CN108940363B - 一种大孔/介孔复合型光催化剂及其制备方法 - Google Patents
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Abstract
本发明涉及一种大孔/介孔复合型光催化剂及其制备方法,以可见光响应的四羧基酞菁铁(III)为光催化剂,通过静电相互作用将其负载在一种环氧基大孔/介孔聚合物载体上,该载体材料具有1~50μm的相互连通的大孔以及平均孔径为20nm的介孔,比表面积达到230m2/g以上,孔隙率在90%以上,在聚合物载体的制备中,使用三羟甲基丙烷熔体作为分散剂,在冷却过程中通过连续结晶达到致孔目的,在复合型光催化剂中铁酞菁配合物的含量在0~5.6wt.%范围内可调,在优化条件下可见光照射1小时就能使罗丹B的降解率达到95%以上,该催化剂稳定性高,可重复使用性好,其它的优势还包括大尺寸任意形状以及较好的机械强度。
Description
技术领域
本发明属于光催化材料技术领域,涉及一种可见光相应的复合型光催化剂及其制备方法,尤其是一种以大孔/介孔聚合物为载体以金属酞菁为催化剂,集吸附与光催化功能为一体的复合型光催化剂。
背景技术
近20年来,以半导体材料作为光催化剂降解各种水污染物得到越来越多的重视。光催化的基本原理是光催化材料在特定波长的光照下,吸收辐射能产生电子跃迁,在表面形成空穴-电子对,空穴从吸附在表面的水的氢氧根离子夺取电子,生成氧化能力很强的羟基自由基,将水中的有机物彻底氧化。金属酞菁具有良好的化学、光和热稳定性,是一种典型的p-型半导体材料,在可见光区有强的跃迁,对600~800nm的可见光具有强烈的吸收,其中酞菁铁是一种仿生的功能化合物,其催化作用类似氧化酶,因此利用酞菁铁作为仿生光催化剂吸收可见光处理水或空气中的有机物污染具有实际意义。金属酞菁是一类平面结构的分子,它们熔点极高,都有很强的分子聚集行为,一旦聚集的话其催化功能就不能很好地发挥,因此如何将其分散是面临的关键问题。本发明采用一种大孔/介孔聚合物作为载体,介孔材料一般都具有较高的比表面积,有很强的吸附能力,可以将四羧基酞菁铁(III)(Fe(III)-taPc)催化剂高效负载,同时大孔的存在可以为反应物的扩散传质提供必要的通道,在保证催化剂大尺寸的前提下,有效提高催化反应的速率,同时将吸附功能与光催化降解功能整合在一起可以大大提高催化剂的环境净化能力,所以这种复合型催化剂在设计上是极为合理的,本发明提出的技术能制备出使用方便,性能稳定,可见光响应好,催化效率高的新型光催化剂。
发明内容
本发明所要解决的首要技术问题是针对环境净化问题提供一种安全、方便、效果良好的光催化降解技术方案,一方面它依赖一种大孔/介孔高分子载体材料,这种材料同时具有1~50μm的大孔以及平均孔径为20nm的介孔,其比表面积达到230m2/g,孔隙率在90%以上,表观密度在0.1g/mL以下,它既有很强的吸附能力,又有高的吸附速率和吸附容量。另一方面利用四羧基酞菁铁(III)作为一种可见光响应的光催化剂,将两者复合在一起就构成一种安全、高效的光催化剂,能够对水或者空气中的有机分子污染物进行净化,对环境与人都无任何危害。
本发明所要解决的另一个技术问题是提供上述大孔/介孔复合型光催化剂的制备方法,它切实可行,操作简便,易于生产。
1、本发明解决首要技术问题所采用的技术方案为:一种大孔/介孔复合型光催化剂,它是通过环氧基高分子载体与四羧基酞菁铁(III)复合而成,其中高分子载体具有如图1所示的结构特征,既有1~50μm的大孔又有平均孔径为20nm的介孔(根据图2所示的结果),其比表面积达到230m2/g,孔隙率在90%以上,表观密度在0.1g/mL以下;四羧基酞菁铁(III)对可见光吸收能力极强,又表现出光催化降解性能,将两者复合就能产生一种综合性能优异的光催化剂。
非常有益的是,上述的聚合物载体可以进行阳离子化,一方面增强其亲水性,为催化降解提供必要的水分,同时阳离子化的载体与带有负电荷的四羧基酞菁铁(III)产生静电相互作用,可以很方便的达到负载的目的;
非常有益的是,介孔结构能使四羧基酞菁铁(III)得到极好的分散,避免了分子之间的相互缔合,大大提高催化剂的稳定性和催化活性;
