CN108855105B - 铁酸锌-铁酸钴异质结复合催化剂及其制备方法和应用 - Google Patents
铁酸锌-铁酸钴异质结复合催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及铁酸锌‑铁酸钴异质结复合催化剂及其制备方法和应用。可见光响应的铁酸锌‑铁酸钴异质结催化剂降解有机污染物,对四环素、金霉素、土霉素进行120min氧化降解,对四环素能达到78%的降解效果,对硝基苯酚进行120min还原降解,能达到60%以上的降解效果。本发明具有简便、温和、高效、成本低、对可见光吸收度高的特点,所制备的铁酸锌‑铁酸钴异质结电极材料具有带隙窄、比表面积大的特点,具有良好的可见光吸收性能和良好的稳定性,光电效率高,光电催化降解有机物效果好,能够应用于光电催化降解有机物以及传感器等领域。
Description
技术领域
本发明涉及可见光响应的铁酸锌-铁酸钴异质结复合催化剂及其在降解有机污染物中的应用,主要针对来自于制药行业的废水,属于水处理领域。
背景技术
光电催化作为一种新型的废水处理技术,其在有机废水的深度处理方面已显示出广阔的应用前景,它以彻底降解有机污染物为显著优点而受到国内外研究者的普遍关注。光电催化过程具有对有机物的降解几乎无选择性,能彻底降解有机污染物,无二次污染,设备简单,投资少,效果好等独特的优点。光电催化氧化技术是半导体催化剂通过太阳光或紫外光作用产生氧化能力很强的空穴,将有机污染物降解为H2O和CO2。该技术具有对有机物的降解选择性低、价廉易得、可回收重复利用、运行费用低等特点。传统的光催化氧化技术采用TiO2为催化剂,具有价廉、无毒、催化活性高、氧化能力强、稳定性好、易于回收的特点。但是,由于TiO2的能带带隙较宽(约为3.2ev),需要能量较高的紫外光才能使其价带中的电子受激发,而表现出光催化活性。而在自然界中,太阳光中的紫外线含量较低,只占太阳光总照度的4%左右,对太阳光的利用率较低。另外,光生电子和电子空穴的复合也导致光量子产率低,限制了该技术在实际中的应用。
研究发现,铁酸盐催化剂具有良好的催化性能,其中铁酸盐由于其廉价及易得的优点受到青睐,铁酸盐的能带带隙较窄(2.0eV左右),其对光的吸收主要集中在500nm左右,材料能够充分利用可见光,但铁酸盐的带隙较窄,光生电子和空穴很容易复合,其氧化还原能力较弱。
发明内容
本发明的目的之一是提供一种可见光响应的铁酸锌-铁酸钴异质结复合催化剂及其制备方法。
本发明的目的之二是提供一种利用铁酸锌-铁酸钴异质结复合催化剂光电催化降解废水中有机污染物的方法。针对有机物废水浓度高、化学需氧量(COD)高、难降解等特点,通过将负载催化剂的碳纸与工作电极连接、铂丝与对电极,甘汞电极与参比电极连接,通过电化学工作站给予0.8V的电压,氙灯给光进行光电催化降解。
本发明采用的技术方案是:铁酸锌-铁酸钴异质结复合催化剂,由铁酸锌和铁酸钴,按摩尔比,ZnFe2O4:CoFe2O4=(5-30):1制成。
铁酸锌-铁酸钴异质结复合催化剂的制备方法,包括如下步骤:将Zn(NO3)2·6H2O、FeSO4·7H2O和十二烷基三甲基溴化铵CTAB溶于水中后,加入Na2C2O4水溶液,使得按摩尔比,Zn2+:Fe2+:CTAB:C2O4 -=1:2:0.25:2,搅拌均匀后,加入铁酸钴CoFe2O4,所得混合溶液放入有特氟隆衬层的反应釜中,100℃水热反应30h,所得固体分别用二次水和无水乙醇洗涤,干燥,所得固体在氮气保护下500℃煅烧2h,升温速率为2℃/min,得到铁酸锌-铁酸钴异质结复合催化剂ZnFe2O4/CoFe2O4。
