CN112536070A - 可见光响应型MIL-100(Fe)光催化复合材料的制备方法 - Google Patents
可见光响应型MIL-100(Fe)光催化复合材料的制备方法 Download PDFInfo
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Abstract
本发明涉及光催化材料的制备，旨在提供一种可见光响应型MIL‑100(Fe)光催化复合材料的制备方法。包括：将相同质量份的均苯三甲酸和氢氧化钠，加入去离子水中；混合均匀得到均苯三甲酸/氢氧化钠复合溶液；将其逐滴加入等量的亚铁盐溶液中，然后加入表面活性剂，混合均匀、充分反应形成悬浊液；过滤悬浊液并洗涤，将获得的固体物干燥，得到MIL‑100(Fe)光催化复合材料。本发明在室温下的合成方法更加便捷，结晶也更稳定，大大提高了催化剂的应用稳定性和循环使用寿命。表面活性剂表面改性工艺有效减小晶粒的尺寸，大大提升材料的比表面积，提高光催化反应效率。能够显著提高材料对可见光的利用效率，获得较强的可见光催化活性。
Description
技术领域
本发明涉及光催化材料的制备，特别涉及一种可见光响应型MIL-100(Fe)光催化复合材料的制备方法。
背景技术
金属有机骨架化合物(英文名称Metal organic Framework，MOFs)在降解有机污染物时具有诸多优点：①具有大的比表面积和孔隙率；②MOFs的孔道具有“择形选择效应”，即通过改变MOFs的金属与配体种类调节MOFs的孔道，使对反应物和生成物进行选择性吸附；③具有结构和功能的可设计性及可控性，可以通过调变配体和金属的种类获得具有高可见光响应的光催化材料；④MOFs材料的拓扑结构决定了其活性位点比较分散，不容易团聚，催化剂的稳定性较高。
在MOFs中，MIL-100(Fe)具有更低的毒性、绿色环保，更为重要的是它具有半导体性质。MIL-100(Fe)的有机配体和Fe(III)O6八面体能够吸收紫外及可见光，发生π-π＊和3d-3d跃迁，产生光生电子/空穴对，是性能优异的光催化材料。但是目前其很高的光生-电子复合率是制约MIL-100(Fe)可见光催化活性之一，同时其制备工艺复杂，需要用到HF等有毒物质辅助合成。
为此，本发明通过在室温下借助表面活性剂的作用一步制备出了具有更小晶粒尺寸、更强光催化性能的MIL-100(Fe)纳米材料。通过配方及室温条件下制备工艺的设计，实现了具有高吸附能力的可见光响应型MIL-100(Fe)复合光催化材料的制备。
发明内容
本发明要解决的技术问题是，克服现有技术的不足，提供一种可见光响应型MIL-100(Fe)光催化复合材料的制备方法。
为解决上述技术问题，本发明的解决方案是：
提供一种可见光响应型MIL-100(Fe)光催化复合材料的制备方法，包括以下步骤：
(1)制备均苯三甲酸/氢氧化钠复合溶液：
取15～30质量份的均苯三甲酸和相同质量的氢氧化钠，加入至400质量份的去离子水中；磁力搅拌混合均匀1～1.5h，得到澄清透明的均苯三甲酸/氢氧化钠复合溶液；
(2)制备亚铁盐溶液：
在室温下将亚铁盐溶解于去离子水中，配制成体积摩尔分数为1mol/L的溶液；
(3)制备可见光响应型MIL-100(Fe)光催化复合材料：
将均苯三甲酸/氢氧化钠复合溶液逐滴加入亚铁盐溶液中，两者质量比1∶1；然后向混合溶液中加入占亚铁盐质量0.5～3％的表面活性剂，磁力搅拌18～24h，混合均匀、充分反应形成悬浊液；过滤悬浊液并用去离子水与乙醇交替洗涤4次，将获得的固体物在60～100℃下干燥，得到MIL-100(Fe)光催化复合材料。
本发明中，所述步骤(1)中，在加入至去离子水中时，均苯三甲酸和氢氧化钠的添加速度控制在8ml/min以内。
本发明中，所述步骤(2)中，亚铁盐是硫酸亚铁、氯化亚铁或硝酸亚铁中的至少一种。
本发明中，所述步骤(3)中，表面活性剂是十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)或聚乙二醇(PEG)中的至少一种。
本发明的实现原理：
申请人通过研究材料的形成机理发现，常温下Fe2+在反应过程中被氧化为Fe3+，对于材料的骨架形成以及结晶有促进作用，因此采用了在常温下使用二价铁盐和均苯三甲酸/氢氧化钠溶液反应生成MIL-100(Fe)的方法。通过对MIL-100(Fe)制备的配方进行设计与研选，对传统水热、溶剂热制备工艺进行了改进。同时，针对以上材料配方体系，采用活化工艺，利用多种活化剂对MIL-100(Fe)进行活化，细化晶粒，从而使得制的的晶粒具有较小的尺寸和较大的比表面积，大大提高了催化剂的可见光催化性能。
