CN112691676A - 一种Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法及其氧化体系和应用 - Google Patents
一种Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法及其氧化体系和应用 Download PDFInfo
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Abstract
本发明提供了一种Zn掺杂α‑Fe2O3/石墨烯气凝胶复合催化剂的制备方法及其氧化体系和应用,该制备方法包括如下步骤:对石墨烯进行预处理得到氧化石墨烯;氧化石墨烯分散于一定量的去离子水中得到氧化石墨烯分散液;向氧化石墨烯分散液中加入预设量的FeSO4·7H2O和Zn(Ac)2·2H2O得到前驱溶液;将前驱溶液放置水热釜内再预设温度和预设时间下进行反应得到初始凝胶;初始凝胶经冷却、透析和干燥处理后得到Zn掺杂α‑Fe2O3/石墨烯气凝胶复合催化剂。该Zn掺杂α‑Fe2O3/石墨烯气凝胶复合催化剂,催化性能好,且具有较好的可见光响应能力。
Description
技术领域
本发明涉及催化材料技术领域,特别是涉及一种Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法及其氧化体系和应用。
背景技术
抗生素是一种由细菌、霉菌或其他微生物产生的次级代谢产物或人工合成的类似物,会对其他生殖细胞发育功能产生影响。抗生素生产废水、生活污水、医疗废水以及兽用与水产养殖业在养殖过程中产生的各种不同种类的抗生素的排放都是导致环境中抗生素问题的来源。
磺胺类药物是现代医学中常用的一类人工合成的抗菌消炎药。因其具有较广的抗菌谱,而且疗效确切、性质稳定、价格便宜,又便于长期保存的特点广泛使用于畜牧业和水产养殖业,用来治疗细菌及特定微生物引起的多种传染疾病。然而研究表明,磺胺类药物的大量使用,会使细菌产生抗药性,还可能和其他兽药、农药等污染物质在生物体内发生交互作用,造成无法预知的后果。此类药物在环境中降解非常缓慢,残留时间长,经过长期的积累和生物链的传递,会在动植物和人体内达到较高的浓度,影响动植物的生长,危害人体健康,导致严重的环境污染。磺胺类药物废水也是典型的难生物降解有机废水之一,采用常规的生物处理去除效果不理想。
发明内容
本发明的一个目的是要提供一种高效催化Oxone降解磺胺类废水的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。
本发明一个进一步的目的是要提高催化效率。
特别地,本发明提供了一种Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,所述制备方法包括如下步骤:
对石墨烯进行预处理得到氧化石墨烯;
所述氧化石墨烯分散于一定量的去离子水中得到氧化石墨烯分散液;
向所述氧化石墨烯分散液中加入预设量的FeSO4·7H2O和Zn(Ac)2·2H2O得到前驱溶液;
将所述前驱溶液放置水热釜内再预设温度和预设时间下进行反应得到初始凝胶;
所述初始凝胶经冷却、透析和干燥处理后得到所述Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。
优选地,所述一定量的去离子水的量为25~35 mL;所述氧化石墨烯分散液的浓度为2~10 mg/mL。
优选地,所述FeSO4·7H2O的用量为0.1~0.4mmol;所述Zn(Ac)2·2H2O的用量为0.05~0.4 mmol。
优选地,所述预设温度为180~190℃;所述预设时间为2.5~3.5h。
优选地,所述透析采用半透膜;所述半透膜为再生纤维滤膜。
优选地,所述干燥为冷冻干燥。
本发明还提供了上述复合催化剂的氧化体系,所述氧化体系为复合催化剂 /Oxone氧化体系。
优选地,所述复合催化剂与所述Oxone的质量比为300~500:1。
本发明还提供了Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的应用,所述Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂用于抗生素废水的处理。
本发明还提供了氧化体系的应用,所述复合催化剂 /Oxone氧化体系用于抗生素废水的处理。
本发明提供的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,制作方法简单,制备条件稳定,采用一锅法制备出易于回收利用的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂,催化性能好,且具有较好的可见光响应能力。在自然光下能够高效催化Oxone降解15mg/L的磺胺间甲氧基嘧啶废水,具有稳定、高效低廉、无毒和可回收循环利用等优点,不但可以避免纳米材料对环境的二次影响,而且可以应用于难生物降解有机污染物的降解,具有较强的市场应用前景。
