CN111774072B - 一种制备碳包覆磁性硫化镉复合光催化剂的方法 - Google Patents
一种制备碳包覆磁性硫化镉复合光催化剂的方法 Download PDFInfo
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Abstract
一种碳包覆磁性硫化镉复合光催化剂的制备方法,其属于无机催化剂领域。本发明先用水热法制备了软磁性材料锰锌铁氧体MnxZn1‑xFe2O4和MnxZn1‑xFe2O4/C,再用浸渍沉淀法制备出了碳包覆磁性硫化镉复合光催化剂(MnxZn1‑xFe2O4/C/CdS)。本发明方法制备工艺简单、使用设备少、能耗低。制备的MnxZn1‑xFe2O4/C/CdS磁性能稳定、光催化活性高,在模拟太阳光氙灯照射下,用0.1g制备的复合磁性光催化剂降解100mL浓度为10mg/L的罗丹明B溶液,140min对罗丹明B的降解率达到97.8%,在外加磁场下对光催化剂的磁回收,重复使用3次后对罗丹明B的降解率为96.8%。本发明制备出的产品可广泛用于光催化降解有机污染物领域。
Description
技术领域
本发明涉及一种制备碳包覆磁性硫化镉(MnxZn1-xFe2O4/C/CdS)复合光催化剂的方法,属于无机环境光催化剂技术领域。
背景技术
CdS光催化剂具有出色的光敏性和可见光吸收特性,直接带隙为2.4eV,适合用于吸收太阳光,因其优秀的光催化性能而被广泛使用。但是,单一的CdS不是光稳定的,在光催化过程中会发生光腐蚀现象。目前,为克服这一缺陷而研究了多种方法,例如与其它半导体、聚合物复合形成异质结,表面负载贵金属,掺杂Zn、Mn等离子形成固溶体。研究者制备了众多改性CdS基光催化剂,例如CdS/BiOI、CdS/Bi2MoO6、CdS/g-C3N4、ZnxCd1-xS等。
由于催化降解反应多是在溶液环境中进行,而CdS光催化剂本身颗粒尺寸非常小,悬浮在溶液中造成了难以回收再利用的难题,这不仅导致CdS光催化剂的流失,也会对水环境造成严重的二次污染,尤其是CdS中含有有毒金属Cd。因此,光催化剂存在的回收问题,极大限制CdS光催化剂的实际应用。为了解决这一问题,将CdS负载到磁性材料上,利用外加磁场的作用进行磁性分离,大大提升了回收效率,而且有效的复合方式能保证原有的催化活性进一步增强。现研究使用较多的磁性基体是Fe3O4和MFe2O4(M=Zn,Co,Ni),它们均属于软磁性材料,矫顽力为零,抗退磁能力较弱。
锰锌铁氧体(MnxZn1-xFe2O4)与传统的软磁材料(如Fe3O4、MFe2O4)相比,不仅具有高饱和磁化强度(Ms)、高磁导率等特点,而且具有生产效率高、成本低及产品性能稳定等优点。因此,以锰锌铁氧体为磁性基体制备的复合磁性光催化剂的磁性强,更便于分离和循环利用。
现阶段对CdS进行的磁性改性主要集中在以Fe3O4为载体的磁性基体上,如“Journal of Materials Chemistry”2011年第21卷中的“Magnetic-field inducedformation of 1D Fe3O4/C/CdS coaxial nanochains as highly efficient andreusable photocatalysts for water treatment”(对比文件1),采用磁场诱导组装与微波辅助沉积法制备出复合光催化剂Fe3O4/C/CdS,即,采用水热法先合成纳米Fe3O4磁性颗粒(利用文献方法),稀硝酸洗涤处理后Fe3O4磁性颗粒和葡萄糖溶液混合物在0.2T外磁场存在下水热法(磁场诱导组装)制备得到核壳结构链状Fe3O4/C,在加热条件下链状Fe3O4/C加入Cd2+溶液中吸附、磁分离、干燥后得到Fe3O4/C/Cd2+颗粒,最后将Fe3O4/C/Cd2+颗粒与硫代乙酰胺在微波回流***反应得到链状夹层纳米Fe3O4/C/CdS复合光催化剂。该方法的不足之处在于:(1)工艺过程复杂,使用水热法、磁诱导水热法、加热吸附法、微波辅助反应法等,所需设备多,成本高;(2)制备的Fe3O4/C/CdS复合光催化剂,催化活性不高,对100mL浓度为5mg/L的罗丹明B溶液30min对的脱色率为94.7%;(3)硫源使用的是有机硫化物硫代乙酰胺,未给出Fe3O4/C/CdS复合光催化剂回收方式及回收率数据。
