CN111250170A - 一种在泡沫镍表面原位生长镍基MOFs膜光催化剂及其制备方法和应用 - Google Patents
一种在泡沫镍表面原位生长镍基MOFs膜光催化剂及其制备方法和应用 Download PDFInfo
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- CN111250170A CN111250170A CN202010107308.1A CN202010107308A CN111250170A CN 111250170 A CN111250170 A CN 111250170A CN 202010107308 A CN202010107308 A CN 202010107308A CN 111250170 A CN111250170 A CN 111250170A
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Abstract
本发明公开了一种在泡沫镍表面上原位生长镍基MOFs膜光催化剂及其制备方法和应用。所述在泡沫镍表面原位生长的镍基MOFs膜光催化剂是先将泡沫镍置于稀酸中浸泡超声，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；将该表面活化处理的泡沫镍浸泡在咪唑类化合物、甲酸钠和溶剂的混合液中，在100～180℃下反应，在泡沫镍表面得到未活化的镍基MOFs膜，冷却至室温后，取出将其浸泡在有机溶剂中活化，干燥制得。本发明在泡沫镍上原位合成的膜光催化剂，不仅能增大材料的比表面积，有利于VOCs的吸附与扩散，并且有更多的催化位点暴露，以至于能在太阳光的驱动下有效地降解VOCs。
Description
技术领域
本发明属于光催化材料技术领域，更具体地，涉及一种在泡沫镍表面原位生长镍基MOFs膜光催化剂及其制备方法和应用。
背景技术
挥发性有机物(VOCs)作为大气污染的一个重要污染源，它不仅是参与灰霾、光化学污染的重要物种和二次有机气溶胶的重要前体物，而且具有生物毒性及“三致作用”，已成为当今大气污染的三大杀手之一。因此，如何经济、有效地净化各种日益增长的VOCs污染问题，已成为我国政府和社会公众迫切需要解决的问题。光催化氧化法是一种新兴的具有良好应用前景的VOCs治理技术，其主要利用半导体为光催化剂，在光照作用下使空气中的O2和H2O被激发形成具有强氧化性的·OH-和·O2自由基，最终将VOCs分解为无二次污染的CO2和H2O。然而，目前已报道的半导体光催化剂大部分仅可以利用紫外光(占太阳光的不足5％)激发下才表现出光催化活性，这极大地限制了他们的实际应用；另一方面，由于实际大气中VOCs浓度较低，而常用半导体催化剂的比表面积小、光生载流子复合率高，致使其对VOCs的降解效率较低。因此，研发具有可见光响应的可高效光催化降解VOCs的催化剂是目前亟待解决的问题。
金属-有机骨架材料(Metal-organic frameworks，MOFs)是一类由金属离子与有机配体自组装而成的具有规则孔道结构的有机-无机杂化纳米多孔材料。与沸石分子筛等无机多孔材料相比，MOFs具有大的比表面积、高的孔隙率和结构性质可调等特性，已在气体储存与分离、气体吸附、催化等领域展现出良好的应用前景。尤其在VOCs光催化降解方面，MOFs材料表现出优异的光催化活性。但在实际应用中，宏观上呈现粉末状态的MOFs材料会存在传质阻力和光的遮蔽等问题，并不适用于实际环境中VOCs的光催化工程应用。因此本发明提供了一种复合材料的制备方法，以具有高导电性/导热性、重量轻和3D交联网格结构的商业泡沫镍为基底，在泡沫镍上原位生长镍基MOFs薄膜(简称为Ni-MOF/NF)。该复合材料不仅有利于增加光催化剂的透光性，也有利于VOCs的吸附与扩散，并且利用泡沫镍的良好导电性有利于光生电子的传输，减少电子-空穴的体相复合，进而提高光生载流子的分离效率，从而达到提高光催化降解VOCs的目的。截至目前，未见关于在泡沫镍表面上原位生长镍基MOFs膜光催化剂及其在VOCs降解方面的相关研究和报道。
发明内容