根据下文对本发明具体实施例的详细描述,本领域技术人员将会更加明了本发明的上述以及其他目的、优点和特征。
附图说明
后文将参照附图以示例性而非限制性的方式详细描述本发明的一些具体实施例。附图中相同的附图标记标示了相同或类似的部件或部分。本领域技术人员应该理解,这些附图未必是按比例绘制的。附图中:
图1是本发明提供的各个实施例制备的不同Fe/Zn摩尔比的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的XRD图谱;
图2是本发明提供的实施例2制得的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的TEM图;
图3是本发明提供的实施例2制得的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的XPS图。
具体实施方式
下面结合实施例对本发明作进一步说明。显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为了提高Zn掺杂α-Fe2O3的催化性能和回收利用性能,本发明采用复合石墨烯气凝胶的催化体系来催化Oxone(2KHSO5·KHSO4·K2SO4)产生SO4•-自由基。Oxone(2KHSO5·KHSO4·K2SO4)为过氧硫酸氢钾复合盐的商品名称,其活性物质为单过氧硫酸氢钾KHSO5。由于一个SO3−取代HOOH形成不对称过氧化物的独特结构,使其易于激发而产生大量的硫酸根自由基(SO4•-)。Zn掺杂α-Fe2O3 /Oxone是一种类似于Fenton试剂的氧化体系,过渡金属Fe3 +、Zn2+能催化Oxone产生大量活泼的、氧化能力强且无选择性的SO4•-自由基,将水体中的有机污染物质彻底氧化为CO2、H2O和无机盐。
由于石墨烯具有独特的电子特征、极大的比表面积和较高的透明度使其成为合成复合催化剂的理想载体;合成的石墨烯复合材料在催化降解有机物中具有许多新的特性,如有效的电荷转移与分离、扩展的光吸收范围和对污染物较好的吸附能力。因此,在本发明中,利用石墨粉和二水合乙酸锌、硫酸亚铁等原材料,将石墨烯与Zn掺杂α-Fe2O3复合,制备出了稳定型的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂,在中性环境下不易溶出,这样既可以利用Zn掺杂α-Fe2O3的催化性能,又可以利用石墨烯气凝胶的吸附和机械稳定性能,使其高效稳定的催化Oxone产生SO4•-自由基。
具体地,本发明提供的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,方法包括如下步骤:
步骤1,对石墨烯进行预处理得到氧化石墨烯。
采用改进的Hummers法,以天然石墨粉为原料制备氧化石墨烯。该石墨烯的处理方法现阶段比较成熟,在此不赘述。
步骤2,氧化石墨烯分散于一定量的去离子水中得到氧化石墨烯分散液。
具体地,氧化石墨烯超声分散在25~35mL去离子水中,得到浓度为2~10mg/mL的氧化石墨烯分散液。
步骤3,向氧化石墨烯分散液中加入预设量的FeSO4·7H2O和Zn(Ac)2·2H2O得到前驱溶液。
具体地,依次加入0.1~0.4mmol FeSO4·7H2O、0.05~0.4 mmol Zn(Ac)2·2H2O 搅拌至溶解且分散均匀后得到前驱溶液。
步骤4,将前驱溶液放置水热釜内再预设温度和预设时间下进行反应得到初始凝胶。
具体地,将前驱溶液放置至水热釜中,180~190℃下保持2.5~3.5h,进行水热反应得到初始凝胶。
步骤5,初始凝胶经冷却、透析和干燥处理后得到Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。该透析采用半透膜,包括但不限于采用再生纤维滤膜,再生纤维滤膜采用美国MD44-1000透析膜。
具体地,初始凝胶冷却至室温,得到水凝胶,经透析处理后冷冻干燥,即得到宏观整体块状的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。
本发明还提供了一种上述复合催化剂的氧化体系,具体为复合催化剂 /Oxone氧化体系,其中复合催化剂与Oxone的质量比为300~500:1。
在下述各个实施例中,充分说明上述制备方法的过程:
空白对照例
在常温室内条件下,1L浓度为30 mg/L 的Oxone溶液对1L浓度为15 mg/L的磺胺间甲氧基嘧啶废水进行降解100min,降解率为1.21%。
实施例1
