CN108554412A - 一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法及其应用 - Google Patents
一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法及其应用，属于材料制备技术领域。本发明先将可溶性高分子用蒸馏水溶解得到溶液A，然后将光催化剂与溶液A中混合后得到悬浊液B，再将饱和可溶性铁盐溶液与悬浊液B混合，后得到悬浊液C；用合适大小的注射器将悬浊液C逐滴滴加到高浓度碱液中生成微球颗粒，滴加完毕后，陈化、干燥，最后将微球在600～1100℃条件下煅烧，冷却后得到本发明的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球。本发明制得的多孔微球不仅能实现催化剂的高效回收，而且其多孔结构有利于大分子反应物在催化剂表面和体相间的扩散和传质，增强催化剂的降解活性，因此在光催化领域有广泛的应用前景。
Description
技术领域
本发明属于材料制备技术领域，具体涉及一种光催化材料的制备方法及其应用，更具地说，本发明涉及一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法及其应用。
背景技术
作为未来解决环境问题的一种重要手段，光催化技术是当前国内外化学与环境领域的研究热点。利用光催化技术不仅可降解和矿化水与空气中各种难降解的持久有毒有机污染物，还可以抗菌除臭以及处理废水中的Hg2+、Ag+、Cr6+等重金属离子。
多年来，国内外众多学者围绕着先进光催化材料的制备与改性开展了大量研究工作，并取得了较大进展。然而，目前光催化材料距离其商业化应用仍存在诸多障碍。一方面，较低的可见光利用率和较高的光生电子—空穴复合率导致催化剂的活性较差。研究表明，掺杂具有多能级结构的过渡金属元素能在材料中引入缺陷，使之成为光生电子—空穴的浅势捕获阱，降低光生电子—空穴的复合率，从而可以有效改善材料的催化性能。在众多过渡金属掺杂剂中，Fe被认为是掺杂效果最好的元素之一。作为在地壳中含量排名第二位的金属元素，Fe元素不仅廉价易得，其化合物通常无毒、无污染，是环境友好材料。以Fe掺杂TiO2光催化剂为例，由于Fe3+离子半径与Ti4+的离子半径非常接近，因此Fe3+可以较为顺畅的进入到晶格中形成捕获中心，可同时捕获光生电子与空穴。其中，Fe3+/Fe2+的电位位于TiO2导带之下，为被光子激发跃迁到导带的电子提供了传输路径；Fe4+/Fe3+的电位位于TiO2价带之上，易于吸引聚集在价带的空穴，从而有效抑制电子—空穴的复合。此外，Fe掺杂还可引入杂质能级，提高TiO2对可见光的响应能力。另一方面，纳米尺度的光催化剂虽然具有较多的表面活性位点，有助于改善其催化活性，然而，随着光催化材料向纳米尺度发展，传统的分离手段如离心、过滤等很难将其从反应体系中有效分离出来；目前，主要是通过构筑磁核结构并利用外加磁场实现催化剂纳米晶的快速回收。但这种方法的主要问题是磁核尺寸太小，磁性太弱，无法显著改善催化剂的回收效率。
发明内容
本发明针对背景技术中所指出的问题及现有技术存在的不足，目的在于提供一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法及其应用。采用本发明方法制得的大尺寸多孔微球不仅能实现催化剂的高效回收，而且其多孔结构有利于大分子反应物在催化剂表面和体相间的扩散和传质，可以为催化剂提供大的比表面积，使得催化剂拥有更多的反应活性位点，从而有效增强催化剂的降解活性，因此在光催化领域有广泛的应用前景。
为了实现本发明的上述的第一个目的，本发明采用如下技术方案：
本发明的一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，所述方法包含如下步骤：
首先，将可溶性高分子用蒸馏水溶解得到浓度为0.5wt％～1.5wt％的溶液A，然后将光催化剂加入到所述溶液A中，混合搅拌均匀后得到悬浊液B，再将饱和可溶性铁盐溶液与所述悬浊液B混合，搅拌均匀后得到悬浊液C；采用合适针头大小的注射器将所述悬浊液C逐滴滴加到高浓度碱液中生成微球颗粒，滴加完毕后，陈化、干燥，最后将干燥后的微球在600～1100℃条件下煅烧30～120min，冷却后即得到本发明所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球。
进一步地，上述技术方案中所述的可溶性高分子优选为田菁粉、羧甲基纤维素、瓜尔豆胶中的任一种。
进一步地，上述技术方案中所述的光催化剂优选为二氧化钛、镧钛酸钾、钛酸锶或氧化锌中的任一种。