本发明的目的是为了克服现有技术的缺陷，提供了一种在泡沫镍表面原位生长镍基MOFs膜光催化剂。
本发明的另一目的在于提供上述方法制备得到泡沫镍表面原位生长的镍基MOFs膜光催化剂的制备方法。该方法以商业的泡沫镍为镍源，利用MOFs构建配体对泡沫镍的刻蚀作用，在水热合成过程中使泡沫镍释放出镍离子，随后利用镍离子与有机配体在泡沫镍表面进行自组装，原位生长MOFs膜。
本发明的再一目的在于提供泡沫镍表面原位生长的镍基MOFs膜光催化剂的应用。
本发明上述目的通过以下技术方案予以实现：
一种在泡沫镍表面原位生长镍基MOFs膜光催化剂，所述在泡沫镍表面原位生长的镍基MOFs膜光催化剂是先将泡沫镍置于稀酸中浸泡超声，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；将该表面活化处理的泡沫镍浸泡在咪唑类化合物、甲酸钠和溶剂的混合液中，在100～180℃下反应，使咪唑类化合物与泡沫镍表面被刻蚀释放的镍离子发生配位作用，在泡沫镍表面得到未活化的镍基MOFs膜，冷却至室温后，取出将其浸泡在有机溶剂中活化，干燥制得。
优选地，所述咪唑类化合物为2-甲基咪唑、咪唑、苯并咪唑或2-乙基咪唑中的一种以上。
优选地，所述稀酸为硝酸、盐酸或硫酸；所述稀酸的浓度为0.5～6mol/L。
优选地，所述咪唑类化合物、甲酸钠和溶剂的摩尔比为(1～10)：1：(100～200)。
优选地，所述溶剂为甲醇、水或DMF中的一种或任意两种，所述有机溶剂为甲醇或乙醇。
优选地，所述超声的时间为5～60min；所述反应的时间为4～18h；所述活化的时间为12～48h。
所述在泡沫镍表面原位生长镍基MOFs膜光催化剂的制备方法，包括如下步骤：
S1.将泡沫镍置于稀酸中浸泡超声，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；
S2.将步骤S1所得表面活化处理的泡沫镍浸在咪唑类化合物、甲酸钠和溶剂混合液中，在100～180℃下反应，使咪唑类化合物与泡沫镍表面被刻蚀释放的镍离子发生配位作用，在泡沫镍表面得到未活化的镍基MOFs膜；
S3.将在泡沫镍表面得到未活化的镍基MOFs膜冷却至室温后，取出将其浸泡在有机溶剂中活化，干燥，得到在泡沫镍表面原位生长的镍基MOFs膜光催化剂。
所述在泡沫镍表面原位生长镍基MOFs膜光催化剂在太阳光驱动下降解大气中挥发性有机物中的应用。
优选地，所述挥发性有机物为油漆喷涂行业排放的VOCs。
更为优选地，所述油漆喷涂行业排放的VOCs为乙酸乙酯。
本发明以具有良好导电/导热的泡沫镍为基底，通过溶剂热合成法，制备出一种新型的在泡沫镍表面原位生长的镍基MOFs膜光催化剂材料。该膜材料在太阳光驱动下可高效催化降解低浓度VOCs，并具有优异的稳定性。这是由于MOFs膜高度分散在具有大孔的泡沫镍表面，既增强了对光的吸收和利用，又提高了VOC的传质；而且由于泡沫镍的导电性有利于光生电子的传输，减少电子-空穴的体相复合，可有效提高光生载流子的分离效率，进而提高复合光催化剂的光催化活性和稳定性。
由于该光催化剂中MOFs膜在泡沫镍表面原位均匀生长，泡沫镍大的孔道结构不仅有利于VOCs的传质而且也有利于增强光的透过，同时导电/导热的泡沫镍与MOFs间良好的界面接触有利于光生电子的快速转移，进而提高光生载流子的分离，使复合材料在太阳光驱动下对VOCs表现出较高的光催化降解性能，为高效光催化降解VOCs的可见光响应催化剂提供了积极的指导意义。
与现有技术相比，本发明具有以下有益效果：
1.本发明结合半导体特性和良好VOCs吸附能力的MOFs，与具有良好导电/导热的泡沫镍相结合，制备出一种泡沫镍表面原位生长MOFs光催化剂膜。由于合成过程中直接以泡沫镍自身提供镍源，不需要额外的镍源及其他辅助合成步骤，显著提高了原子利用率；而且由于泡沫镍具有大量三维孔道结构和良好的电子传导能力，相比于对应的粉末状镍基MOF，本发明提供的复合光催化剂具有更好的透光性、快速的分子传质和光生载流子分离能力。
