CN114618529B - 磁性石墨烯基光催化剂GO-Fe3O4@SiO2@CdS及其制备方法和应用 - Google Patents
磁性石墨烯基光催化剂GO-Fe3O4@SiO2@CdS及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种磁性石墨烯基光催化剂GO‑Fe3O4@SiO2@CdS及其制备方法和应用，涉及光催化剂技术领域。本发明采用溶胶‑凝胶工艺在Fe3O4上负载SiO2壳层，得到Fe3O4@SiO2的纳米球；然后以氯化镉为原料，将CdS的小颗粒分散在Fe3O4@SiO2的纳米球上；最后将氧化石墨烯(GO)和Fe3O4@SiO2@CdS在超声分散于乙醇‑水的混合溶液，采用水热法制备得到GO‑Fe3O4@SiO2@CdS复合光催化剂。利用本发明方法所制备的光催化剂在短时间内可使得废水中的菲和芘几乎完全降解。所以其在处理多环芳烃废水方面具有广阔的应用前景。
Description
技术领域
本发明属于光催化技术领域，具体涉及磁性石墨烯基光催化剂GO-Fe3O4@SiO2@CdS及其制备方法和应用。
背景技术
水环境中的PAHs由于具有高毒性和致癌性，已对人类的健康造成了严重威胁。而在处理PAHs废水的方法中，光催化降解PAHs因其操作简单，成本低、无二次污染等优点而受到广泛关注。其中TiO2光催化剂因其低成本、无毒性和高活性而受到广泛关注。
但是，TiO2由于是宽带隙半导体，只能吸收紫外光(占太阳光的5％)，不能有效地利用可见光(占太阳光的45％)。因此，迫切需要开发对可见光有响应的高效光催化剂。而CdS半导体由于其合适的带隙使其可吸收可见光。然而，其光生电子空穴容易复合和易发生光腐蚀的问题限制了其应用。
近年来，通过将石墨烯与CdS耦合可以有效地缓解上述发生的问题。这主要是因为石墨烯具有优异的电子导电性、独特的二维表面和体积比和化学稳定性，可使得CdS中的光生电子可以转移到石墨烯上，从而促进电子空穴的分离，进而有效地缓解CdS发生光腐蚀的问题。而进一步在实际应用光催化剂降解PAHs的过程中，发现催化剂存在难以回收的问题，将光催化剂与Fe3O4复合可以很方便地实现光催化剂的回收再利用。到目前为止，关于复合光催化剂GO-Fe3O4@SiO2@CdS的报道非常少。
发明内容
有鉴于此，本发明的目的在于提供一种可磁性可分离的GO-Fe3O4@SiO2@CdS光催化剂的制备方法。
本发明的另一个目的在于提供一种磁性可分离的GO-Fe3O4@SiO2@CdS光催化剂降解菲和芘的应用。
为达到上述第一个目的，本发明采用如下技术方案：
磁性可分离GO-Fe3O4@SiO2@CdS光催化剂的制备方法如下：
(1)Fe3O4的制备：将一定量的FeCl3溶于100mL乙二醇中，使其完全溶解后，再加入一定量的柠檬酸钠和醋酸钠混合；然后将混合液转移至反应釜中，在180-200℃下保持10-12h；将得到的黑色产物在磁场中进行分离洗涤并干燥后，得到磁性Fe3O4。
(2)Fe3O4@SiO2的制备：将一定量步骤(1)得到的Fe3O4超声分散于乙醇溶液中；接着量取一定量的水、乙醇和浓氨水加入到上述溶液中；然后将一定量的正硅酸四乙酯滴加进混合溶液中，并搅拌10-12h；最后将磁选得到的Fe3O4@SiO2产物洗涤干燥；其中乙醇和水的体积比为4:1。
(3)Fe3O4@SiO2@CdS的制备：将一定量步骤(2)得到的Fe3O4@SiO2超声分散于水溶液中，再分别滴加一定浓度的柠檬酸钠水溶液和氯化镉水溶液，并搅拌1-2h；随后再分别滴加一定量的的氨水和硫脲水溶液，并加热至60-80℃，并搅拌3-5h；最后磁选分离得到Fe3O4@SiO2@CdS；其中柠檬酸钠水溶液和氯化镉水溶液的浓度比为1:1；氨水和硫脲水溶液的体积比为1:1。