与现有技术相比，本发明的有益效果是：
1、采用室温水相合成工艺一步制备了MIL-100(Fe)纳米颗粒，有效避免了传统水热、溶剂热制备工艺繁琐的问题。该室温下的合成方法更加便捷，结晶也更稳定，大大提高了催化剂的应用稳定性和循环使用寿命。
2、本发明表面活性剂表面改性工艺，解决了传统MIL-100(Fe)纳米颗粒尺寸较大的问题，有效减小了晶粒的尺寸，大大提升了材料的比表面积，对甲醛、染料等有机污染物具有更强的吸附捕捉能力，有利于提高光催化反应效率。
3、在纳米结构构筑的同时，有效抑制了光生载流子的复合，增加了光生载流子的寿命，显著提高了材料对可见光的利用效率，获得较强的可见光催化活性。
附图说明
图1为实施例4所制备可见光响应型MIL-100(Fe)的扫描电镜照片。
图2为实施例4所制备可见光响应型MIL-100(Fe)对亚甲基蓝的可见光催化降解曲线。
具体实施方式
下面结合具体实施方式对本发明作进一步详细描述，实施例可以使本专业的专业技术人员更全面地理解本发明，但不以任何方式限制本发明。
本发明所述可见光响应型MIL-100(Fe)光催化复合材料的制备方法，包括以下步骤：
(1)制备均苯三甲酸/氢氧化钠复合溶液：
取15～30质量份的均苯三甲酸和相同质量的氢氧化钠，加入至400质量份的去离子水中；磁力搅拌1～1.5h，得到混合均匀的澄清透明溶液；
(2)制备亚铁盐溶液：
在室温下将亚铁盐溶解于去离子水中，配制成体积摩尔分数为1mol/L的溶液；
(3)制备可见光响应型MIL-100(Fe)光催化复合材料：
将均苯三甲酸/氢氧化钠复合溶液逐滴加入亚铁盐溶液中，两者质量比1∶1；然后向混合溶液中加入占亚铁盐质量0.5～3％的表面活性剂，磁力搅拌18～24h，混合均匀、充分反应形成悬浊液；过滤悬浊液并用去离子水与乙醇交替洗涤4次，将获得的固体物在60～100℃下干燥，得到MIL-100(Fe)光催化复合材料。该复合材料呈纳米颗粒状(如图1所示)。
本发明分别通过8个实施例制得可见光响应型MIL-100(Fe)纳米颗粒，各实施例中的制备过程记载的试验数据见下表1。
表1实施例数据表
光催化剂性能试验方法：
将20mg光催化复合材料加入40mL浓度为50mg/L的亚甲基蓝水溶液中，经功率为5W的LED灯光照2h后，测算对亚甲基蓝的光催化分解效率。
与现有催化材料的比对情况：
使用常规的MOFs材料ZIF-8作为对比，发现相同测试条件下ZIF-8对亚甲基蓝的光催化分解效率仅为49.3％，其光催化活性明显低于本发明中所制备的MIL-100(Fe)光催化材料。
最后，还需要注意的是，以上列举的仅是本发明的具体实施例子。显然，本发明不限于以上实施例子，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。
Claims (4)
1.一种可见光响应型MIL-100(Fe)光催化复合材料的制备方法，其特征在于，包括以下步骤：
(1)制备均苯三甲酸/氢氧化钠复合溶液：
取15～30质量份的均苯三甲酸和相同质量的氢氧化钠，加入至400质量份的去离子水中；磁力搅拌混合均匀1～1.5h，得到澄清透明的均苯三甲酸/氢氧化钠复合溶液；
(2)制备亚铁盐溶液：
在室温下将亚铁盐溶解于去离子水中，配制成体积摩尔分数为1mol/L的溶液；
(3)制备可见光响应型MIL-100(Fe)光催化复合材料：
将均苯三甲酸/氢氧化钠复合溶液逐滴加入亚铁盐溶液中，两者质量比1∶1；然后向混合溶液中加入占亚铁盐质量0.5～3％的表面活性剂，磁力搅拌18～24h，混合均匀、充分反应形成悬浊液；过滤悬浊液并用去离子水与乙醇交替洗涤4次，将获得的固体物在60～100℃下干燥，得到MIL-100(Fe)光催化复合材料。
2.根据权利要求1中所述的制备方法，其特征在于，所述步骤(1)中，在加入至去离子水中时，均苯三甲酸和氢氧化钠的添加速度控制在8ml/min以内。
3.根据权利要求1中所述的制备方法，其特征在于，所述步骤(2)中，亚铁盐是硫酸亚铁、氯化亚铁或硝酸亚铁中的至少一种。
4.根据权利要求1中所述的制备方法，其特征在于，所述步骤(3)中，表面活性剂是十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)或聚乙二醇(PEG)中的至少一种。
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