进一步地，上述技术方案中所述悬浊液B的固含量为35wt％～65wt％。
进一步地，上述技术方案中所述的可溶性铁盐优选为氯化铁或硝酸铁中的任一种。
进一步地，上述技术方案所述的铁盐溶液中Fe3+离子与光催化剂的摩尔比优选为15～45：100。
进一步地，上述技术方案中所述的碱液优选为浓氨水、尿素饱和溶液、六次甲基四胺饱和溶液中的任一种。
进一步地，上述技术方案中所述陈化时间优选为30～120min，干燥温度优选为60～80℃。
上述所述的注射器针头大小可根据成球颗粒大小进行选择调整。
本发明的另一目的在于提供采用上述方法制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的应用，所述光催化磁性多孔微球可用于催化降解有机染料。
进一步地，上述技术方案中所述的有机染料优选为亚甲基蓝染料。
本发明的原理在于：一方面，基于表面张力原理，悬浊液C中的可溶性高分子使液滴在碱液中形成球状；另一方面，该球状液滴表面的Fe3+与碱液中的OH-迅速发生沉淀反应，从而使球状液滴表面迅速固化，一定时间陈化后完全固化。此外，在高温煅烧过程中，可溶性高分子热分解形成还原性气氛，使部分Fe3+还原成Fe2+获得磁性Fe3O4。
与现有技术相比，本发明的制备方法具有如下有益效果：
(1)本发明的制备方法，能够一步法同时实现光催化剂微球的掺杂与磁性制备，其原位生成的Fe3O4不仅可以使催化剂在外磁场的作用下得到高效回收，而且Fe掺杂能进一步改善催化剂的催化性能。该方法工艺简单，无需气氛保护，重现性好，不仅价格低廉、环境友好，且能得到多种粒径范围的磁性微球；
(2)本发明制得的大尺寸多孔微球不仅能实现催化剂的高效回收，而且其多孔结构有利于大分子反应物在催化剂表面和体相间的扩散和传质，可以为催化剂提供大的比表面积，使得催化剂拥有更多的反应活性位点，从而有效增强催化剂的降解活性，因此在光催化领域有广泛的应用前景。
附图说明
图1为本发明所述大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备工艺流程图；
图2为本发明所述大尺寸高孔隙率Fe掺杂光催化磁性多孔微球制备工艺中涉及的具体滴定成球过程示意图；
图3为本发明实施例1制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的扫描电镜图片；
图4为本发明实施例1制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的XRD图谱；
图5为本发明实施例1制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球首次用于催化降解亚甲基蓝染料时的降解率随时间的变化曲线图；
图6为本发明实施例1制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球多次重复用于催化降解亚甲基蓝染料的降解率对比图；
具体实施方式
下面对本发明的实施案例作详细说明。本实施案例在本发明技术方案的前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施案例。
根据本申请包含的信息，对于本领域技术人员来说可以轻而易举地对本发明的精确描述进行各种改变，而不会偏离所附权利要求的精神和范围。应该理解，本发明的范围不局限于所限定的过程、性质或组分，因为这些实施方案以及其他的描述仅仅是为了示意性说明本发明的特定方面。实际上，本领域或相关领域的技术人员明显能够对本发明实施方式作出的各种改变都涵盖在所附权利要求的范围内。
为了更好地理解本发明而不是限制本发明的范围，在本申请中所用的表示用量、百分比的所有数字、以及其他数值，在所有情况下都应理解为以词语“大约”所修饰。因此，除非特别说明，否则在说明书和所附权利要求书中所列出的数字参数都是近似值，其可能会根据试图获得的理想性质的不同而加以改变。各个数字参数至少应被看作是根据所报告的有效数字和通过常规的四舍五入方法而获得的。
实施例1
本实施例的一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，所述方法包含如下步骤：
(1)称取0.5g田菁粉溶于100mL蒸馏水中，得到浓度为0.5wt％的溶液A；
(2)称取35g(0.438mol)二氧化钛(分子式为TiO2，分子量为79.87)光催化剂(简称：P-25)加入到溶液A中，混合搅拌均匀后得到悬浊液B，所述悬浊液B的固含量为35wt％；