(4)GO的制备：将一定量的石墨和硝酸钠超生分散到浓硫酸中；接着在冰浴环境下缓慢加入一定量的高锰酸钾，并搅拌10-12h；然后滴加一定量的蒸馏水并在40-50℃下继续搅拌10-12h；随后在35℃下继续搅拌20-24h，并缓慢加入一定量的H2O2，继续搅拌1-3h；最后分别用5％HCl溶液、乙醇和水依次洗涤，直至上清液的pH值变为中性，得到GO。
(5)GO-Fe3O4@SiO2@CdS的制备：将一定量步骤(4)得到GO超声分散于乙醇-水的混合溶液中；然后，在GO分散液中加入一定量步骤(3)得到的Fe3O4@SiO2@CdS；随后待混合液搅拌1-2h后，将其转移到反应釜中，在100-120℃下反应20-24h；最后磁选收集得到GO-Fe3O4@SiO2@CdS；其中乙醇和水的体积比为2:1。
为达到上述第二个目的，本发明采用如下技术方案：
(1)配置0.1mg/L的菲和芘溶液。
(2)将GO-Fe3O4@SiO2@CdS光催化剂加入到装有菲或芘溶液的反应器中，先在黑暗环境中吸附30-100min以达到吸附平衡，然后用150W的模拟太阳光照射反应器，在相应的时间间隔下取样并进行荧光测试计算菲或芘的浓度。
有益效果
(1)利用GO修饰Fe3O4@SiO2@CdS可以抑制光生电子-空穴对的快速复合，并且有利于缓解CdS发生光腐蚀，进而提高光催化剂的稳定性。
(2)利用磁铁来分离光催化剂，使其可以被快速回收，从而有效地避免其给环境带来的二次污染。
(3)将本发明的GO-Fe3O4@SiO2@CdS光催化剂应用在分别降解含菲和芘的废水时，其可达到86％和93％的去除率。
附图说明
图1为GO-Fe3O4@SiO2@CdS的扫描电子显微镜图；
图2为Fe3O4@SiO2@CdS和GO-Fe3O4@SiO2@CdS的光电流图；
图3为Fe3O4@SiO2@CdS和GO-Fe3O4@SiO2@CdS的交流阻抗图；
图4为Fe3O4@SiO2@CdS和GO-Fe3O4@SiO2@CdS降解菲的效果图；
图5为是Fe3O4@SiO2@CdS和GO-Fe3O4@SiO2@CdS降解芘的效果图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明的技术方案做任何形式的限定。
实施例1：GO-Fe3O4@SiO2@CdS光催化剂的制备
(1)Fe3O4的制备：首先将3.25g FeCl3溶于100mL乙二醇中，使其完全溶解后，再加入1.2g柠檬酸钠，搅拌15min；然后加入6g醋酸钠，在80℃下连续搅拌1h后将混合物转移到150ml的聚四氟乙烯不锈钢高压釜中，在190℃反应11h后，得到Fe3O4产物。
(2)Fe3O4@SiO2的制备：将步骤(1)得到的Fe3O4(3.0mL,0.05g/mL)乙醇分散液超声分散于140mL乙醇、35mL H2O和4ml浓氨水溶液中，再超声15min后将4.0ml的正硅酸四乙酯在16min内滴加进溶液中，在室温下连续机械搅拌11h后，得到Fe3O4@SiO2。
(3)Fe3O4@SiO2@CdS的制备：将步骤(2)得到的300mg Fe3O4@SiO2分散于200ml的H2O中并超声15min，再缓慢地滴加1ml的2mol/l的柠檬酸钠水溶液和1ml的2mol/l的氯化镉水溶液，机械搅拌1h。随后在分别滴加4ml的氨水和4ml的1mol/l的硫脲水溶液。并在70℃下搅拌5h后，待其自然冷却后，得到Fe3O4@SiO2@CdS。
