CN111185152A - 一种多功能耦合的PAC/Bi2O3/TiO2复合材料制备方法 - Google Patents
一种多功能耦合的PAC/Bi2O3/TiO2复合材料制备方法 Download PDFInfo
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Abstract
一种多功能耦合的PAC/Bi2O3/TiO2复合材料制备方法，属水处理领域。将钛酸四丁酯和冰醋酸缓慢加入无水乙醇中得A液，五水硝酸铋充分溶于去离子水中得B液，B液逐滴加入A液后形成溶胶；溶胶中加入粉末活性炭浸渍5～8h；浸渍后的溶胶移入水热反应釜，水热反应12～18h后取出倒入蒸发舟，在烘箱干燥后研磨成粉末；粉末置于管式炉中，在空气氛围下300℃热处理2h，在氮气或氩气氛围下500℃～750℃热处理3h。本发明公开方法所制备的复合材料，能够有效减少PAC质量损耗，在可见光催化氧化持续降解污染物的同时，实现PAC动态的非饱和吸附与原位再生，同步完成污染物吸附、可见光催化氧化和原位再生的耦合作用。
Description
技术领域
本发明属水处理领域，涉及一种多功能耦合的PAC/Bi2O3/TiO2复合材料制备方法，制备的PAC/Bi2O3/TiO2复合材料具有吸附/可见光催化氧化/原位再生耦合功能。
背景技术
近年来，水环境污染问题日益突出，很多污染物难以采用常规净化技术得到有效去除。随着高新科技的进步和材料科学的发展，新型除污染技术和材料得到不断研发和应用。光催化氧化技术以及光催化半导体材料具有绿色节能、操作条件可控、反应条件温和、有机物氧化能力强等特点，得到了业界的高度关注，亟需开展深入研究和广泛应用。目前光催化氧化技术的研发和应用主要集中在光源效率的提高、催化剂的改良和回用等方面。
二氧化钛(TiO2)是一种高效的光催化氧化剂，具有无毒、光催化活性高、稳定性高等优点，已经得到深入研究和广泛应用，但仍存在仅能利用紫外光、降解反应速率低、易团聚和难以回收等问题。为了提高TiO2对可见光的利用率，可通过半导体掺杂方法拓展TiO2的吸光域。铋系半导体催化剂氧化铋(Bi2O3)具有较窄带隙(2.8eV)、高介电常数等优良特性，与TiO2复合后可形成具有可见光响应的异质结构复合材料Bi2O3/TiO2，能够有效抑制光生载流子的复合、改善光催化活性，但Bi2O3/TiO2复合材料在氧化和降解污染物过程中存在易结团、选择性氧化、反应速率低、不易分离回收、再利用难等问题。
现有的Bi2O3/TiO2制备方法中仍存在制备过程繁琐、药剂种类较多、可见光利用率不高等缺陷，难以获得高效、可靠、绿色、经济的光催化材料。为了提高光催化氧化剂的回收利用率，可将光催化氧化剂负载到多孔吸附载体上，以解决其易团聚、再利用难等问题。载体材料的选择和负载技术是影响复合材料的结构、性质和催化活性的关键性要素。目前对于TiO2负载催化剂的研究较多，如TiO2/石墨烯、TiO2/V2O5、TiO2/硅藻土等复合材料，这些复合材料仍集中于解决可见光响应问题，对光催化氧化剂的易团聚和再利用没有明显改善。在水处理工艺中广泛应用的粉末活性炭(PAC)具有发达的空隙结构和良好的吸附性能，但PAC存在易吸附饱和、需频繁更换、定期再生等问题，回用过程复杂、再生成本高等问题。
本发明提出将具有光催化作用的Bi2O3和TiO2材料耦合负载到PAC上，制备出PAC/Bi2O3/TiO2复合材料，构建出同时具有吸附、原位再生、可见光催化氧化功能的耦合作用体系，构建的多功能复合材料既能保证可见光催化氧化活性，又能使复合材料本身具有较强的吸附性能，同时将PAC吸附的污染物进行可见光催化氧化降解，实现PAC原位再生，同步完成污染物吸附、可见光催化氧化和原位再生的耦合作用。