(3)取11.5mL的FeCl3饱和溶液(其中：FeCl3饱和溶液浓度为92g/100mL)与步骤(2)所述悬浊液B混合，搅拌均匀后得到悬浊液C，所述Fe3+离子与二氧化钛的摩尔比为15：100；
(4)采用6号针头大小的注射器将悬浊液C逐滴滴入浓氨水中生成微球颗粒，滴加完毕后，陈化60min，再在80℃条件下干燥；
(5)将步骤(4)干燥后的微球在600℃下煅烧120min，制得Fe掺杂二氧化钛光催化磁性多孔微球。
将本实施例上述制得的磁性多孔微球的扫描电镜(SEM)照片如图3所示，所述磁性多孔微球的XRD测试结果如图4所示。由图3可以看出，本实施例上述制得的磁性多孔微球的平均粒径为650μm、孔隙率高达82％。由图4可以看出，样品的晶相主要为光催化剂P-25和磁性Fe3O4。
应用实施例1
将实施例1制得的Fe掺杂二氧化钛光催化磁性多孔微球用于催化降解有机染料，有机染料选择亚甲基蓝，光催化性能测试方法如下：取50mg/L的亚甲基蓝溶液100mL置于烧杯中，加入50mg实施例1制得的多孔微球并在未开汞灯的反应仪箱体中搅拌30min以达到吸附-脱附平衡；然后打开汞灯(500W)光源照射溶液，取样测量时间为每10min一次，经离心分离后汲取上层清液；利用紫外-可见光分光光度计测量光催化反应后亚甲基蓝溶液在664nm(最大吸收波长)处的吸光度，最后根据获得的数据计算亚甲基蓝溶液在各个时间点的浓度，将上述使用过的光催化剂重新收集，经烘干后再次进行光催化性能测试，反复进行6次并获取其降解数据。
图5为上述实施例1制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球首次用于催化降解亚甲基蓝染料时的降解率随时间的变化曲线图，由图5的光催化性能测试结果可以看出，实施例1制得的磁性多孔微球光催化降解亚甲基蓝40min的降解率可达93.1％。
将本发明实施例1制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球用于重复催化降解亚甲基蓝染料，共重复使用6次，每次降解30min时的降解率对比图如图6所示，由图6重复使用后的降解性能测试数据可以看出，经6次循环使用后，磁性多孔微球的催化性能无显著变化。
实施例2
本实施例的一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，所述方法包含如下步骤：
(1)称取1.5g羧甲基纤维素溶于100mL蒸馏水中，得到浓度为1.5wt％的溶液A；
(2)称取65g(0.1mol)镧钛酸钾(分子式：K2La2Ti3O10，分子量为659.5)光催化剂加入到溶液A中，混合搅拌均匀后得到悬浊液B，所述悬浊液B的固含量为65wt％；
(3)取8mL的FeCl3饱和溶液(其中：FeCl3饱和溶液浓度为92g/100mL)与步骤(2)所述悬浊液B混合，搅拌均匀后得到悬浊液C，所述Fe3+离子与镧钛酸钾的摩尔比为45：100；
(4)采用4号针头大小的注射器将悬浊液C逐滴滴入尿素饱和溶液中生成微球颗粒，滴加完毕后，陈化90min，再在60℃条件下干燥；
(5)将步骤(4)干燥后的微球在1100℃下煅烧90min，制得Fe掺杂镧钛酸钾光催化磁性多孔微球。
将本实施例上述制得的磁性多孔微球进行测试，测试结果表明，本实施例制得的磁性多孔微球的平均粒径为430μm、孔隙率高达75％。
采用应用实施例1相同的测试方法进行光催化性能测试，结果表明，本实施例制得的Fe掺杂镧钛酸钾光催化磁性多孔微球首次用于降解亚甲基蓝时，在降解40min时的降解率可达94.6％。经6次循环使用后，样品的催化性能无显著变化。
实施例3
本实施例的一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，所述方法包含如下步骤：
(1)称取0.5g瓜尔豆胶溶于100mL蒸馏水中，得到浓度为0.5wt％的溶液A；
(2)称取65g(0.354mol)钛酸锶(分子式：SrTiO3，分子量为183.46)光催化剂加入到溶液A中，混合搅拌均匀后得到悬浊液B，所述悬浊液B的固含量为65wt％；
(3)取9.5mL的Fe(NO3)3饱和溶液(其中：Fe(NO3)3饱和溶液浓度为138g/100mL)与步骤(2)所述悬浊液B混合，搅拌均匀后得到悬浊液C，所述Fe3+离子与钛酸锶的摩尔比为15：100；
(4)采用6号针头大小的注射器将悬浊液C逐滴滴入浓氨水中生成微球颗粒，滴加完毕后，陈化120min，再在60℃条件下干燥；
(5)将步骤(4)干燥后的微球在1000℃下煅烧120min，制得Fe掺杂镧钛酸钾光催化磁性多孔微球。