优选的,上述的铁酸锌-铁酸钴异质结复合催化剂的制备方法,所述的铁酸钴CoFe2O4的制备方法为:将Fe(NO3)3·9H2O、Co(NO3)2·6H2O溶于水中,搅拌均匀,调节混合液的pH为12,继续搅拌60min,将所得溶液放入有特氟隆衬层的反应釜中,180℃水热反应12h,所得固体分别用二次水和无水乙醇洗涤,干燥,得铁酸钴CoFe2O4。
上述的铁酸锌-铁酸钴异质结复合催化剂在光电催化降解有机污染物中的应用。方法如下:将上述的铁酸锌-铁酸钴异质结复合催化剂涂覆在碳纸或导电玻璃上作为工作电极,铂丝为对电极,甘汞电极为参比电极,置于反应容器中,构成三电极体系;将含有有机污染物的废水和电解质溶液加入反应容器中,调节pH为7-10,在电化学工作站给予0.8V电压和氙灯照射120min。
优选的,所述的有机污染物是四环素类抗生素和对硝基苯酚。优选的,所述的四环素类抗生素是四环素、金霉素、或土霉素。
优选的,所述的电解质溶液是浓度为1mol/L的Na2SO4溶液。
优选的,调节pH为9。
优选的,氙灯距有机污染物和电解质溶液的混合溶液的液面距离为10cm。
本发明的有益效果是:本发明通过铁酸锌和铁酸钴两种材料复合的方式,进一步提高光响应范围及光催化性能,提高其捕捉光子的效率,抑制电子空穴对的复合,提高电子从价带跃迁至导带的利用率,提高光催化活性。采用本发明的方法处理抗生素类和对硝基苯酚废水工艺简单、降低能耗、降解速度快。对四环素、金霉素、土霉素进行120min氧化降解,对四环素能达到78%的降解效果,对硝基苯酚进行120min还原降解,能达到60%以上的降解效果。
本发明具有简便、温和、高效、成本低、对可见光吸收度高的特点,所制备的铁酸锌-铁酸钴异质结电极具有带隙窄、比表面积大的特点,具有良好的可见光吸收性能和良好的稳定性,光电效率高,光电催化降解有机物效果好,能够应用于光电催化降解有机物以及传感器等领域。
附图说明
图1是铁酸锌、铁酸钴和铁酸锌-铁酸钴异质结复合催化剂(摩尔比10:1)的XRD。
图2是铁酸锌(a)、铁酸钴(b)和铁酸锌-铁酸钴异质结复合催化剂(c)(摩尔比10:1)的电镜。
图3a是Zn的XPS。
图3b是Fe的XPS。
图3c是O的XPS。
图3d是Co的XPS。
图4是电压对降解率的影响。
图5是溶液pH对降解率的影响。
具体实施方式
实施例1
(一)铁酸钴的制备
将1.72g Fe(NO3)3·9H2O和0.62g Co(NO3)2·6H2O溶于25ml水中,搅拌30min,得到均匀的溶液,用6M的NaOH将溶液的pH调节为12,继续搅拌60min,将所得溶液放入有特氟隆衬层的反应釜中,180℃水热12h,将得到的固体分别用二次水和无水乙醇洗涤三次,在烘箱中60℃干燥12h,得铁酸钴CoFe2O4。
(二)铁酸锌的制备
将4.16g Zn(NO3)2·6H2O、7.78g FeSO4·7H2O和1.23g十二烷基三甲基溴化铵(CTAB)溶于35ml水中,得到均匀的溶液。然后,加入Na2C2O4水溶液(3.75g Na2C2O4溶于35ml水中),使n(Zn2+):n(Fe2+):n(CTAB):n(C2O4 -)=1:2:0.25:2,所得溶液搅拌20min,将所得混合溶液放入有特氟隆衬层的反应釜中,100℃水热反应30h,所得固体分别用二次水和无水乙醇洗涤三次,在烘箱中60℃干燥12h,得铁酸锌ZnFe2O4。
(三)铁酸锌-铁酸钴异质结复合催化剂ZnFe2O4/CoFe2O4的制备
将4.16g Zn(NO3)2·6H2O、7.78g FeSO4·7H2O和1.23g十二烷基三甲基溴化铵(CTAB)溶于35ml水中,得到均匀的溶液。然后,加入Na2C2O4水溶液(3.75g Na2C2O4溶于35ml水中),使按摩尔比,n(Zn2+):n(Fe2+):n(CTAB):n(C2O4 -)=1:2:0.25:2,所得溶液搅拌20min,获得铁酸锌ZnFe2O4反应体系。
