CN113000071A - 一种多孔可见光光催化ZnFe2O4-TiO2/PVDF复合膜的制备方法及再生方法 - Google Patents
一种多孔可见光光催化ZnFe2O4-TiO2/PVDF复合膜的制备方法及再生方法 Download PDFInfo
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Abstract
本发明是可见光催化膜材料,具体多孔可见光光催化ZnFe2O4‑TiO2/PVDF复合膜制备及再生方法。本发明以PVDF为粘黏剂,NMP为有机溶剂,PEG‑400为膜造孔剂,溶胶凝胶法制备得到的ZnFe2O4‑TiO2为光催化剂,将各试剂超声后搅拌分散,制备得到均匀的分散液,通过线棒涂布器于处理过的玻璃载玻片上成型,后于恒温烘箱内干燥定型,将定型后的膜材料置于排出剂中排出PEG‑400最后得到膜材料。多次循环利用后的膜材料光催化性能急剧下降,经过含Cr6+的废水浸泡处理后,膜材料恢复活性,实现活性的再生。过程中控制复合膜中各试剂材料的比例、浸泡时间、PEG‑400排出剂比例等因素来制备膜材料。
Description
技术领域
本发明涉及复合膜材料领域,尤其是涉及ZnFe2O4-TiO2/PVDF可见光催化复合膜的制备方法及再生方法。
背景技术
染料广泛应用于印染、食品、医药、化妆品等行业,在染料生产和使用过程中会产生大量的染料废水。染料废水是工业废水中最难处理的废水之一。国内外目前对于染料污染的处理方法有化学法、物理法和生物法。光催化剂TiO2由于其具有无毒、化学性质稳定等诸多优点,一直是光催化研究领域的热点。
自1972年Fujishima等人发现TiO2具有光催化效应以来,光激发TiO2分解和矿化染料污染物得到了广泛的关注和研究,但由于其宽禁带,只能被紫外光区光子所激发,紫外光能量在太阳光总能量不到5%。
近年来有较多报道关于通过掺杂无机非金属元素,如N、P、S等;金属元素,如Pt、Ag、Mn等,金属化合物,如ZnO、WO3、CdS元素,来提高TiO2在可见光下的光催化性能。关于利用吸收边在可见光下的铁氧体材料进行TiO2掺杂,提高其可见光下的光催化性能的报道逐渐增多,但都研究效果不是太理想。
另外TiO2粉体直接作为光催化剂进行染料废水降解,降解后的废水和催化剂不易分离,TiO2难以回收,催化剂的流失带来环境的二次污染。因此光催化剂的回收也是一个迫切需要解决的问题。
为了回收催化剂,人们开始研究对催化剂进行改性,如改磁性,通过与其他无机离子交联加速沉降等。但是在流动性较大的半开放水体中,仍然难以实现催化剂有较高的回收率。
近年来又有研究人员通过利用憎水粘黏剂如PVDF,将光催化剂固定于玻璃片,高岭石,云母片等基材上。虽然实现了光催化剂的有效回收,但是固定于膜内部的光催化剂不能接触到染料污染物,也不能很好的接触到光照。因此固定化后的光催化剂,其光催化效率较低。
催化剂在经过几次循环使用后,催化剂活性大大降低。失去催化活性的光催化剂要实现再生,往往需要高温条件下进行再生,且再生后的光催化剂活性依然不高。
发明内容
(一)发明目的
本发明的目的是提供一种ZnFe2O4-TiO2/PVDF可见光催化复合膜的制备方法及再生方法。该制备方法通过线棒涂布器制备固定厚度膜材料,将膜烘干后静置于无水乙醇-水混合液中8-10小时,能够使PEG从膜中溶解进入混合液,得到孔隙丰富的ZnFe2O4-TiO2/PVDF膜材料。膜材料具有较发达的孔隙,染料废水污染物能够进入膜内部,接触膜内部的光催化剂,能够增大光催化复合膜的表面积,且光照能够很好的照射进入孔洞内。提高了可见光下的光催化效率。循环使用多次后的膜材料,光催化活性降低,将活性降低后的膜材料置于含Cr6+的废水中再生处理18-24小时,可以实现光催化剂活性的再生
(二)技术方案