复合材料的铋源、钛源和载体的选取以及制备工艺、制备过程、制备参数控制等条件是决定复合材料性能的关键性要素，需要根据PAC/Bi2O3/TiO2复合材料的应用需求进行测试、调配和改变，以制备出具有吸附功能与可见光催化氧化功能相协同的复合材料，以便适用于不同污染物浓度、不同吸附要求的应用环境。研究和开发高效可循环利用的耦合于粉末活性炭的氧化铋掺杂二氧化钛(PAC/Bi2O3/TiO2)复合材料，对光催化氧化技术的发展和水处理工艺的改进具有重要意义。
发明内容
本发明为一种多功能耦合的PAC/Bi2O3/TiO2复合材料制备方法，制备的PAC/Bi2O3/TiO2复合材料具有吸附/可见光催化氧化/原位再生耦合功能，采用溶胶-浸渍-水热-两级煅烧法，将Bi-Ti溶胶和PAC耦合同步煅烧，形成多功能复合材料PAC/Bi2O3/TiO2，使PAC吸附作用、Bi2O3/TiO2可见光催化氧化降解作用、PAC再生作用可以在复合材料上同步原位实现。
发明所采用的技术方案如下：
取一定量钛酸四丁酯和冰醋酸缓慢加入到无水乙醇中，在350～500rpm条件下磁力搅拌2h后得到A液；取一定量五水硝酸铋溶于去离子水中，经超声震荡和磁力搅拌至充分溶解后得到B液。将B液逐滴加入A液后形成溶胶。在溶胶中加入一定量经过筛选的粉末活性炭，在室温下磁力搅拌浸渍5～8h；将浸渍后的溶胶移入水热反应釜，在150～200℃下反应12～18h后取出倒入蒸发舟中，在120～130℃下在烘箱中干燥3～4h，取出后研磨成粉末。将粉末置于管式炉中，在空气氛围下以一定的升温速率从室温升温至300℃热处理2h，然后在氮气或氩气氛围下以一定的升温速率升温至500℃～750℃热处理3h后冷却至室温。
本发明中所述Bi与Ti摩尔比为6％～14％，粉末活性炭、五水硝酸铋与钛酸四丁酯的质量比约为(1～1.5):(2.1～4.9):24.7，冰醋酸与无水乙醇摩尔比为1:6～1:9；每2-3mL钛酸四丁酯对应1mL冰醋酸，每1g五水硝酸铋对应约50mL水；所述筛选的粉末活性炭种类包括木质活性炭、椰壳活性炭、煤质活性炭等中的一种或几种，粒径范围在50～150μm；所述的以一定的升温速率为5-20℃/min。
本发明所得的多功能耦合的PAC/Bi2O3/TiO2复合材料作为光催化剂的应用，用于可见光催化降解吸附有机污染物，具有吸附/可见光催化氧化/原位再生多功能耦合作用，同时具有较好的循环应用性。
本发明的优点
与现有的催化材料相比，本发明具有如下优点：
(1)该复合材料在可见光催化氧化持续降解污染物的同时，可实现PAC动态的非饱和吸附与原位再生过程，确保该复合材料的连续吸附/再生、高效降解和循环利用；
(2)该复合材料在可见光波段响应能力比TiO2显著增强并可保持稳定，能够高效利用可见光催化氧化降解污染物，大幅度提高可见光催化效率和性能；
(3)该复合材料通过PAC的吸附和富集作用为Bi2O3/TiO2提供更高的污染物浓度，可加快光催化氧化反应速率；
(4)该复合材料同时具有TiO2的锐钛矿和金红石晶相，晶相一定比例掺杂有利于提高光催化效率，二级煅烧技术使金属晶体成型的同时降低了PAC在制备过程中的质量损耗，有效保障了复合材料的吸附功能。
附图说明
图1为PAC/Bi2O3/TiO2复合材料的紫外-可见漫反射光谱；
图2为PAC/Bi2O3/TiO2复合材料的扫描电镜图像；
图3为PAC/Bi2O3/TiO2复合材料的X射线衍射图谱。
具体实施方式
通过以下实例对本发明作详细说明，但本发明并不限于以下实施例。
实施例1：取16mL钛酸四丁酯和6mL冰醋酸缓慢加入到50mL无水乙醇中，在500rpm磁力搅拌2h，得到A液；称取2.2256g五水硝酸铋溶于100mL去离子水中，经超声和磁力搅拌后得到B液；将B液逐滴加入A液后形成溶胶，再加入0.6gPAC，在室温下磁力搅拌和浸渍6h后，将浸渍后的溶胶移入水热反应釜，在150℃下烘箱中反应12h后取出溶胶倒入蒸发舟中，再移入130℃的烘箱中干燥4h后取出碾成粉末，将粉末置于管式炉中，在空气氛围下以10℃/min的速率从室温升温至300℃热处理2h，然后在氮气氛围下以15℃/min的速率升温至700℃热处理3h，即可制得Bi/Ti摩尔比为10％、二级煅烧温度为300/700℃的PAC/Bi2O3/TiO2复合材料(10％-300/700℃-PAC/Bi2O3/TiO2)。