(4)GO的制备：将2.0g石墨、1.2g硝酸钠和60mL浓H2SO4滴加到250mL圆底烧瓶中。并将所得混合物进一步超声处理30min，然后将烧瓶置于冰水浴中搅拌30min。随后，缓慢加入4.4g高锰酸钾，在冰浴环境下连续搅拌10h。然后，滴加72mL蒸馏水并在反应温度为50℃下继续搅拌10h。将反应温度改为35℃，再搅拌22h。缓慢加入22mL H2O2，将混合物搅拌3h。最后用5％HCl溶液、乙醇和水依次洗涤，直至上清液的pH值变为中性，得到GO。
(5)GO-Fe3O4@SiO2@CdS的制备：将步骤(4)得到的5mg GO在超声作用下分散于100ml乙醇/水(2:1v/v)溶液中超声1h。然后，在GO分散液中加入步骤(3)得到的0.5g Fe3O4@SiO2@CdS，再超声30min。随后在室温下将上述混合液搅拌2h形成均匀悬浮液，将其转移到150ml的不锈钢高压釜中，在120℃下反应24h后，得到GO-Fe3O4@SiO2@CdS。
实施例2：GO-Fe3O4@SiO2@CdS光催化剂的制备
(1)Fe3O4的制备：首先将3.25g FeCl3溶于100mL乙二醇中，使其完全溶解后，再加入1.2g柠檬酸钠，搅拌15min；然后加入6g醋酸钠，在80℃下连续搅拌1h后将混合物转移到150ml的聚四氟乙烯不锈钢高压釜中，在200℃反应12h后，得到Fe3O4产物。
(2)Fe3O4@SiO2的制备：将步骤(1)得到的Fe3O4(3.0mL,0.05g/mL)乙醇分散液超声分散于280mL乙醇、70mL H2O和4ml浓氨水溶液中，再超声15min后将4.0ml的正硅酸四乙酯在16min内滴加进溶液中，在室温下连续机械搅拌12h后，得到Fe3O4@SiO2。
(3)Fe3O4@SiO2@CdS的制备：将步骤(2)得到的300mg Fe3O4@SiO2分散于200ml的H2O中并超声15min，再缓慢地滴加1ml的2mol/l的柠檬酸钠水溶液和1ml的2mol/l的氯化镉水溶液，机械搅拌1h。随后在分别滴加4ml的氨水和4ml的1mol/l的硫脲水溶液并在60℃下搅拌5h后，待其自然冷却后，得到Fe3O4@SiO2@CdS。
(4)GO的制备：将2.0g石墨、1.2g硝酸钠和60mL浓H2SO4滴加到250mL圆底烧瓶中。并将所得混合物进一步超声处理30min，然后将烧瓶置于冰水浴中搅拌30min。随后，缓慢加入6.6g高锰酸钾，在冰浴环境下连续搅拌12h。然后，滴加72mL蒸馏水并在反应温度为50℃下继续搅拌11h。将反应温度改为35℃，再搅拌23h。缓慢加入22mL H2O2，将混合物搅拌3h。最后用5％HCl溶液、乙醇和水依次洗涤，直至上清液的pH值变为中性，得到GO。
(5)GO-Fe3O4@SiO2@CdS的制备：将步骤(3)得到的5mg GO在超声作用下分散于120ml乙醇/水(2:1v/v)溶液中超声1h。然后，在GO分散液中加入步骤(3)得到的0.5g Fe3O4@SiO2@CdS，再超声30min。随后在室温下将上述混合液搅拌2h形成均匀悬浮液，将其转移到150ml的不锈钢高压釜中，在120℃下反应22h后，得到GO-Fe3O4@SiO2@CdS。
实施例3：GO-Fe3O4@SiO2@CdS光催化剂的制备
(1)Fe3O4的制备：首先将3.25g FeCl3溶于100mL乙二醇中，使其完全溶解后，再加入1.2g柠檬酸钠，搅拌15min；然后加入6g醋酸钠，在80℃下连续搅拌1h后将混合物转移到150ml的聚四氟乙烯不锈钢高压釜中，在180℃反应12h后，得到Fe3O4产物。