分别将不同量的(一)获得的铁酸钴CoFe2O4加入到上述获得的铁酸锌ZnFe2O4反应体系中,充分搅拌,混合均匀,形成均匀的悬浮液,将所得的悬浮液放入特氟隆反应釜中进行水热反应,100℃水热反应30h,所得固体分别用二次水和无水乙醇洗涤三次后,在烘箱中60℃干燥12h,所得固体在氮气保护下500℃煅烧2h,升温速率为2℃/min,制得不同比例的铁酸锌-铁酸钴异质结复合催化剂ZnFe2O4/CoFe2O4。按摩尔比,铁酸锌:铁酸钴=5:1、10:1、20:1、30:1。
由图1、图2和图3a-图3d可以证明复合材料已经成功制备,CoFe2O4成功的负载在ZnFe2O4上,形成异质结,做成光电极材料。
实施例2
方法:分别将实施例1制备的不同比例的铁酸锌-铁酸钴异质结复合催化剂溶解在二次水中,然后用移液枪均匀的负载在碳纸上,用红外灯烤20min左右,将催化剂烤干,分别作为工作电极,铂丝为对电极,甘汞电极为参比电极,置于反应容器中,构成三电极体系。
将含有有机污染物的废水和电解质溶液加入反应容器中,调节pH为7-10,Na2SO4作为导电介质,然后将三电极体系浸入到溶液中,使液面刚刚没过催化剂,在电化学工作站给予0.8V电压和氙灯提供光源,氙灯照射120min。氙灯距有机污染物和电解质溶液的混合溶液的液面距离为10cm,对四环素溶液进行光电降解。
(一)ZnFe2O4/CoFe2O4的比例对降解率的影响
在50mL含10ppm四环素的废水加入0.7102g Na2SO4形成混合溶液,ZnFe2O4/CoFe2O4比例不同的复合材料负载在导电玻璃上做光电阳极,对有机物进行光电降解,降解时间为60min。结果如表1。
表1
ZnFe<sub>2</sub>O<sub>4</sub>:CoFe<sub>2</sub>O<sub>4</sub> | 5:1 | 10:1 | 20:1 | 30:1 |
降解率% | 27.17% | 34.57% | 26.1% | 25.4% |
由表1可见,随着比例的增加,四环素的降解率呈现先增加后减少的趋势,根据其降解效果,优选ZnFe2O4:CoFe2O4=10:1作为降解材料。
(二)电压对降解率的影响
将实施例1制备的,摩尔比为,铁酸锌:铁酸钴=10:1的铁酸锌-铁酸钴异质结复合催化剂溶解在二次水中,然后用移液枪均匀的负载在碳纸上,用红外灯烤20min左右,将催化剂烤干,作为工作电极。
在50mL二次水中加入0.7102g Na2SO4形成溶液,利用线性扫描伏安法确定光电阳极的最佳工作电位,结果如图4。
由图4可见,当电压小于0.6V时,电流几乎没有变化,当电压大于0.6V时,电流开始有明显的变化,且随着电压的增大迅速,当电压大于0.8V时,增量明显减小,在电压为0.8V时选为最佳电压。
(三)pH对降解率的影响
将实施例1制备的,摩尔比为,铁酸锌:铁酸钴=10:1的铁酸锌-铁酸钴异质结复合催化剂溶解在二次水中,然后用移液枪均匀的负载在碳纸上,用红外灯烤20min左右,将催化剂烤干,作为工作电极。
在50mL含10ppm四环素的废水中,加入0.7102g Na2SO4形成混合溶液,通过向溶液中加入氢氧化钠改变溶液的pH值为:7.0、8.0、9.0、10.0,利用电化学工作站给予0.8V电压,氙灯提供光源,氙灯照射120min。对混合溶液进行光电催化降解,然后利用紫外分光光度计测其吸光度A。计算降解率η,η=(A0-A)/A0×100%。结果如图5所示。
由图5可见,pH为9时,降解率为78%,在此pH值下降解率最高,因此本发明优选调节pH值为9.0。