首先是采用改进的Hummers法,以天然石墨粉为原料制备氧化石墨烯。将氧化石墨烯分散在30mL水溶液中,得到浓度为2mg/mL的氧化石墨烯分散液。然后加入0.1mmolFeSO4·7H2O、0.05mmol Zn(Ac)2·2H2O,搅拌至溶解且分散均匀后,将溶液转移至水热釜中,180℃下保持3h。冷却至室温,得水凝胶,经透析处理后冷冻干燥,即得宏观整体块状Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。在常温室内条件下,10g Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂加入到1L浓度为30 mg/L 的Oxone溶液,对1L浓度为15mg/L的磺胺间甲氧基嘧啶废水进行降解100min,降解率为72.1%。该催化剂在光催化降解过程中受水流冲击会略微变碎,无法整体回收,机械稳定性有待提高。
实施例2
首先是采用改进的Hummers法,以天然石墨粉为原料制备氧化石墨烯。将氧化石墨烯分散在30mL水溶液中,得到浓度为4mg/mL的氧化石墨烯分散液。然后加入0.2mmolFeSO4·7H2O、0.15mmol Zn(Ac)2·2H2O,搅拌至溶解且分散均匀后,将溶液转移至水热釜中,190℃下保持2.5h。冷却至室温,得水凝胶,经透析处理后冷冻干燥,即得宏观整体块状Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。在常温室内条件下,10g Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂加入到1L浓度为30 mg/L 的Oxone溶液,对1L浓度为15mg/L的磺胺间甲氧基嘧啶废水进行降解100min,降解率为83.8%。该催化剂在光催化降解过程中受水流冲击不会有变化,机械稳定性较好,且可以通过挤压方式排除间隙水,整体回收,便于循环利用。
实施例3
首先是采用改进的Hummers法,以天然石墨粉为原料制备氧化石墨烯。将氧化石墨烯分散在30mL水溶液中,得到浓度为6mg/mL的氧化石墨烯分散液。然后加入0.4mmolFeSO4·7H2O、0.2mmol Zn(Ac)2·2H2O,搅拌至溶解且分散均匀后,将溶液转移至水热釜中,180℃下保持3.5h。冷却至室温,得水凝胶,经透析处理后冷冻干燥,即得宏观整体块状Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。在常温室内条件下,10g Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂加入到1L浓度为25 mg/L 的Oxone溶液,对1L浓度为15mg/L的磺胺间甲氧基嘧啶废水进行降解100min,降解率为80.9%。该催化剂在光催化降解过程中受水流冲击不会有变化,机械稳定性较好,且可以通过挤压方式排除间隙水,整体回收,便于循环利用。
实施例4
首先是采用改进的Hummers法,以天然石墨粉为原料制备氧化石墨烯。将氧化石墨烯分散在30mL水溶液中,得到浓度为8mg/mL的氧化石墨烯分散液。然后加入0.36mmolFeSO4·7H2O、0.12mmol Zn(Ac)2·2H2O,搅拌至溶解且分散均匀后,将溶液转移至水热釜中,180℃下保持3h。冷却至室温,得水凝胶,经透析处理后冷冻干燥,即得宏观整体块状Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。在常温室内条件下,10g Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂加入到1L浓度为20 mg/L 的Oxone溶液,对1L浓度为15mg/L的磺胺间甲氧基嘧啶废水进行降解100min,降解率为79.7%。该催化剂在光催化降解过程中受水流冲击不会有变化,机械稳定性较好,且可以通过挤压方式排除间隙水,整体回收,便于循环利用。
实施例5
首先是采用改进的Hummers法,以天然石墨粉为原料制备氧化石墨烯。将氧化石墨烯分散在30mL水溶液中,得到浓度为10mg/mL的氧化石墨烯分散液。然后加入0.32mmolFeSO4·7H2O、0.4mmol Zn(Ac)2·2H2O,搅拌至溶解且分散均匀后,将溶液转移至水热釜中,180℃下保持3h。冷却至室温,得水凝胶,经透析处理后冷冻干燥,即得宏观整体块状Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。在常温室内条件下,10g Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂加入到1L浓度为33 mg/L 的Oxone溶液,对1L浓度为15mg/L的磺胺间甲氧基嘧啶废水进行降解100min,降解率为68.8%。该催化剂在催化降解过程中受水流冲击会略微变碎,无法整体回收,机械稳定性有待提高。
进一步地,图1是本发明提供的上述各个实施例制备的不同Fe/Zn摩尔比的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的XRD图谱。从图中可以看到,制备的催化剂在24.44°、33.39°、35.96°、41.11°、49.80°、54.23°、62.74°和64.34°的2θ衍射角分别与菱型赤铁矿α-Fe2O3晶型的(012)、(104)、(110)、(113)、(024)、(116)、(214)和(300)晶面相吻合,只是整体向大角度方向略微偏移了一些,这可能是Zn掺杂引起的晶格结构改变。