为解决上述问题,本发明的第一方面提供了一种ZnFe2O4-TiO2/PVDF可见光催化复合膜的制备方法,包括先通过溶胶凝胶法制备得到ZnFe2O4掺杂TiO2复合材料;将PVDF溶解于NMP中;将一定量PEG-400加入到溶液中;将一定量的ZnFe2O4-TiO2分散于混合溶液中。将所述混合液在玻璃片上涂膜干燥成型,得到玻璃基复合膜材料。将膜材料静置于无水乙醇-去离子水混合液中8-10小时,以使膜中PEG-400溶解于混合溶液中,得到多孔膜材料,将膜材料继续烘干得到ZnFe2O4-TiO2/PVDF可见光催化复合膜。
优选的,通过改变ZnFe2O4的掺杂量得到不同掺杂量的ZnFe2O4-TiO2复合材料,包括:通过共沉淀法制备,按照0%,0.1%,0.5%,2%,5%掺杂量制备得到ZnFe2O4-TiO2复合材料。
优选的,可见光下光催化效率较好的复合材料为掺杂量为0.5%的ZnFe2O4-TiO2复合材料。
优选的,将PVDF、PEG溶解于NMP中得到混合溶液,并将ZnFe2O4-TiO2复合材料分散在混合溶液中,包括:将PVDF、PEG加入NMP中,并在60℃水浴锅中搅拌得到澄清溶液;将ZnFe2O4-TiO2复合材料加入混合澄清液以后超声分散1H,继续水浴中搅拌,得到均匀的前体。
优选的,混合液中PVDF:PEG:NMP:ZnFe2O4-TiO2质量比为1:0.5:8:0.5。
优选的,得到的带有孔隙的ZnFe2O4-TiO2/PVDF可见光催化复合膜厚度为200um。
根据发明的第二方面,提供了一种第一方面提供方法制备的ZnFe2O4-TiO2/PVDF可见光催化复合膜的用途,用于作为可见光下光催化剂。
根据发明的第三方面,提供了一种ZnFe2O4-TiO2/PVDF可见光催化复合膜光催化性能的再生方法,包括:将光催化性能较差的ZnFe2O4-TiO2/PVDF可见光催化复合膜,静置于Cr6+废水中18-24小时,去离子水冲洗后得到再生后的ZnFe2O4-TiO2/PVDF可见光催化复合膜,且光催化效率明显提高,由循环5次后亚甲基蓝降解率为88.5%升高到99.7%。
(三)有益效果
本发明的上述技术方案具有如下有益的技术效果:
(1)本发明实施例提供的多孔ZnFe2O4-TiO2/PVDF可见光催化复合膜的制备方法,先通过掺杂ZnFe2O4掺杂TiO2,实现光催化剂在可见光下的光催化,利用涂布器制备得到固定厚度的膜,干燥成型后将膜静置于无水乙醇/水混合溶液中,使膜中PEG-400溶解于混合液中,得到具有丰富孔隙的膜,增大了膜与污染物的接触面积,提高了光催化效率。
(2)本发明实施例提供对失去光催化活性的ZnFe2O4-TiO2/PVDF可见光催化复合膜的再生方法,将失活后的膜静置于Cr6+废水中,后用去离子水浸泡膜,能够让复合膜材料光催化性能实现再生。
(3)本发明实施例在再生光催化剂的同时,实现了将毒性较高的Cr6+转化为低毒的Cr3+。
附图说明
图1为可见光下多孔ZnFe2O4-TiO2/PVDF复合膜的循环使用效率。
图2为Cr6+废水处理后的循环使用效率。
图3为吸附亚甲基蓝后,可见光照射前复合膜材料。
图4为吸附亚甲基蓝后,可见光照射40分钟后的复合膜材料。
具体实施方式
以下实施例用来说明本发明,但不限制本发明申请请求保护的范围;
实施例1,高可见光催化性能多孔ZnFe2O4-TiO2/PVDF复合膜的合成:通过共沉淀法制备得到可见光光电转换性能较强的ZnFe2O4粉体。21.4ml钛酸四丁酯与85.6ml无水乙醇搅拌混合均匀调节pH<3,得到A液;107ml去离子水与64.2ml无水乙醇搅拌混合均匀得到B 液。将前述ZnFe2O4粉体按照与钛酸四丁酯摩尔比为0.1%-3%加入B液,超声混合均匀。将 A液缓慢滴加进入B液,边滴加边搅拌,控制滴速为每2秒3滴。A液滴加完后继续搅拌2H 得到淡黄色或褐色溶胶。30℃恒温箱内陈化24H得到凝胶。60℃恒温烘箱内烘干,研磨过200 目筛,后在管式炉内氩气氛围下300-700℃煅烧得到较高光催化性能的ZnFe2O4-TiO2复合材料。称取ZnFe2O4-TiO2、PEG-400、PVDF与NMP按照质量比0.5:0.5:1:8先超声1H,再继续搅拌2H得到均匀的分散体。先将玻璃载玻片置于1mol/L NaOH中超声处理0.5H,后用自来水冲洗,再用去离子水浸泡洗净,烘干待用。将前述分散体先办涂布器涂布于载玻片成型,后再恒温烘箱内烘干定型。将定型后的膜材料置于去无水乙醇和离子水混合液中浸泡 18-24小时,后用去离子水清洗,后烘干。上述膜对亚甲基蓝等偶氮染料污染物具有可见光下高催化性能的多孔复合膜。