实施例3
方法:将实施例1制备的,摩尔比为,铁酸锌:铁酸钴=10:1的铁酸锌-铁酸钴异质结复合催化剂溶解在二次水中,然后用移液枪均匀的负载在碳纸上,用红外灯烤20min左右,将催化剂烤干,作为工作电极,铂丝为对电极,甘汞电极为参比电极,置于反应容器中,构成三电极体系。
在50mL含10ppm如表2所示的有机污染物的废水中,加入0.7102g Na2SO4形成混合溶液,通过向溶液中加入氢氧化钠改变溶液的pH值为9,利用电化学工作站给予0.8V电压,氙灯提供光源,氙灯照射120min。对混合溶液进行光电催化降解,然后利用紫外分光光度计测其吸光度A。计算降解率η,η=(A0-A)/A0×100%。结果如表2所示。
表2
四环素 | 金霉素 | 土霉素 | 对硝基苯酚 | |
降解率 | 78% | 70.2% | 64.8% | 61.1%(pH=4) |
由表2可见,经过条件的优化,在pH=9时,复合材料对四环素类的抗生素的降解率可以达到70%左右,其中对四环素的降解效果最好,可以达到78%;另外测试材料的还原能力,在pH=4时,复合材料降解对硝基苯酚在60%左右。由此可见,此复合材料可作为双功能催化剂,既可做光电阳极氧化降解有机污染物,也可做光电阴极还原降解有机污染物。
Claims (9)
1.铁酸锌-铁酸钴异质结复合催化剂的制备方法,其特征在于,所述铁酸锌-铁酸钴异质结复合催化剂为ZnFe2O4/CoFe2O4,按摩尔比,ZnFe2O4:CoFe2O4=(5-30):1,制备方法包括如下步骤:将Zn(NO3)2·6H2O、FeSO4·7H2O和十二烷基三甲基溴化铵CTAB溶于水中后,加入Na2C2O4水溶液,使得按摩尔比,Zn2+:Fe2+:CTAB:C2O4 - = 1:2:0.25:2,搅拌均匀后,加入铁酸钴CoFe2O4,所得混合溶液放入有特氟隆衬层的反应釜中,100℃水热反应30h,所得固体分别用二次水和无水乙醇洗涤,干燥,所得固体在氮气保护下500℃煅烧2h,升温速率为2℃/min,得到铁酸锌-铁酸钴异质结复合催化剂ZnFe2O4/CoFe2O4。
2.根据权利要求1所述的铁酸锌-铁酸钴异质结复合催化剂的制备方法,其特征在于,所述的铁酸钴CoFe2O4的制备方法为:将Fe(NO3)3·9H2O、Co(NO3)2·6H2O溶于水中,搅拌均匀,调节混合液的pH为12,继续搅拌60min,将所得溶液放入有特氟隆衬层的反应釜中,180℃水热反应12h,所得固体分别用二次水和无水乙醇洗涤,干燥,得铁酸钴CoFe2O4。
3.按照权利要求1所述的方法制备的铁酸锌-铁酸钴异质结复合催化剂在光电催化降解有机污染物中的应用。
4.根据权利要求3所述的应用,其特征在于,方法如下:将权利要求1所述的铁酸锌-铁酸钴异质结复合催化剂涂覆在碳纸或导电玻璃上作为工作电极,铂丝为对电极,甘汞电极为参比电极,置于反应容器中,构成三电极体系;将含有有机污染物的废水和电解质溶液加入反应容器中,调节pH为7-10,在0.8V电压下,氙灯照射120min。
5.根据权利要求3或4所述的应用,其特征在于,所述的有机污染物是四环素类抗生素和对硝基苯酚。
6.根据权利要求5所述的应用,其特征在于,所述的四环素类抗生素是四环素、金霉素、或土霉素。
7.根据权利要求4所述的应用,其特征在于,所述的电解质溶液是浓度为1mol/L的Na2SO4溶液。
8.根据权利要求4所述的应用,其特征在于,调节pH为9。
9.根据权利要求4所述的应用,其特征在于,氙灯距有机污染物和电解质溶液的混合溶液的液面距离为10cm。
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