发明内容
本发明的目的是针对CdS的催化活性不稳定、现有磁性CdS光催化剂回收中的问题,提出一种磁性碳包覆锰磁性硫化镉(MnxZn1-xFe2O4/C/CdS)复合光催化剂的制备方法,制备方法简单、成本低。制备的磁性MnxZn1-xFe2O4/C/CdS复合光催化剂在模拟太阳光照射下具有较高的光催化活性,且便于通过外加磁场从液相体系中分离和回收,回收后的催化剂仍具有较高的光催化活性。该方法既简易、高效地实现了资源再利用,又避免了催化剂回收不全可能带来的二次污染。
本发明碳包覆磁性硫化镉(MnxZn1-xFe2O4/C/CdS)复合光催化剂的制备方法如下:
(1)MnxZn1-xFe2O4/C的制备
按照摩尔比n(MnO):n(ZnO):n(Fe2O3)=32.8:13.3:53.9,分别称取一定量的MnSO4·H2O、ZnSO4·7H2O和Fe2(SO4)3,加入一定量的去离子水,充分搅拌得到均匀的混合溶液;称取一定量的NaOH作为沉淀剂,配制成浓度为2mol/L的NaOH溶液;磁力搅拌下将NaOH溶液缓慢地滴入混合溶液,溶液中有棕褐色絮状沉淀物生成时,快速滴加NaOH溶液,调节pH至13,继续搅拌20min;将搅拌后的溶液转入100mL的反应釜中,在烘箱中200℃加热反应5h;水热反应完成后,取出放置冷却至室温,在外加磁铁的作用下,用蒸馏水和无水乙醇反复清洗样品,放置在烘箱中60℃烘干12h,最后研磨得到粉末状MnxZn1-xFe2O4样品;
称取3g葡萄糖,超声溶解到30mL去离子水中,得到浓度为0.5mol/L葡萄糖溶液;称取0.2g制备的MnxZn1-xFe2O4粉末,加入到溶液中并剧烈搅拌1h;然后,将溶液转移至50mL反应釜中,在烘箱中180℃加热5h;放置冷却至室温,同样利用外加磁铁,用蒸馏水和无水乙醇反复清洗样品,放置在烘箱中60℃烘干12h,最后研磨得到粉末状MnxZn1-xFe2O4/C样品。
(2)磁性复合光催化剂MnxZn1-xFe2O4/C/CdS的制备
按照摩尔比n(Cd2+):n(S2-)=1:1.25,称取0.8g的Cd(Ac)2·2H2O超声溶解到40mL去离子水中,加入与理论生成CdS质量比为5~15:100的MnxZn1-xFe2O4/C,机械搅拌30min得到悬浊液A;称取0.9g的Na2S·9H2O超声溶解到40mL去离子水中,得到溶液B;用胶头滴管将溶液B以一定速率滴加到持续搅拌的悬浊液A中,继续搅拌后放置24h;用离心机以4000rpm转速离心,固形物用蒸馏水和无水乙醇各洗涤3次后,置入烘箱,60℃下烘干12h,研磨得到粉末状MnxZn1-xFe2O4/C/CdS样品。
本发明采用上述技术方案,主要有以下效果:
(1)本发明方法制备的磁性MnxZn1-xFe2O4/C/CdS复合光催化剂具有较高的光催化活性,在模拟太阳光氙灯照射下,0.1g制备的磁性MnxZn1-xFe2O4/C/CdS复合光催化材剂,分散于100mL浓度为10mg/L的罗丹明B溶液中,光照140min后对罗丹明B的降解率达到97.8%(在罗丹明B溶液浓度提高1倍的前提下,仍高于对比文件1制备的Fe3O4/C/CdS复合光催化剂)。
(2)本发明方法制备的磁性MnxZn1-xFe2O4/C/CdS复合光催化剂在外加磁场作用下的回收,3次重复使用后的降解率仍达到96.8%。
(3)本发明方法制备的磁性MnxZn1-xFe2O4/C/CdS复合光催化剂比表面积为96.20m2·g-1,远高于CdS的18.93m2·g-1。
(4)本发明方法制备的磁性MnxZn1-xFe2O4/C/CdS复合光催化剂,制备操作方法简单,所需设备少,能耗低。
附图说明
图1为MnxZn1-xFe2O4、MnxZn1-xFe2O4/C、CdS和MnxZn1-xFe2O4/C/CdS的X射线衍射图谱。
图2为MnxZn1-xFe2O4、MnxZn1-xFe2O4/C、CdS和MnxZn1-xFe2O4/C/CdS的扫描电子显微镜图。