将本实施例上述制得的磁性多孔微球进行测试，测试结果表明，本实施例制得的磁性多孔微球的平均粒径为680μm、孔隙率高达76％。
采用应用实施例1相同的测试方法进行光催化性能测试，结果表明，将本实施例Fe掺杂钛酸锶光催化磁性多孔微球首次用于降解亚甲基蓝时，在降解40min时的降解率可达92.8％。经6次循环使用后，样品的催化性能无显著变化。
实施例4
本实施例的一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，所述方法包含如下步骤：
(1)称取1.0g瓜尔豆胶溶于100mL蒸馏水中，得到浓度为1.0wt％的溶液A；
(2)称取50g(0.973mol)氧化锌光催化剂(分子式为ZnO，分子量为81.38)光催化剂加入到溶液A中，混合搅拌均匀后得到悬浊液B，所述悬浊液B的固含量为50wt％；
(3)取34mL的Fe(NO3)3饱和溶液(其中：Fe(NO3)3饱和溶液浓度为138g/100mL)与步骤(2)所述悬浊液B混合，搅拌均匀后得到悬浊液C，所述Fe3+离子与氧化锌的摩尔比为20：100；
(4)采用4号针头大小的注射器将悬浊液C逐滴滴入浓氨水中生成微球颗粒，滴加完毕后，陈化30min，再在80℃条件下干燥；
(5)将步骤(4)干燥后的微球在1050℃下煅烧90min，制得Fe掺杂氧化锌光催化磁性多孔微球。
将本实施例上述制得的磁性多孔微球进行测试，测试结果表明，本实施例制得的磁性多孔微球的平均粒径为480μm、孔隙率高达84％。
采用应用实施例1相同的测试方法进行光催化性能测试，结果表明，将本实施例的Fe掺杂氧化锌光催化磁性多孔微球首次用于降解亚甲基蓝，在降解40min时的降解率可达89.6％。经6次循环使用后，样品的催化性能无显著变化。
实施例5
本实施例的一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，所述方法包含如下步骤：
(1)称取1.2g田菁粉溶于100ml蒸馏水中，得到浓度为1.2wt％的溶液A；
(2)称取40g(0.5mol)二氧化钛(分子式为TiO2，分子量为79.87)光催化剂(简称：P25)加入到溶液A中，混合搅拌均匀后得到悬浊液B，所述悬浊液B的固含量为40wt％；
(3)取26.5mL的FeCl3饱和溶液(其中：FeCl3饱和溶液浓度为92g/100ml)与步骤(2)所述悬浊液B混合，搅拌均匀后得到悬浊液C，所述Fe3+离子与二氧化钛的摩尔比为30：100；
(4)采用4号针头大小的注射器将悬浊液C逐滴滴入六次甲基四胺饱和溶液中生成微球颗粒，滴加完毕后，陈化60min，再在70℃条件下干燥；
(5)将步骤(4)干燥后的微球在600℃下煅烧120min，制得Fe掺杂二氧化钛光催化磁性多孔微球。
将本实施例上述制得的磁性多孔微球进行测试，测试结果表明，本实施例制得的磁性多孔微球的平均粒径为540μm、孔隙率高达81％。
采用应用实施例1相同的测试方法进行光催化性能测试，结果表明，将本实施例的Fe掺杂二氧化钛光催化磁性多孔微球首次用于降解亚甲基蓝，在降解40min时的降解率可达90.9％。经6次循环使用后，样品的催化性能无显著变化。
Claims (10)
1.一种大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述方法包含如下步骤：
首先，将可溶性高分子用蒸馏水溶解得到浓度为0.5wt％～1.5wt％的溶液A，然后将光催化剂加入到所述溶液A中，混合搅拌均匀后得到悬浊液B，再将饱和可溶性铁盐溶液与所述悬浊液B混合，搅拌均匀后得到悬浊液C；采用合适针头大小的注射器将所述悬浊液C逐滴滴加到高浓度碱液中生成微球颗粒，滴加完毕后，陈化、干燥，最后将干燥后的微球在600～1100℃条件下煅烧30～120min，冷却后即得到本发明所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球。
2.根据权利要求1所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述的可溶性高分子为田菁粉、羧甲基纤维素、瓜尔豆胶中的任一种。
3.根据权利要求1或2所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述的光催化剂为二氧化钛、镧钛酸钾、钛酸锶或氧化锌中的任一种。
4.根据权利要求1所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述悬浊液B的固含量为35wt％～65wt％。
5.根据权利要求1所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述的可溶性铁盐为氯化铁或硝酸铁中的任一种。