投加1g/L的10％-300/700℃的PAC/Bi2O3/TiO2复合材料在避光的黑暗条件下吸附20mg/L的磺胺甲嘧啶溶液，吸附30min后达到平衡，磺胺甲嘧啶的吸附去除率达到38.8％；继续在可见光下进行光催化氧化2h，光催化氧化过程结束时溶液中磺胺甲嘧啶去除率达到96.8％。将PAC/Bi2O3/TiO2复合材料进行过滤回收，并在70℃下干燥12h后，在相同条件下重复上述试验，去除率仍可达90.4％。
实施例2：取10mL钛酸四丁酯和5mL冰醋酸缓慢加入到40mL无水乙醇中，在500rpm磁力搅拌2h，得到A液；称取1.6692g五水硝酸铋溶于80mL去离子水中，经超声和磁力搅拌后得到B液；将B液逐滴加入A液后形成溶胶，再加入0.5gPAC，在室温下磁力搅拌和浸渍5h后，将浸渍后的溶胶移入水热反应釜，在150℃下烘箱中反应12h后取出溶胶倒入蒸发舟中，再移入130℃的烘箱中干燥4h后取出碾成粉末，将粉末置于管式炉中，在空气氛围下以10℃/min的速率从室温升温至300℃热处理2h，然后在氩气氛围下以10℃/min的速率升温至600℃热处理3h，即可制得Bi/Ti摩尔比为12％、二级煅烧温度为300/600℃的PAC/Bi2O3/TiO2复合材料。
投加1g/L的12％-300/600℃的PAC/Bi2O3/TiO2复合材料在避光的黑暗条件下吸附25mg/L的甲基橙溶液，吸附60min后达到平衡，甲基橙的吸附去除率达到47.5％；继续在可见光下进行光催化氧化2h，光催化氧化过程结束时溶液中甲基橙去除率达到97.4％。将PAC/Bi2O3/TiO2复合材料进行过滤回收，并在70℃下干燥12h后，在相同条件下重复上述试验，去除率仍可达92.3％。
Claims (6)
1.一种多功能耦合的PAC/Bi2O3/TiO2复合材料制备方法，制备的PAC/Bi2O3/TiO2复合材料具有吸附/可见光催化氧化/原位再生耦合功能，其特征在于，包括以下步骤：
取一定量钛酸四丁酯和冰醋酸缓慢加入到无水乙醇中，在350～500rpm条件下磁力搅拌2h后得到A液；取一定量五水硝酸铋溶于去离子水中，经超声震荡和磁力搅拌至充分溶解后得到B液。将B液逐滴加入A液后形成溶胶。在溶胶中加入一定量经过筛选的粉末活性炭，在室温下磁力搅拌浸渍5～8h；将浸渍后的溶胶移入水热反应釜，在150～200℃下反应12～18h后取出倒入蒸发舟中，在120～130℃下在烘箱中干燥3～4h，取出后研磨成粉末。将粉末置于管式炉中，在空气氛围下以一定的升温速率从室温升温至300℃热处理2h，然后在氮气或氩气氛围下以一定的升温速率升温至500℃～750℃热处理3h后冷却至室温。
2.按照权利要求1所述的方法，其特征在于，Bi与Ti摩尔比为6％～14％，粉末活性炭、五水硝酸铋与钛酸四丁酯的质量比约为(1～1.5):(2.1～4.9):24.7，冰醋酸与无水乙醇摩尔比为1:6～1:9；每2-3mL钛酸四丁酯对应1mL冰醋酸，每1g五水硝酸铋对应约50mL水。
3.按照权利要求1所述的方法，其特征在于，所述筛选的粉末活性炭种类包括木质活性炭、椰壳活性炭、煤质活性炭等中的一种或几种，粒径范围在50～150μm。
4.按照权利要求1所述的方法，其特征在于，所述的以一定的升温速率为5～20℃/min。
5.按照权利要求1-4任一项所述的方法制备得到的PAC/Bi2O3/TiO2复合材料。
6.按照权利要求1-4任一项所述的方法制备得到的PAC/Bi2O3/TiO2复合材料的应用，用于吸附/可见光催化降解有机污染物。
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