(2)Fe3O4@SiO2的制备：将步骤(1)得到的Fe3O4(3.0mL,0.05g/mL)乙醇分散液超声分散于80mL乙醇、20mL H2O和4ml浓氨水溶液中，再超声15min后将4.0ml的正硅酸四乙酯在16min内滴加进溶液中，在室温下连续机械搅拌11h后，得到Fe3O4@SiO2。
(3)Fe3O4@SiO2@CdS的制备：将步骤(2)得到300mg的Fe3O4@SiO2分散于200ml的H2O中并超声15min，再缓慢地滴加1ml的2mol/l的柠檬酸钠水溶液和1ml的2mol/l的氯化镉水溶液，机械搅拌1h。随后在分别滴加4ml的氨水和4ml的1mol/l的硫脲水溶液并在75℃下搅拌4h后，待其自然冷却后，得到Fe3O4@SiO2@CdS。
(4)GO的制备：将2.0g石墨、1.2g硝酸钠和60mL浓H2SO4滴加到250mL圆底烧瓶中。并将所得混合物进一步超声处理30min，然后将烧瓶置于冰水浴中搅拌30min。随后，缓慢加入3.3g高锰酸钾，在冰浴环境下连续搅拌10h。然后，滴加72mL蒸馏水并在反应温度为50℃下继续搅拌10h。将反应温度改为35℃，再搅拌22h。缓慢加入22mL H2O2，将混合物搅拌3h。最后用5％HCl溶液、乙醇和水依次洗涤，直至上清液的pH值变为中性，得到GO。
(5)GO-Fe3O4@SiO2@CdS的制备：将步骤(4)得到5mg GO在超声作用下分散于90ml乙醇/水(2:1v/v)溶液中超声1h。然后，在GO分散液中加入0.5g步骤(3)得到的Fe3O4@SiO2@CdS，再超声30min。随后在室温下将上述混合液搅拌2h形成均匀悬浮液，将其转移到150ml的不锈钢高压釜中，在120℃下反应23h后，得到GO-Fe3O4@SiO2@CdS。
本发明以实施例1～3所制备的GO-Fe3O4@SiO2@CdS复合物进行光催化降解有机污染物实验。
GO-Fe3O4@SiO2@CdS在光催化降解含菲和芘的废水中的应用，步骤如下：
(1)配置0.1mg/L的菲和芘溶液。
(2)将实施例1、实施例2、实施例3得到的GO-Fe3O4@SiO2@CdS光催化剂加入到装有菲或芘溶液的反应器中，先在黑暗环境中吸附30-100min以达到吸附平衡，然后用150W的模拟太阳光照射反应器，在相应的时间间隔下取样并进行荧光测试计算菲或芘的浓度。
GO-Fe3O4@SiO2@CdS的微观形貌通过扫描电镜结果得到，如图1所示，可以看到Fe3O4@SiO2@CdS纳米球负载在GO的片层上。
另外，GO-Fe3O4@SiO2@CdS的光电化学性质如图2和图3所示，结果表明GO-Fe3O4@SiO2@CdS的电子-空穴分离效率比纯Fe3O4@SiO2@CdS强。
同时，在模拟太阳光照射下菲和芘的光催化降解情况如图4和图5所示，GO-Fe3O4@SiO2@CdS能降解更多的菲和芘，说明GO-Fe3O4@SiO2@CdS的光催化性能比Fe3O4@SiO2@CdS强。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (1)
1.磁性石墨烯基光催化剂GO-Fe3O4@SiO2@CdS在降解废水中菲和芘中的应用，所述磁性石墨烯基光催化剂GO-Fe3O4@SiO2@CdS的制备方法，包括以下步骤：(1)在磁性Fe3O4上负载SiO2壳层，得到Fe3O4@SiO2纳米球；
(2)在Fe3O4@SiO2的纳米球上负载CdS的小颗粒，得到Fe3O4@SiO2@CdS；
(3)将氧化石墨烯和Fe3O4@SiO2@CdS共同超声分散于乙醇-水的混合溶液，采用水热法制备得到GO-Fe3O4@SiO2@CdS复合光催化剂。
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