图3为MnxZn1-xFe2O4、MnxZn1-xFe2O4/C和MnxZn1-xFe2O4/C/CdS的磁滞回线图。
具体实施方式
下面结合具体实施方式,进一步说明本发明。
实施例1
一种碳包覆磁性硫化镉复合光催化剂MnxZn1-xFe2O4/C/CdS的制备方法,具体步骤如下:
(1)MnxZn1-xFe2O4/C的制备
按照摩尔比n(MnO):n(ZnO):n(Fe2O3)=32.8:13.3:53.9,分别称取一定量的MnSO4·H2O、ZnSO4·7H2O和Fe2(SO4)3,加入一定量的去离子水,充分搅拌得到均匀的混合溶液;称取一定量的NaOH作为沉淀剂,配制成浓度为2mol/L的NaOH溶液;磁力搅拌下将NaOH溶液缓慢地滴入混合溶液,溶液中有棕褐色絮状沉淀物生成时,快速滴加NaOH溶液,调节pH至13,继续搅拌20min;将搅拌后的溶液转入100mL的反应釜中,在烘箱中200℃加热反应5h;水热反应完成后,取出放置冷却至室温,在外加磁铁的作用下,用蒸馏水和无水乙醇反复清洗样品,放置在烘箱中60℃烘干12h,最后研磨得到粉末状MnxZn1-xFe2O4样品;
称取3g葡萄糖,超声溶解到30mL去离子水中,得到浓度为0.5mol/L葡萄糖溶液;称取0.2g制备的MnxZn1-xFe2O4粉末,加入到溶液中并剧烈搅拌1h;然后,将溶液转移至50mL反应釜中,在烘箱中180℃加热5h;放置冷却至室温,同样利用外加磁铁,用蒸馏水和无水乙醇反复清洗样品,放置在烘箱中60℃烘干12h,最后研磨得到粉末状MnxZn1-xFe2O4/C样品;
(2)磁性复合光催化剂MnxZn1-xFe2O4/C/CdS的制备
按照摩尔比n(Cd2+):n(S2-)=1:1.25,称取0.8g的Cd(Ac)2·2H2O超声溶解到40mL去离子水中,加入与理论生成CdS质量比为5:100的MnxZn1-xFe2O4/C,机械搅拌30min得到悬浊液A;称取0.9g的Na2S·9H2O超声溶解到40mL去离子水中,得到溶液B;用胶头滴管将溶液B以一定速率滴加到持续搅拌的悬浊液A中,继续搅拌后放置24h;用离心机以4000rpm转速离心,固形物用蒸馏水和无水乙醇各洗涤3次后,置入烘箱,60℃下烘干12h,研磨得到粉末状MnxZn1-xFe2O4/C/CdS样品。
实施例2
一种碳包覆磁性硫化镉复合光催化剂MnxZn1-xFe2O4/C/CdS的制备方法,具体步骤如下:
(1)MnxZn1-xFe2O4/C的制备
同实施例1中(1)。
(2)磁性复合光催化剂MnxZn1-xFe2O4/C/CdS的制备
按照摩尔比n(Cd2+):n(S2-)=1:1.25,称取0.8g的Cd(Ac)2·2H2O超声溶解到40mL去离子水中,加入与理论生成CdS质量比为10:100的MnxZn1-xFe2O4/C,机械搅拌30min得到悬浊液A;称取0.9g的Na2S·9H2O超声溶解到40mL去离子水中,得到溶液B;用胶头滴管将溶液B以一定速率滴加到持续搅拌的悬浊液A中,继续搅拌后放置24h;用离心机以4000rpm转速离心,固形物用蒸馏水和无水乙醇各洗涤3次后,置入烘箱,60℃下烘干12h,研磨得到粉末状MnxZn1-xFe2O4/C/CdS样品。
实施例3
一种碳包覆磁性硫化镉复合光催化剂MnxZn1-xFe2O4/C/CdS的制备方法,具体步骤如下:
(1)MnxZn1-xFe2O4/C的制备
同实施例1中(1)。
(2)磁性复合光催化剂MnxZn1-xFe2O4/C/CdS的制备
按照摩尔比n(Cd2+):n(S2-)=1:1.25,称取0.8g的Cd(Ac)2·2H2O超声溶解到40mL去离子水中,加入与理论生成CdS质量比为15:100的MnxZn1-xFe2O4/C,机械搅拌30min得到悬浊液A;称取0.9g的Na2S·9H2O超声溶解到40mL去离子水中,得到溶液B;用胶头滴管将溶液B以一定速率滴加到持续搅拌的悬浊液A中,继续搅拌后放置24h;用离心机以4000rpm转速离心,固形物用蒸馏水和无水乙醇各洗涤3次后,置入烘箱,60℃下烘干12h,研磨得到粉末状MnxZn1-xFe2O4/C/CdS样品。
