CN110240484B - 一种3d打印高比表面积高效率催化剂-载体体系的方法 - Google Patents

一种3d打印高比表面积高效率催化剂-载体体系的方法 Download PDF

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CN110240484B
CN110240484B CN201910526259.2A CN201910526259A CN110240484B CN 110240484 B CN110240484 B CN 110240484B CN 201910526259 A CN201910526259 A CN 201910526259A CN 110240484 B CN110240484 B CN 110240484B
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ceramic
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oxide
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CN110240484A (zh
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梅辉
黄伟钊
成来飞
张立同
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Northwestern Polytechnical University
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Abstract

本发明涉及一种3D打印高比表面积高效率催化剂‑载体体系的方法，陶瓷粉末或前驱体单独研磨后分散到光固化树脂的工艺有效避免了混合球磨过程中因碰撞产生的局部高温和部分变性；打印机参数的设定对所配置浆料具有选择性，决定了每层打印厚度适中，有利于快速成型；陶瓷载体预制件的二段保温工艺保证了交联固化及裂解成型时间，避免了煅烧后结构变形。本发明制备的陶瓷载体由于其高稳定性，可适用于不同合成方法搭载催化剂，对催化剂的作用环境无苛刻要求，为结构‑功能一体化的催化剂大规模工业应用提供了新的思路。