2.本发明制备出的泡沫镍表面原位生长镍基MOFs膜光催化剂对典型VOCs乙酸乙酯展现出一定的吸附能力和优异的催化活性。暗吸附实验结果表明，在60min内，复合材料对乙酸乙酯达到吸脱附平衡。光催化实验结果表明，复合材料对气相乙酸乙酯的降解效率在360min后仍高达95％，对应的矿化率仍保持在40％。该复合催化剂的制备为高效VOCs的光催化剂设计提供了新的思路，也对其工程应用提供了科学思路。
附图说明
图1为实施例1所得Ni-MOF/NF的扫描电镜照片；
图2为实施例1所得Ni-MOF/NF膜光催化剂对气相乙酸乙酯的吸附动力学曲线和光催化降解动力学曲线。
具体实施方式
下面结合说明书附图和具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.使用稀盐酸(0.5mol/L)和去离子水分别浸泡超声尺寸为1cm2的泡沫镍，洗去泡沫镍表面污渍、氧化膜和有机物等，让泡沫镍露出新鲜表面。然后，把洗净的泡沫镍放入真空干燥箱中60℃干燥，得到表面活化的泡沫镍。
2.将表面活化处理的泡沫镍浸入摩尔比为1：1：100的2-甲基咪唑、甲醇和甲酸钠混合液的聚四氟乙烯的反应釜中，放置烘箱中，设置程序，1℃/min升至120℃，并在此温度下保持12h，反应完成后，降温至室温，得到泡沫镍表面生长的未活化镍基MOFs膜；
3.将得到的泡沫镍表面生长的未活化镍基MOFs膜用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中120℃，干燥24h，得到在泡沫镍上原位生长的镍基MOFs膜光催化剂(Ni-MOF/NF)。
图1为实施例1所得Ni-MOF/NF的扫描电镜照片；从图1中可知，镍基MOFs材料原位生长在泡沫镍上且呈片状均匀分布。图2为本实施例所得泡沫镍表面原位合成的镍基MOFs膜光催化剂(Ni-MOF/NF)对气相乙酸乙酯的吸附动力学曲线和光催化降解动力学曲线。由图2可看出，在60min内，Ni-MOF/NF对乙酸乙酯的吸附达到吸脱附平衡，在60min内，Ni-MOF/NF对气相乙酸乙酯的光催化降解效率达到95％。结果表明，该镍基MOFs膜光催化剂具有一定的吸附性能，并且具有很高的光催化活性。在泡沫镍表面原位生长的镍基MOFs膜光催化剂可对VOCs具有一定吸附能力和高光催化活性的新型材料。
实施例2
1.使用稀盐酸(6mol/L)和去离子水分别浸泡超声尺寸为1cm2的泡沫镍，洗去泡沫镍表面污渍、氧化膜和有机物等，让泡沫镍露出新鲜表面。然后，把洗净的泡沫镍放入真空干燥箱中60℃干燥，得到表面活化的泡沫镍；
2.将表面活化处理的泡沫镍浸入摩尔比为10：1：200的2-甲基咪唑、甲醇和甲酸钠混合加入带聚四氟乙烯的反应釜中，放置烘箱中，设置程序，5℃/min升至100℃，并且在此温度下保持12h，反应完成后，降温至室温，得到泡沫镍表面生长的未活化镍基MOFs膜；
3.将得到的泡沫镍表面生长的未活化镍基MOFs膜用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中120℃，干燥24h，得到在泡沫镍表面原位生长的镍基MOFs膜光催化剂。
实施例3
1.使用稀盐酸(3mol/L)和去离子水分别浸泡超声尺寸为1cm2的泡沫镍，洗去泡沫镍表面污渍、氧化膜和有机物等，让泡沫镍露出新鲜表面。然后，把洗净的泡沫镍放入真空干燥箱中60℃干燥，得到表面活化的泡沫镍；
2.将表面活化处理的泡沫镍浸入摩尔比为5：1：150的咪唑、DMF和甲酸钠混合加入带聚四氟乙烯的反应釜中，放置烘箱中，设置程序，10℃/min升至180℃，并且在此温度下保持4h，反应完成后，降温至室温，得到泡沫镍表面生长的未活化镍基MOFs膜；
3.将得到的泡沫镍表面生长的未活化镍基MOFs膜用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中120℃，干燥24h，得到在泡沫镍表面原位生长的镍基MOFs膜光催化剂。
实施例4
1.使用稀硝酸(1mol/L)和去离子水分别浸泡超声尺寸为4cm2的泡沫镍，洗去泡沫镍表面污渍、氧化膜和有机物等，让泡沫镍露出新鲜表面。然后，把洗净的泡沫镍放入真空干燥箱中80℃干燥，得到表面活化的泡沫镍；