实验结果
实施例2制备的磁性复合光催化剂MnxZn1-xFe2O4/C/CdS催化降解活性最佳。为了方便对比,制备了CdS样品。CdS制备方法为实施例2步骤(2)中不加入MnxZn1-xFe2O4/C。
CdS的X射线衍射图如图1(b)所示,各衍射峰与国际标准卡片(JCPDS NO.80-0019)能很好地匹配,2θ为26.57°、44.67°和54.61°处的衍射峰分别对匹配CdS的(111)、(220)和(311)晶面,说明制备的纯的样品是面心立方体结构的CdS。
MnxZn1-xFe2O4的X射线衍射图如图1(d)所示,各衍射峰与国际标准卡片(JCPD 24-7400)相对应,在2θ为18.2°、29.9°、35.2°、42.6°、52.9°、56.3°和61.9°处的衍射峰分别对应其(111)、(220)、(311)、(400)、(422)、(511)和(440)晶面,证明实验所制备的MnxZn1- xFe2O4为四方晶型MnxZn1-xFe2O4。
MnxZn1-xFe2O4/C的X射线衍射图如图1(c)所示,其衍射峰位置、强度与MnxZn1-xFe2O4基本吻合,说明包覆碳层没有影响MnxZn1-xFe2O4晶体结构。
MnxZn1-xFe2O4/C/CdS的X射线衍射图如图1(a)所示,三个较强的衍射峰与CdS的主要晶面(111)、(220)、(311)基本吻合,在2θ为35.2°位置出现一个较小的衍射峰,能够与MnxZn1-xFe2O4/C最高峰对应的(311)晶面相匹配。MnxZn1-xFe2O4/C/CdS的XRD分析说明磁性基体和CdS成功复合,它们的衍射峰都能很好地匹配,其晶型和物相没有互相影响,从而有效保证了复合磁性光催化剂MnxZn1-xFe2O4/C/CdS的磁性能和光催化性能。
CdS颗粒的SEM扫描图如图2(a)所示,CdS颗粒小,最小粒径在纳米级别,因此在颗粒表面存在非常大的表面能,使颗粒趋于聚集,发生团聚现象。
MnxZn1-xFe2O4和MnxZn1-xFe2O4/C的SEM扫描图分别如图2(b)和图2(c)所示,两者形貌均是由不规则颗粒团聚而成,而MnxZn1-xFe2O4/C表面由于被碳层包覆而发生明显改变,表明了MnxZn1-xFe2O4/C的成功制备。
MnxZn1-xFe2O4/C/CdS的SEM扫描图如图2(d)所示,由于MnxZn1-xFe2O4/C提供了较大比表面积和吸附性,而且CdS颗粒小,从而使CdS均匀分布覆盖在MnxZn1-xFe2O4/C的表面,最终形成拥有MnxZn1-xFe2O4、C和CdS三层结构的复合样MnxZn1-xFe2O4/C/CdS。
MnxZn1-xFe2O4、MnxZn1-xFe2O4/C和MnxZn1-xFe2O4/C/CdS的磁滞回线如图3所示,MnxZn1-xFe2O4和MnxZn1-xFe2O4/C的饱和磁化强度分别为66.08emu/g、30.82emu/g,MnxZn1- xFe2O4/C饱和磁化强度的减少可归因于其表面覆盖了碳层;MnxZn1-xFe2O4/C/CdS的饱和磁化强度为2.17emu/g,相比MnxZn1-xFe2O4/C下降较多,但利用外加磁场对分散在水溶液中的复合样进行回收,能迅速被磁介质完全聚集,表明MnxZn1-xFe2O4/C/CdS仍具备出色的磁性能,能够满足磁回收的磁性要求,说明磁性复合光催化剂MnxZn1-xFe2O4/C/CdS的成功制备。
比表面积测试表明,磁性MnxZn1-xFe2O4/C/CdS复合光催化剂比表面积为96.20m2·g-1,远高于CdS的18.93m2·g-1。
光催化结果表明,在模拟太阳光氙灯照射下,0.1g制备的磁性复合光催化剂降解100mL浓度为10mg/L的罗丹明B溶液,140min的降解率达到97.8%,在外加磁场下对光催化剂的磁回收重复使用,3次后降解率为96.8%,说明采用本发明制备的磁性复合光催化剂MnxZn1-xFe2O4/C/CdS具有较高的光催化活性和稳定的磁回收性能。
Claims (1)
1.一种制备碳包覆磁性硫化镉复合光催化剂的方法,具体步骤如下:
(1)MnxZn1-xFe2O4/C的制备