Description

一种3D打印高比表面积高效率催化剂-载体体系的方法
技术领域
本发明属于增材制造技术领域，涉及一种3D打印高比表面积高效率催化剂-载体体系的方法，特别涉及三维结构设计、催化剂载体打印制备、催化剂合成到载体表面，从而制备具有高比表面积、高催化效率和高稳定性的催化剂-载体材料体系的方法。
背景技术
新型催化剂体系的开发以及催化剂结构与性能之间的关系受到关注，具有精细宏观、微观结构的功能材料通过化学气相沉积等复杂的方法制备，阻碍了催化材料潜在的大规模工业应用，需要更简单和更灵活的方法制备专门的3D功能结构。陶瓷材料由于其耐高温、抗氧化、高强度、耐腐蚀等特点是理想的载体结构材料，但难以加工和成型复杂。高温烧结后留下丰富的孔可为催化剂提供大量的附着位点，增大与催化物质的接触面积，进而提高催化效率，这对陶瓷材料作为催化剂载体是有利的。3D打印技术可设计和精确控制催化剂载体多样化的结构，避免了传统制备方法所需的复杂制造工艺；打印催化剂的成本降低到合理的范围，以相对较低的成本实现精细结构的制备。通过增材制造来制备催化剂-载体材料体系将是合理可行的，这对催化剂的工业应用至关重要。
文献“Mei等A novel approach to strengthen naturally pored wood forhighly efficient photodegradation[J].Carbon,2018,139:378-385.”公开了一种生物形态多孔碳材料载体的制备方法，通过在惰性气氛下高温裂解获得连续有序的微通道结构，再通过水热法将光催化剂二硫化钼搭载到多孔载体表面，所制备的催化剂-载体复合体系的光降解效率由51％提高到98％，但该方法严重依赖载体的生物微形态，结构不可控。中国发明专利CN 107297204 A公开了一种碳纤维布/毡表面生长氧化钛纳米颗粒的制备方法，通过溶胶凝胶法和薄膜诱导法先后在碳纤维表面生成二氧化钛薄膜和纳米棒，制备得到二氧化钛催化网用于空气有机污染物降解。中国发明专利CN 108976734 A公开了一种聚乳酸3D打印线材的制备方法，通过聚乳酸树脂与无机矿物粉体及其他添加剂挤出造粒制备母体，线材生产线螺杆挤出机制备挤出定型收卷，获得了具有可见光光催化性能的线材。制备过程决定了大量的催化剂被包覆在线材内部无法参与光催化反应，光催化性能提高有限无法实现大规模应用。
中国发明专利CN 108724428 A公开了一种3D打印汽车用堇青石蜂窝陶瓷载体的方法，通过选择性激光烧结工艺打印陶瓷粉末与低温强化剂的混合物，再经浸渗高温粘结剂、脱除低温强化剂等工艺步骤获得汽车用蜂窝陶瓷。该方法仅要求单一蜂窝陶瓷结构，前处理及后处理工艺复杂，选择性激光烧结工艺容易造成内应力过大，不适用于大型载体结构的快速制备。中国发明专利CN 106891007 A公开了一种通孔结构金属材料的制备方法，通过金属粉末原料铺粉控制成型厚度，通过控制截面形状选择性粘结，紫外线扫描后产生光固化，通过热处理、脱脂和烧结获得多孔材料制件。中国发明专利CN 109095912 A提出根据通孔的基本参数以及排列方式与堇青石多孔蜂窝陶瓷载体的物理参数间关系，利用规则或不规则几何形状以及常规平行或异性交叉通孔设计多孔陶瓷载体微观结构，通过3D打印技术实现多孔蜂窝状陶瓷件一体化设计与快速制造。上述专利在制备多孔陶瓷/金属结构方面进行了尝试，但不具备作为载体材料的轻量化、结构可控和高比表面积，无法控制载体材料的微观形貌和孔结构，宏观结构仅限于通孔且未要求设计原则和载体与催化剂的关联，对催化剂效率和稳定性提高有限。
催化剂与载体复合后的材料体系具有显著提高的化学稳定性、热稳定性和机械稳定性，通过搭载到高比表面积载体表面可与反应物充分接触进而提高催化效率。因而本发明旨在实现一种适用于3D打印技术、微结构可调控、具备高比表面积、可显著提高催化剂效率和稳定性的轻质催化剂-载体材料体系的制备。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种3D打印高比表面积高效率催化剂-载体体系的方法，将催化剂与轻质高比表面积3D打印载体复合，构建催化剂-载体材料体系，实现高性能催化剂的大规模工业化应用。
技术方案
一种3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于步骤如下：
步骤1：将陶瓷粉末或陶瓷前驱体、光引发剂、表面活性剂、烧结助剂和造孔剂通过球磨机混合48-72h，以5-10g/min的速率缓慢加入到转速为60-180r/min磁力搅拌机搅拌的树脂中，待所有粉末完全加入后持续搅拌5-10h均匀混合，得到适用于3D 打印的陶瓷浆料；
所述各组份的重量百分数为：20-70％的陶瓷粉末或陶瓷前驱体、30-70％的光固化树脂；0.5-5％的光引发剂、0.5-5％的表面活性剂、5-10％的烧结助剂和5-20％的造孔剂；各种材料百分比之和为100％；
步骤2：将陶瓷浆料置入3D打印机，3D打印机根据打印数据进行打印陶瓷载体预制件，打印参数：高层曝光时间为2000-10000ms，高层静止时间为2000-8000ms，底层曝光时间为20000-60000ms，底层静止时间为0-50000ms，光照电流强度为6-18 A，分离速度为40-60mm/min；
步骤3：将陶瓷载体预制件置于管式炉中进行高温烧结；烧结气氛为活性气体或惰性气体，高温烧结的升温速率为0.5-2℃/min，采用两段升温和两段保温，然后在 1250-1500℃下烧结完成；
烧结完成后在60-100℃水浴中4-8h去除杂质，制备得到具有高比表面积的陶瓷载体；
所述两段升温和两段保温是：第一段：升温至100-200℃，保温60-120min；第二段：升温至500-600℃，保温60-120min；
步骤4：以陶瓷载体为基底，将催化剂合成在载体表面，制备催化剂-载体复合体系；所述催化剂搭载合成方法包括但不限于：水热法、溶剂热法、凝胶溶胶法、自组装法、化学气相沉积法、微乳液法、溶胶热法、模板辅助溶剂法或浸渍法。