非常有益的是,孔径在1~50μm范围的相互连通的大孔结构,为催化反应提供了极为丰富的分子扩散通道,降低了传质阻力,大大改善了污染物的吸附速率以及催化反应的速率,同事催化剂可以保持大尺寸外形,有利于分离操作;
非常有益的是,在可见光作用下聚合物基本上不会受到侵害,可以保持长期的稳定性,使催化剂长久耐用。
2、本发明解决另一个技术问题所采用的技术方案为:一种上述高分子吸附材料制备方法,其特征步骤为:1)三羟甲基丙烷加热融化至能流动液体,加入环氧树脂(牌号E-51)快速搅拌得到白色分散液,三羟甲基丙烷与环氧树脂的质量比在20/1~30/1范围,迅速加入二乙烯三胺,环氧树脂与二乙烯三胺的质量比在8/1~6/1范围;2)用冰水冷却并剧烈搅拌使其放热均匀,最后得到粘稠的半固体,迅速倒入模具中,待彻底固化后置于冰箱中进一步冷却2~3小时,经过冷冻后得到坚硬的白色固体;3)将固体在45℃下固化12~15小时,固体产物放入水中浸泡,彻底洗去三羟甲基丙烷,然后放入真空烘箱中常温下干燥,得到白色的稳定的聚合物多孔材料;4)将聚合物材料放入硫酸二乙酯的乙醇溶液中,溶液的浓度保持在2wt.%~4wt.%范围,40℃下浸泡反应2~3小时,然后放入水中浸泡5~6小时,处理后的材料有明显的膨胀软化现象,然后再放入真空烘箱中常温下干燥,得到阳离子化的聚合物;5)将四羧基酞菁铁(III)(Fe(III)-taPc)溶解在pH为9~10的NaOH水溶液中,其浓度保持在0.2~0.5wt.%范围,将称重后的阳离子聚合物浸泡在此水溶液中,一小时后取出并用清水洗涤浸泡,得到深蓝色的样品,真空中常温下干燥后称重,若要增加负载量可以重复浸泡操作。
非常有益的是,三羟甲基丙烷对环氧树脂既有一定的亲和性,但又不能将环氧树脂完全溶解,这种状态非常有利于连续结晶,形成从微米尺度到纳米尺度的结晶,从而制造出孔径分布极宽的多孔结构;
非常有益的是,环氧树脂是在低于三羟甲基丙烷熔点的温度下,也就是固体状态下发生固化反应,这样就能完全避免相分离对产物形貌造成的影响,保证了产物内部形貌的连续性以及宏观上的机械强度;
非常有益的是,在分散液中环氧树脂的浓度可以非常低,因而所得到的多孔材料其表观密度也非常低,孔隙率很大,其内部的三维孔道完全贯通。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
材料制备:
实施例1
60.0g三羟甲基丙烷加热融化至透明能流动液体,加入3.0g环氧树脂E-51搅拌分散,加入0.44g二乙烯三胺,用冰水冷却并剧烈搅拌使其放热均匀,得到粘稠的半固体,其中含有大量微小晶体,倒入塑料模具,待彻底固化后置于冰箱中进一步冷却结晶3小时,经过冷冻后得到坚硬的白色固体,在45℃下固化12小时,水中反复浸泡至三羟甲基丙烷彻底去除后,真空中常温干燥,得到白色泡沫状材料,将聚合物材料放入硫酸二乙酯的乙醇溶液中,溶液的浓度保持在4wt.%,40℃下浸泡反应2小时,然后放入水中浸泡5~6小时,处理后的材料有明显的膨胀软化现象,然后再放入真空烘箱中常温下干燥得到阳离子化聚合物,将四羧基酞菁铁(III)(Fe(III)-taPc)溶解在pH为9~10的NaOH水溶液中,其浓度保持在0.2wt.%,将称重后的阳离子聚合物浸泡在此水溶液中,1小时后取出并用清水洗涤浸泡,得到深蓝色的样品,真空中常温下干燥后称重,如果再重复将样品浸泡在新配的Fe(III)-taPc溶液中,将获得负载量更高的样品。
实施例2
90.0g三羟甲基丙烷加热融化至透明能流动液体,加入3.0g环氧树脂E-51搅拌分散,再加入0.50g二乙烯三胺,不断搅拌得到良好的分散液,用冰水冷却并剧烈搅拌使其放热均匀,得到粘稠的半固体,其中含有大量微小晶体,倒入塑料模具,待彻底固化后置于冰箱中进一步冷却结晶4小时,经过冷冻后得到坚硬的白色固体,在45℃下固化14小时,在水中反复浸泡至三羟甲基丙烷彻底去除后,真空中常温干燥,得到白色泡沫材料,将聚合物材料放入硫酸二乙酯的乙醇溶液中,溶液的浓度保持在2wt.%,40℃下浸泡反应3小时,然后放入水中浸泡5~6小时,处理后的材料有明显的膨胀软化现象,然后再放入真空烘箱中常温下干燥,得到阳离子化聚合物,将四羧基酞菁铁(III)(Fe(III)-taPc)溶解在pH为9~10的NaOH水溶液中,其浓度保持在0.5wt.%,将称重后的阳离子聚合物浸泡在此水溶液中,1小时后取出并用清水洗涤浸泡,得到深蓝色的样品,真空中常温下干燥后称重,如果再重复将样品浸泡在新配的Fe(III)-taPc溶液中,将获得负载量更高的样品。