实施例2,可见光高催化效率多孔ZnFe2O4-TiO2/PVDF复合膜的再生。将实施例1中制备得到的复合膜循环数次处理偶氮染料废水后,其光催化活性降低。通过将低活性的复合膜浸泡于含Cr6+的废水中18-24H,既能使膜的活性再生,又能实现高毒Cr6+向低毒Cr3+的转化。
Claims (7)
1.一种多孔可见光光催化ZnFe2O4-TiO2/PVDF复合膜的制备方法及再生方法,具体步骤如下:
(1)先通过共沉淀法制备得到可见光下较强光电转化效率的粉体ZnFe2O4材料;
(2)以钛酸四丁酯为二氧化钛前驱体,钛酸四丁酯与无水乙醇体积比1∶3混合搅拌得到A液,去离子水与无水乙醇1∶1调节至pH<3,加入一定量前述ZnFe2O4粉体,继续搅拌0.5H混合搅拌得到B液;
(3)在30℃水浴条件下将A液缓慢滴加进入B液体,边滴加边搅拌,滴加完A液后继续搅拌2H,得到微黄色透明溶胶;
(4)将溶胶置于30℃恒温箱内陈华12-24H,使晶体成长成熟;
(5)将陈化好的凝胶于60℃下烘干得到ZnFe2O4-TiO2复合材料;
(6)将上述得到的ZnFe2O4-TiO2复合材料在氩气氛围下300-700℃煅烧,得到可见光下光催化效果较好的复合光催化剂ZnFe2O4-TiO2;
(7)将PVDF、PEG-400加入NMP一定量的NMP中,60℃水浴搅拌得到澄清透明的混合液;
(8)将(6)中制备得到的复合光催化剂ZnFe2O4-TiO2加入(7)中先超声1H后继续搅拌2H制备得到均匀的分散液,搅拌2H。其中PVDF∶PEG-400∶NMP∶ZnFe2O4-TiO2比例为1∶0.5∶8∶0.5;
(9)将玻璃载玻片于1mol/L NaOH中超声处理0.5H,后用自来水冲洗,再用去离子水浸泡洗净,烘干待用;
(10)将(8)中制得均匀分散液通过使用线棒涂布器涂布于载玻片上,后在恒温烘箱内烘干定型得到ZnFe2O4-TiO2/PVDF可见光催化复合膜,烘箱温度为60℃;
(11)将(10),浸泡于无水乙醇和去离子水的混合液中排出PEG-400得到多孔ZnFe2O4-TiO2/PVDF可见光催化复合膜;浸泡时间为18-24小时;无水乙醇与去离子水为2∶8;
(12)多孔ZnFe2O4-TiO2/PVDF可见光催化复合膜,循环使用后光催化效率急剧下降,使用Cr6+废水处理活性降低后的复合膜材料,膜材料恢复光催化效率至99.7%,处理时间18-24小时。
2.根据权利要求1所述的制备方法,其特征在于,TiO2通过掺杂可见光下光电转换率高的ZnFe2O4,制备得到具有高可见光光催化性能的ZnFe2O4-TiO2复合材料,通过使用PVDF 做粘黏剂,PEG-400做发泡剂,玻璃载玻片做基底制备得到多孔ZnFe2O4-TiO2/PVDF可见光催化复合膜。
3.根据权利要求1或2所述的制备方法,其特征在于,所述可见光催化以为可见光电转换性能高的ZnFe2O4为掺杂剂。
4.根据权利要求1或2所述的制备方法,其特征在于,以PEG-400作为多孔膜发泡剂。
5.根据权利要求1或2所述的制备方法,其特征在于,所述载体为玻璃载玻片,其表面先用NaOH处理表面。
6.根据权利要求1或2所述的制备方法,其特征在于,以无水乙醇和去离子水排出PEG-400造孔。
7.根据权利要求1或2所述的再生方法,其特征在于,以高毒Cr6+废水做再生剂,既使得光催化剂活性再生,也将高毒Cr6+处理得到低毒的Cr3+。
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