所述陶瓷粉末为氧化物陶瓷、非氧化物陶瓷或氧化物陶瓷和非氧化物陶瓷的混合物。所述氧化物陶瓷包括但不限于：氧化铝或氧化锆；所述非氧化物陶瓷包括但不限于：碳化硅、硼化钛或氮化硅；所述陶瓷前驱体包括但不限于：甲基有机硅树脂、聚碳硅烷、聚硅氧烷、硅硼碳氮或聚碳硅烷。
所述光引发剂为：裂解型引发剂、光敏引发剂或阳离子光引发剂；所述裂解型引发剂包括但不限于：三甲基苯甲酰基-二苯基氧化膦或2-异丙基硫杂蒽酮。
所述表面活性剂包括但不限于：Triton X-100、单十二烷基磷酸酯钾或醇醚磷酸酯。
所述烧结助剂包括但不限于：氧化钇、氧化镁或氧化硅。
所述造孔剂为：水溶性试剂、有机物试剂或可裂解发泡剂。
所述水溶性试剂包括但不限于：氯化钠或氯化钙。
所述有机物试剂包括但不限于：葡萄糖或聚乙烯醇。
所述可裂解发泡剂包括但不限于：碳酸氢钠或碳酸氢铵。
所述打印数据是：利用切片软件对几何图案阵列结构的载体三维模型进行切片，切片厚度为25-100μm，添加底板层数2-5层，获得切片数据并导入3D打印机。
有益效果
本发明提出的一种3D打印高比表面积高效率催化剂-载体体系的方法，陶瓷粉末或前驱体单独研磨后分散到光固化树脂的工艺有效避免了混合球磨过程中因碰撞产生的局部高温和部分变性；打印机参数的设定对所配置浆料具有选择性，决定了每层打印厚度适中，有利于快速成型；陶瓷载体预制件的二段保温工艺保证了交联固化及裂解成型时间，避免了煅烧后结构变形。本发明制备的陶瓷载体由于其高稳定性，可适用于不同合成方法搭载催化剂，对催化剂的作用环境无苛刻要求，为结构-功能一体化的催化剂大规模工业应用提供了新的思路。
本发明提高催化剂效率和稳定性的方法简单可行，复合催化剂高效转化与载体高化学、热及机械稳定性的优点，赋予了催化剂材料可回收再使用性能。本发明制备催化剂-载体体系相比其他方法具有更高的比表面积，通过三维软件可定制适用于不同合成条件和服役环境的复杂结构，无需对载体进行复杂的前处理及后处理，微观形貌和孔结构简单可控。
附图说明
图1：发明实施过程流程示意图
图2：实施例一中设计三维结构：底板为10*10*0.8mm3正方形薄片，设计的几何阵列单元边长0.8mm、深度0.8mm的正方形孔，相邻孔间壁厚为0.2mm
图3：实施例二中设计三维结构：底板为10*10*0.6mm3正方形薄片，设计的几何阵列单元为底面边长为0.8mm、顶面边长为0.4mm、高为1mm的正四棱台，相邻棱台底面正方形间的距离为0.2mm
图4：实施例三中设计三维结构：底板为10*10*0.8mm3正方形薄片，设计的几何阵列单元为底面直径为0.8mm、顶面直径为0.4mm、高为0.8mm的圆台形通孔，相邻通孔底面圆心间的距离为1mm。
图5：a，3D打印载体；b，MoS2搭载到陶瓷载体后微观形貌
具体实施方式
现结合实施例、附图对本发明作进一步描述：
实施例一：
通过SolidWorks软件设计载体结构，底板为10*10*0.8mm3正方形薄片，设计的几何阵列单元边长0.8mm、深度0.8mm的正方形孔，相邻孔间壁厚为0.2mm，如图 2所示。通过3D打印机制造商绑定软件进行切片，切片厚度为50μm，添加底板层数 3层，并导入3D打印机。称量氧化铝粉末50wt.％、三甲基苯甲酰基-二苯基氧化膦1 wt.％、Triton X-100 1wt.％、氧化镁2wt.％、氧化硅2wt.％和氯化钠16wt.％，通过球磨机混合48h。将得到的粉末以5g/min的速率加入以120r/min搅拌的30wt.％光固化树脂中，持续搅拌8h得到陶瓷浆料。设置3D打印机参数为高层曝光时间6000ms、高层静止时间3000ms、底层曝光时间30000ms、底层静止时间8000ms、光照电流强度6A、分离速度48mm/min。将打印得到的载体预制件在氮气中以1℃/min升温至 1400℃，并在150℃和300℃各保温60min。将烧结后的载体于80℃水浴8h并干燥。通过溶胶凝胶法、水热法或溶剂热法分别在陶瓷载体表面合成MoS2等光催化剂。
实施例二：
通过SolidWorks软件设计载体结构，底板为10*10*0.6mm3正方形薄片，设计的几何阵列单元为底面边长为0.8mm、顶面边长为0.4mm、高为1mm的正四棱台，相邻棱台底面正方形间的距离为0.2mm，如图3所示。通过3D打印机制造商绑定软件进行切片，切片厚度为50μm，添加底板层数3层，并导入3D打印机。称量氧化锆粉末40wt.％、三甲基苯甲酰基-二苯基氧化膦2wt.％、Triton X-100 2wt.％、氧化镁2wt.％、氧化硅2wt.％和聚乙烯醇12wt.％，通过球磨机混合72h。将得到的粉末以5g/min的速率加入以180r/min搅拌的40wt.％光固化树脂中，持续搅拌10h得到陶瓷浆料。设置3D打印机参数为高层曝光时间8000ms、高层静止时间6000ms、底层曝光时间 60000ms、底层静止时间50000ms、光照电流强度12A、分离速度55mm/min。将打印得到的载体预制件在空气中以1℃/min升温至1400℃，并在150℃和300℃各保温60min。通过化学气相沉积法或自组装法分别在陶瓷载体表面合成BiOI等热催化剂。
实施例三：
通过SolidWorks软件设计载体结构，底板为10*10*0.8mm3正方形薄片，设计的几何阵列单元为底面直径为0.8mm、顶面直径为0.4mm、高为0.8mm的圆台形通孔，相邻通孔底面圆心间的距离为1mm，如图4所示。通过3D打印机制造商绑定软件进行切片，切片厚度为50μm，添加底板层数3层，并导入3D打印机。称量三甲基苯甲酰基-二苯基氧化膦2wt.％、Triton X-100 1wt.％、氧化镁2wt.％、氧化硅2wt.％和碳酸氢钠8wt.％，通过球磨机混合48h。将得到的粉末以5g/min的速率加入以120r/min 搅拌的55wt.％液态聚碳硅烷和30wt.％光固化树脂中，持续搅拌8h得到陶瓷浆料。设置3D打印机参数为高层曝光时间6000ms、高层静止时间3000ms、底层曝光时间 10000ms、底层静止时间1000ms、光照电流强度10A、分离速度50mm/min。将打印得到的载体预制件在氮气中以1℃/min升温至1400℃，并在300℃保温120min。通过微乳液法、溶胶热法或模板辅助溶剂法在陶瓷载体表面合成TiO2等电催化剂。

