据权利要求1所述的一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，所述步骤(1)中的生物质，选自小球藻、浒苔、螺旋藻、藻渣中的一种或几种。
4.根据权利要求1所述的一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，所述步骤(1)中基体树脂和生物质分别真空干燥8-12h。
5.根据权利要求1所述的一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，步骤(1)中3D打印条件为：打印温度为180-250℃、底板温度为50-100 ℃、打印速度为20-150mm/s、打印层厚为0.1-0.4mm。
6.根据权利要求1所述的一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，步骤(2)中Bi2WO6的水热法合成中的钨酸盐、铋盐、有机酸、水的质量比为：0.5:1.5:4.5:25；所述步骤(2)中钨酸盐为：钨酸钠、钨酸钾中的一种；所述步骤(2)有机酸为：醋酸、草酸、柠檬酸中的一种；所述步骤(2)中碱溶液的滴入速率为：10-20mL/min以调节PH=2-4。
7.根据权利要求1所述的一种3D打印骨架@钨酸铋的光催器件的制备方法，其特征在于，步骤(3)中步骤(1)中得到的3D打印骨架与步骤(2)中得到的悬浮液体积比为：0.01-0.05:1。
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| CN109174203A (zh) * | 2018-07-09 | 2019-01-11 | 福建师范大学 | 一种具有光催化功能的皮芯结构3d打印线材及其制备方法 |
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| CN102489298A (zh) * | 2011-12-15 | 2012-06-13 | 江南大学 | 一种贵金属负载型Bi2WO6可见光催化剂的制备方法 |
| KR20160135633A (ko) * | 2015-05-18 | 2016-11-28 | (주)비앤케이 | 유해물질 저감용 3d 프린터 필라멘트 조성물 및 그 제조 방법 |
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