6.根据权利要求1所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述的铁盐溶液中Fe3+离子与光催化剂的摩尔比为15～45：100。
7.根据权利要求1所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述的碱液为浓氨水、尿素饱和溶液、六次甲基四胺饱和溶液中的任一种。
8.根据权利要求1所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的制备方法，其特征在于：所述陈化时间为30～120min，干燥温度为60～80℃。
9.一种根据权利要求1所述方法制得的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的应用，其特征在于：所述光催化磁性多孔微球可用于催化降解有机染料。
10.根据权利要求9所述的大尺寸高孔隙率Fe掺杂光催化磁性多孔微球的应用，其特征在于：所述的有机染料为亚甲基蓝染料。
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407116A (zh) * | 2011-10-13 | 2012-04-11 | 西北工业大学 | 一种大孔高比表面磁性可见光催化剂Fe3O4/TiO2的制备方法 |
| CN102533716A (zh) * | 2012-01-20 | 2012-07-04 | 安徽农业大学 | 一种用于有机氯污染土壤修复的磁性纳米生物微球制备方法 |
| CN102658082A (zh) * | 2012-04-25 | 2012-09-12 | 武汉理工大学 | 一种用于吸附净化多金属离子工业废水的无机复合材料及其应用方法 |
| KR101292965B1 (ko) * | 2011-03-15 | 2013-08-02 | 금오공과대학교 산학협력단 | 전이금속 도핑 이산화티탄 광촉매의 제조방법 |
| CN103447038A (zh) * | 2013-09-18 | 2013-12-18 | 天津城建大学 | 介孔TiO2负载纳米铁催化剂的制备方法 |
| CN103638912A (zh) * | 2013-12-06 | 2014-03-19 | 中国烟草总公司郑州烟草研究院 | 一种多孔羧甲基纤维素微球的制备方法及其产品与在卷烟滤嘴中的应用 |
| CN103831093A (zh) * | 2014-03-06 | 2014-06-04 | 浙江师范大学 | 一种氧化锌基复合光催化纳米材料及其制备方法 |
| CN106179246A (zh) * | 2016-08-04 | 2016-12-07 | 东北林业大学 | 一种纤维素基TiO2/β‑CD双网凝胶笼微球及其制备方法和应用 |
| CN106492761A (zh) * | 2016-11-01 | 2017-03-15 | 河南工业大学 | 一种磁性水凝胶微球的制备方法 |
| CN106964352A (zh) * | 2017-03-31 | 2017-07-21 | 山东师范大学 | 新型光催化材料TiO2@Fe2O3、SrTiO3@Fe2O3的制备及应用 |
| CN107175089A (zh) * | 2017-06-06 | 2017-09-19 | 大连民族大学 | 一种掺杂钴离子的铁镍磁性微球及其应用 |
| CN107376914A (zh) * | 2017-08-09 | 2017-11-24 | 苏州汉力新材料有限公司 | 一种四氧化三铁‑二氧化钛复合材料及其制备方法 |
| CN107626315A (zh) * | 2017-10-23 | 2018-01-26 | 烟台智本知识产权运营管理有限公司 | 一种Fe掺杂的ZnO光催化剂的制备方法 |
| CN107973367A (zh) * | 2017-12-02 | 2018-05-01 | 延海平 | 一种Fe掺杂包裹型TiO2光催化剂降解废水的工艺 |
| CN107983353A (zh) * | 2017-12-22 | 2018-05-04 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | 一种TiO2-Fe2O3复合粉体的制备方法及其应用 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015007230A1 (zh) * | 2013-07-18 | 2015-01-22 | 中国石油大学(北京) | 一种铁基加氢催化剂及其应用 |