Claims (6)

1.一种3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于步骤如下：
步骤1：将陶瓷粉末或陶瓷前驱体、光引发剂、表面活性剂、烧结助剂和造孔剂通过球磨机混合48-72h，以5-10g/min的速率缓慢加入到转速为60-180r/min磁力搅拌机搅拌的树脂中，待所有粉末完全加入后持续搅拌5-10h均匀混合，得到适用于3D打印的陶瓷浆料；
各组份的重量百分数为：20-70％的陶瓷粉末或陶瓷前驱体、30-70％的光固化树脂；0.5-5％的光引发剂、0.5-5％的表面活性剂、5-10％的烧结助剂和5-20％的造孔剂；各种材料百分比之和为100％；
步骤2：将陶瓷浆料置入3D打印机，3D打印机根据打印数据进行打印陶瓷载体预制件，打印参数：高层曝光时间为2000-10000ms，高层静止时间为2000-8000ms，底层曝光时间为20000-60000ms，底层静止时间为0-50000ms，光照电流强度为6-18A，分离速度为40-60mm/min；
步骤3：将陶瓷载体预制件置于管式炉中进行高温烧结；烧结气氛为活性气体或惰性气体，高温烧结的升温速率为0.5-2℃/min，采用两段升温和两段保温，然后在1250-1500℃下烧结完成；
烧结完成后在60-100℃水浴中4-8h去除杂质，制备得到具有高比表面积的陶瓷载体；
所述两段升温和两段保温是：第一段：升温至100-200℃，保温60-120min；第二段：升温至500-600℃，保温60-120min；
步骤4：以陶瓷载体为基底，将催化剂合成在载体表面，制备催化剂-载体复合体系；所述催化剂搭载合成方法包括：溶剂热法、凝胶溶胶法、自组装法、化学气相沉积法、微乳液法、溶胶热法、模板辅助溶剂法或浸渍法；
所述陶瓷粉末为氧化物陶瓷、非氧化物陶瓷或氧化物陶瓷和非氧化物陶瓷的混合物；所述氧化物陶瓷包括：氧化铝或氧化锆；所述非氧化物陶瓷包括：碳化硅、硼化钛或氮化硅；所述陶瓷前驱体包括：甲基有机硅树脂、聚碳硅烷、聚硅氧烷、硅硼碳氮或聚碳硅烷。
2.根据权利要求1所述3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于：所述光引发剂为：裂解型引发剂、光敏引发剂或阳离子光引发剂；所述裂解型引发剂包括：三甲基苯甲酰基-二苯基氧化膦或2-异丙基硫杂蒽酮。
3.根据权利要求1所述3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于：所述表面活性剂包括：Triton X-100、单十二烷基磷酸酯钾或醇醚磷酸酯。
4.根据权利要求1所述3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于：所述烧结助剂包括：氧化钇、氧化镁或氧化硅。
5.根据权利要求1所述3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于：所述造孔剂为：水溶性试剂、有机物试剂或可裂解发泡剂；所述水溶性试剂包括：氯化钠或氯化钙；所述有机物试剂包括：葡萄糖或聚乙烯醇；所述可裂解发泡剂包括：碳酸氢钠或碳酸氢铵。
6.根据权利要求1所述3D打印高比表面积高效率催化剂-载体体系的方法，其特征在于：所述打印数据是：利用切片软件对几何图案阵列结构的载体三维模型进行切片，切片厚度为25-100μm，添加底板层数2-5层，获得切片数据并导入3D打印机。
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