图2是本发明提供的实施例2制得的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的TEM图。实施例2制备的Fe/Zn摩尔比为2:1.5的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的TEM图像,从图中可以看到清晰的石墨烯层状结构,Zn掺杂α-Fe2O3纳米颗粒均匀分散在石墨烯的网状结构中。
图3是本发明提供的实施例2制得的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的XPS图。实施例2制备的Fe/Zn摩尔比为2:1.5的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的XPS图谱,从图中可以看到样品中含有C、O、Fe和Zn四种元素。
本发明Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,制作方法简单,制备条件稳定,采用一锅法制备出易于回收利用的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂,催化性能好,且具有较好的可见光响应能力。在自然光下能够高效催化Oxone降解15mg/L的磺胺间甲氧基嘧啶废水,具有稳定、高效低廉、无毒和可回收循环利用等优点,不但可以避免纳米材料对环境的二次影响,而且可以应用于难生物降解有机污染物的降解,具有较强的市场应用前景。
至此,本领域技术人员应认识到,虽然本文已详尽示出和描述了本发明的多个示例性实施例,但是,在不脱离本发明精神和范围的情况下,仍可根据本发明公开的内容直接确定或推导出符合本发明原理的许多其他变型或修改。因此,本发明的范围应被理解和认定为覆盖了所有这些其他变型或修改。
Claims (10)
1.一种Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,其特征在于,所述制备方法包括如下步骤:
对石墨烯进行预处理得到氧化石墨烯;
所述氧化石墨烯分散于一定量的去离子水中得到氧化石墨烯分散液;
向所述氧化石墨烯分散液中加入预设量的FeSO4·7H2O和Zn(Ac)2·2H2O得到前驱溶液;
将所述前驱溶液放置水热釜内再预设温度和预设时间下进行反应得到初始凝胶;
所述初始凝胶经冷却、透析和干燥处理后得到所述Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂。
2. 根据权利要求1所述的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,其特征在于,所述一定量的去离子水的量为25~35ml;所述氧化石墨烯分散液的浓度为2~10 mg/mL。
3. 根据权利要求1所述的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,其特征在于,所述FeSO4·7H2O的用量为0.1~0.4mmol;所述Zn(Ac)2·2H2O的用量为0.05~0.4mmol。
4.根据权利要求1所述的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,其特征在于,所述预设温度为180~190℃;所述预设时间为2.5~3.5h。
5.根据权利要求1所述的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,其特征在于,
所述透析采用半透膜;
所述半透膜为再生纤维滤膜。
6.根据权利要求1所述的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的制备方法,其特征在于,所述干燥为冷冻干燥。
7. 一种使用所述权利要求1至6任一项所述的复合催化剂的氧化体系,其特征在于,所述氧化体系为复合催化剂 /Oxone氧化体系。
8.根据权利要求7所述的氧化体系,其特征在于,
所述复合催化剂与所述Oxone的质量摩尔比为300~500:1。
9.一种权利要求1至6任一项的制备方法制得的Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂的应用,其特征在于,
所述Zn掺杂α-Fe2O3/石墨烯气凝胶复合催化剂用于抗生素废水的处理。
10.一种权利要求7或8任一项的氧化体系的应用,其特征在于,
所述复合催化剂 /Oxone氧化体系用于抗生素废水的处理。
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