按照摩尔比MnO:ZnO:Fe2O3=32.8:13.3:53.9,分别称取一定量的MnSO4·H2O、ZnSO4·7H2O和Fe2(SO4)3,加入一定量的去离子水,充分搅拌得到均匀的混合溶液;称取一定量的NaOH作为沉淀剂,配制成浓度为2mol/L的NaOH溶液;磁力搅拌下将NaOH溶液缓慢地滴入混合溶液,溶液中有棕褐色絮状沉淀物生成时,快速滴加NaOH溶液,调节pH至13,继续搅拌20min;将搅拌后的溶液转入100mL的反应釜中,在烘箱中200℃加热反应5h;水热反应完成后,取出放置冷却至室温,在外加磁铁的作用下,用蒸馏水和无水乙醇反复清洗样品,放置在烘箱中60℃烘干12h,最后研磨得到粉末状MnxZn1-xFe2O4样品;
称取3g葡萄糖,超声溶解到30mL去离子水中,得到浓度为0.5mol/L葡萄糖溶液;称取0.2g制备的MnxZn1-xFe2O4粉末,加入到溶液中并剧烈搅拌1h;然后,将溶液转移至50mL反应釜中,在烘箱中180℃加热5h;放置冷却至室温,同样利用外加磁铁,用蒸馏水和无水乙醇反复清洗样品,放置在烘箱中60℃烘干12h,最后研磨得到粉末状MnxZn1-xFe2O4/C样品;
(2)磁性复合光催化剂MnxZn1-xFe2O4/C/CdS的制备
按照摩尔比Cd2+:S2-=1:1.25,称取0.8g的Cd(Ac)2·2H2O超声溶解到40mL去离子水中,加入与理论生成CdS质量比为5~15:100的MnxZn1-xFe2O4/C,机械搅拌30min得到悬浊液A;称取0.9g的Na2S·9H2O超声溶解到40mL去离子水中,得到溶液B;用胶头滴管将溶液B以一定速率滴加到持续搅拌的悬浊液A中,继续搅拌后放置24h;用离心机以4000rpm转速离心,固形物用蒸馏水和无水乙醇各洗涤3次后,置入烘箱,60℃下烘干12h,研磨得到粉末状MnxZn1- xFe2O4/C/CdS样品。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102350365A (zh) * | 2011-08-16 | 2012-02-15 | 淮阴师范学院 | CdS-凹凸棒土光电复合材料的合成方法 |
CN103785476A (zh) * | 2014-01-15 | 2014-05-14 | 江苏大学 | 基于磁性碳质材料的表面印迹CdS复合光催化剂的制备方法 |
CN104275196A (zh) * | 2014-10-24 | 2015-01-14 | 浙江师范大学 | 四氧化三铁/碳/硫化镉复合纳米材料及其制备方法 |
CN106111211A (zh) * | 2016-06-25 | 2016-11-16 | 董晓 | 一种改性核壳结构Fe3O4/C/TiO2复合材料的制备方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102350365A (zh) * | 2011-08-16 | 2012-02-15 | 淮阴师范学院 | CdS-凹凸棒土光电复合材料的合成方法 |
CN103785476A (zh) * | 2014-01-15 | 2014-05-14 | 江苏大学 | 基于磁性碳质材料的表面印迹CdS复合光催化剂的制备方法 |
CN104275196A (zh) * | 2014-10-24 | 2015-01-14 | 浙江师范大学 | 四氧化三铁/碳/硫化镉复合纳米材料及其制备方法 |
CN106111211A (zh) * | 2016-06-25 | 2016-11-16 | 董晓 | 一种改性核壳结构Fe3O4/C/TiO2复合材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
"新型磁性Mn0.6Zn0.4Fe2O4@CdS纳米复合光催化剂的制备及其吸附和光催化特性";黄华等;《环境科学学报》;20200119;第40卷(第1期);第128-137页 * |
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