2.将表面活化处理的泡沫镍浸入摩尔比为2：1：150的苯并咪唑、甲醇和甲酸钠混合加入带聚四氟乙烯的反应釜中，放置烘箱中，设置程序，3℃/min升至140℃，并且在此温度下保持12h，反应完成后，降温至室温，得到泡沫镍表面生长的未活化镍基MOFs膜；
3.将得到的泡沫镍表面生长的未活化镍基MOFs膜用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中120℃，干燥48h，得到在泡沫镍表面原位生长的镍基MOFs膜光催化剂。
实施例5
1.使用稀硫酸(浓度4mol/L)和去离子水分别浸泡超声尺寸为4cm2的泡沫镍，洗去泡沫镍表面污渍、氧化膜和有机物等，让泡沫镍露出新鲜表面。然后，把洗净的泡沫镍放入真空干燥箱中80℃干燥，得到表面活化的泡沫镍；
2.将表面活化处理的泡沫镍浸入摩尔比例为10：1：200的2-乙基咪唑、水和甲酸钠混合加入带聚四氟乙烯的反应釜中，放置烘箱中，设置程序，0.5℃/min升至140℃，并且在此温度下保持18h，反应完成后，降温至室温，得到泡沫镍表面生长的未活化镍基MOFs膜；
3.将得到的泡沫镍表面生长的未活化镍基MOFs膜用醇类物质和去离子水交叉洗涤后，放入真空干燥箱中150℃，干燥24h，得到在泡沫镍表面原位生长的镍基MOFs膜光催化剂。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种在泡沫镍表面原位生长镍基MOFs膜光催化剂，其特征在于，所述在泡沫镍表面原位生长的镍基MOFs膜光催化剂是先将泡沫镍置于稀酸中浸泡超声，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；将该表面活化处理的泡沫镍浸泡在咪唑类化合物、甲酸钠和溶剂的混合液中，在100～180℃下反应，使咪唑类化合物与泡沫镍表面被刻蚀释放的镍离子发生配位作用，在泡沫镍表面得到未活化的镍基MOFs膜，冷却至室温后，取出将其浸泡在有机溶剂中活化，干燥制得。
2.根据权利要求1所述的在泡沫镍表面原位生长镍基MOFs膜光催化剂，其特征在于，所述咪唑类化合物为2-甲基咪唑、咪唑、苯并咪唑或2-乙基咪唑中的一种以上。
3.根据权利要求1所述的在泡沫镍表面原位生长镍基MOFs膜光催化剂，其特征在于，所述稀酸为硝酸、盐酸或硫酸；所述稀酸的浓度为0.5～6mol/L。
4.根据权利要求1所述的在泡沫镍表面原位生长镍基MOFs膜光催化剂，其特征在于，所述咪唑类化合物、甲酸钠和溶剂的摩尔比为(1～10)：1：(100～200)。
5.根据权利要求1所述的在泡沫镍表面原位生长镍基MOFs膜光催化剂，其特征在于，所述溶剂为甲醇、水或DMF中的一种或任意两种，所述有机溶剂为甲醇或乙醇。
6.根据权利要求1所述的在泡沫镍表面原位生长镍基MOFs膜光催化剂，其特征在于，所述超声的时间为5～60min；所述反应的时间为4～18h；所述活化的时间为12～48h。
7.一种根据权利要求1-6任一项所述在泡沫镍表面原位生长镍基MOFs膜光催化剂的制备方法，其特征在于，包括如下步骤：
S1.将泡沫镍置于稀酸中浸泡超声，然后用去离子水清洗干净，经干燥制得表面活化处理的泡沫镍；
S2.将步骤S1所得表面活化处理的泡沫镍浸在咪唑类化合物、甲酸钠和溶剂混合液中，在100～180℃下反应，使咪唑类化合物与泡沫镍表面被刻蚀释放的镍离子发生配位作用，在泡沫镍表面得到未活化的镍基MOFs膜；
S3.将在泡沫镍表面得到未活化的镍基MOFs膜冷却至室温后，取出将其浸泡在有机溶剂中活化，干燥，得到在泡沫镍表面原位生长的镍基MOFs膜光催化剂。
8.权利要求1-6任一项所述在泡沫镍表面原位生长镍基MOFs膜光催化剂在太阳光驱动下降解大气中挥发性有机物中的应用。
9.根据权利要求8所述的在泡沫镍表面原位生长镍基MOFs光催化剂膜在太阳光驱动下降解大气中挥发性有机物中的应用，其特征在于，所述挥发性有机物为油漆喷涂行业排放的VOCs。
10.根据权利要求9所述的在泡沫镍表面原位生长镍基MOFs光催化剂膜在太阳光驱动下降解大气中挥发性有机物中的应用，其特征在于，所述油漆喷涂行业排放的VOCs为乙酸乙酯。
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