| CN105727963B (zh) * | 2016-04-18 | 2018-05-18 | 盐城工学院 | 一种Fe、Cu共掺杂纳米ZnO光催化剂及其制备方法 |
-
2018
- 2018-05-11 CN CN201810447613.8A patent/CN108554412B/zh active Active
-
2019
- 2019-04-25 US US16/395,218 patent/US10933406B2/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101292965B1 (ko) * | 2011-03-15 | 2013-08-02 | 금오공과대학교 산학협력단 | 전이금속 도핑 이산화티탄 광촉매의 제조방법 |
| CN102407116A (zh) * | 2011-10-13 | 2012-04-11 | 西北工业大学 | 一种大孔高比表面磁性可见光催化剂Fe3O4/TiO2的制备方法 |
| CN102533716A (zh) * | 2012-01-20 | 2012-07-04 | 安徽农业大学 | 一种用于有机氯污染土壤修复的磁性纳米生物微球制备方法 |
| CN102658082A (zh) * | 2012-04-25 | 2012-09-12 | 武汉理工大学 | 一种用于吸附净化多金属离子工业废水的无机复合材料及其应用方法 |
| CN103447038A (zh) * | 2013-09-18 | 2013-12-18 | 天津城建大学 | 介孔TiO2负载纳米铁催化剂的制备方法 |
| CN103638912A (zh) * | 2013-12-06 | 2014-03-19 | 中国烟草总公司郑州烟草研究院 | 一种多孔羧甲基纤维素微球的制备方法及其产品与在卷烟滤嘴中的应用 |
| CN103831093A (zh) * | 2014-03-06 | 2014-06-04 | 浙江师范大学 | 一种氧化锌基复合光催化纳米材料及其制备方法 |
| CN106179246A (zh) * | 2016-08-04 | 2016-12-07 | 东北林业大学 | 一种纤维素基TiO2/β‑CD双网凝胶笼微球及其制备方法和应用 |
| CN106492761A (zh) * | 2016-11-01 | 2017-03-15 | 河南工业大学 | 一种磁性水凝胶微球的制备方法 |
| CN106964352A (zh) * | 2017-03-31 | 2017-07-21 | 山东师范大学 | 新型光催化材料TiO2@Fe2O3、SrTiO3@Fe2O3的制备及应用 |
| CN107175089A (zh) * | 2017-06-06 | 2017-09-19 | 大连民族大学 | 一种掺杂钴离子的铁镍磁性微球及其应用 |
| CN107376914A (zh) * | 2017-08-09 | 2017-11-24 | 苏州汉力新材料有限公司 | 一种四氧化三铁‑二氧化钛复合材料及其制备方法 |
| CN107626315A (zh) * | 2017-10-23 | 2018-01-26 | 烟台智本知识产权运营管理有限公司 | 一种Fe掺杂的ZnO光催化剂的制备方法 |
| CN107973367A (zh) * | 2017-12-02 | 2018-05-01 | 延海平 | 一种Fe掺杂包裹型TiO2光催化剂降解废水的工艺 |
| CN107983353A (zh) * | 2017-12-22 | 2018-05-04 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | 一种TiO2-Fe2O3复合粉体的制备方法及其应用 |
Non-Patent Citations (1)
| Title |
|---|
| 鲁启鹏等: "《基于金属氧化物TiO2和Y2O3纳米材料光电性能的研究》", 31 May 2015, 北京交通大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560960A (zh) * | 2022-03-10 | 2022-05-31 | 广东省科学院生物与医学工程研究所 | 一种纤维素催化热解制备左旋葡聚糖的方法 |
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