材料测试:
采用扫描电子显微镜(JSM-5600LV型)观察样品的形貌,样品喷铂后在5kV的加速电压下进行表面形貌表征;用比表面积及孔径分布测试仪(JW-K型)测试比表面积,用BET公式计算其比表面积;复合物样品中Fe(III)-taPc的含量用重量法测定。
光催化性能测试:
以有机染料罗丹明B为目标降解物,氧气为氧化剂,进行光催化反应,考察了不同负载量Fe(III)-taPc/SiO2的光催化活性及循环使用性。以150W的卤灯(λ≥400nm)为可见光光源,光源距离反应器10cm。分别称取50mg不同负载量的Fe(III)-taPc/SiO2催化剂,制成颗粒状样品(尺寸约为1mm),分散于50ml 10μmol/L的罗丹明B水溶液,置于自制的密闭光反应器中,通入氧气。在磁力搅拌下,将反应体系置于暗处1h,确保吸附平衡后开启光源进行光催化反应。反应过程中每隔10min取样,离心取其上清液,以紫外-可见分光光度计测定罗丹明B在552nm处的吸光度,并计算其浓度。根据公式Ct/C0计算光催化降解率,式中C0和Ct分别为原溶液和每隔10min所取样品溶液中罗丹明B的浓度。
光催化降解罗丹明B的实验结果如图3所示,负载量在0~5.6wt.%范围内可调,随着负载量的增加,降解速率明显加快,这说明Fe(III)-taPc的分散性良好,分子聚集现象得到明显的遏制,这要归功于介孔载体的分散能力,从图中可以发现,在现有的实验条件下,罗丹明的降解率很容易达到95%以上,最高的可以达到99%,证明这种光催化剂的高效降解能力。
附图说明
图1吸附材料在不同放大倍数下的扫描电镜图像,左边的图可以看到大孔部分的形貌,右边的图可以看到孔壁内部的小孔形貌。
图2吸附-脱附法测定介孔材料的孔径分布数据。
图3为不同负载量光催化剂对罗丹明B的降解曲线。
Claims (2)
1.一种大孔/介孔复合型光催化剂,其特征在于聚合物载体拥有1~50μm的相互贯通的大孔和平均孔径为20nm的介孔,比表面积达到230m2/g以上,孔隙率在90%以上;
所述的大孔/介孔复合型光催化剂以四羧基酞菁铁(III)为可见光响应的光催化剂,光催化剂的负载量在1.3~5.6wt.%范围;
所述的聚合物载体是通过环氧树脂/有机物分散体系在固体状态下固化后再水洗除去分散剂、最后通过阳离子亲水化处理而获得;
所述的聚合物载体制备方法,其特征在于使用三羟甲基丙烷熔体作为有机分散剂,利用其在冷却过程中的连续结晶而致孔。
2.一种权利要求1所述的大孔/介孔复合型光催化剂制备方法,其特征在于步骤依次为:
1)三羟甲基丙烷加热融化至能流动液体,加入环氧树脂E-51快速搅拌得到白色分散液,三羟甲基丙烷与环氧树脂的质量比在20/1~30/1范围,迅速加入二乙烯三胺,环氧树脂与二乙烯三胺的质量比在8/1~6/1范围;
2)用冰水冷却并剧烈搅拌使其放热均匀,最后得到粘稠的半固体,迅速倒入模具中,待彻底固化后置于冰箱中进一步冷却2~3小时,经过冷冻后得到坚硬的白色固体;
3)将固体在45℃下固化12~15小时,固体产物放入水中浸泡,彻底洗去三羟甲基丙烷,然后放入真空烘箱中常温下干燥,得到白色的稳定的聚合物多孔材料;
4)将聚合物材料放入硫酸二乙酯的乙醇溶液中,硫酸二乙酯乙醇溶液的浓度在2wt.%~4wt.%范围,40℃下浸泡反应2~3小时,然后放入水中浸泡5~6小时,处理后的材料有明显的膨胀软化现象,然后再放入真空烘箱中常温下干燥,得到阳离子化的聚合物;
5)将四羧基酞菁铁(III)溶解在pH为9~10的NaOH水溶液中,其浓度保持在0.2~0.5wt.%范围,将称重后的阳离子聚合物浸泡在此水溶液中,一小时后取出并用清水洗涤浸泡,得到深蓝色的样品,真空中常温下干燥后称重。
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