CN112169791B - 一种片层状三相复合光催化材料的制备方法 - Google Patents
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Abstract
本发明公开了一种片层状三相复合光催化材料的制备方法，具体按照以下步骤实施：步骤1：石墨烯分散液和K2PtCl6溶液混合均匀；步骤2：然后逐滴加入与K2PtCl6溶液相同体积的NaBH4溶液反应后制得石墨烯/纳米铂复合材料；步骤3：取木质素磺酸钠加入蒸馏水中，在冰水浴中搅拌10min，得到木质素磺酸钠溶液；将步骤2制得的石墨烯/纳米铂复合材料分散于木质素磺酸钠溶液后，分别加入吡咯和FeCl3溶液制备石墨烯/纳米铂/聚吡咯三相复合光催化材料。采用该方法制备的层状三相复合光催化材料具有高的可见光捕获能力、电子和空穴分离、传输效果好、在可将光照射条件下具有较高的光催化降解性能。
Description
技术领域
本发明属于光催化材料领域，具体涉及一种片层状三相复合光催化材料的制备方法。
背景技术
在过去的几个世纪里，环境污染及其控制是人类面临的重大挑战之一，每年纺织工业中排放的大量含有有机染料的废水。这些大分子具有潜在的致癌性、毒性、和顽固的不可生物降解性，由于其有害的生态效应和对人类健康的巨大风险，有机污染物的高效清除方法是急需解决的重大科学问题。石墨烯由于其独特的二维蜂窝状的结构、化学稳定性、同时对于载流子还具有高迁移率等优点，基于石墨烯(GO)的复合材料日渐成为可见光光催化领域研究的热点。但是，石墨烯之间范德华力很强，容易发生团聚，严重限制了石墨烯的光催化性能及其应用。纳米金属颗粒(MNP)由于其独特的物理、化学和电子性能而广泛应用于各种复合材料的构建。人们已经将MNP与GO复合，用于改善石墨烯的光催化性能。但目前所得的复合光催化材料对可见光捕获能力和电子传输效率低、对有机污染物降解性能差等缺点。
发明内容
本发明所要解决的技术问题是提供一种制备工艺简单、对可将光响应性能高，且具有高光催化能力的片层状复合光催化材的制备方法。
本发明采用的技术方案是：一种片层状三相复合光催化材的制备方法，具体操作步骤如下：
步骤1：取通过超声剥离制备的2.5g/L石墨烯分散液和预先经过超声处理30min的5mM的K2PtCl6溶液混合均匀；
步骤2：然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂复合材料；
步骤3：取木质素磺酸钠加入蒸馏水中，在冰水浴中搅拌10min，得到木质素磺酸钠溶液；将步骤2制得的石墨烯/纳米铂复合材料分散于木质素磺酸钠溶液后，分别逐滴加入吡咯和0.2892M的FeCl3溶液；在冰水浴条件下边搅拌边反应后过滤、洗涤和干燥后得石墨烯/纳米铂/聚吡咯三相复合光催化材料。
本发明的特点还在于，
步骤1石墨烯分散液和K2PtCl6溶液的体积比为1:2～6。
步骤3木质素磺酸钠与蒸馏水的比例为1g:100mL。
步骤3吡咯和FeCl3溶液的体积比为0.6mL～1.0mL：50mL；FeCl3溶液与步骤1石墨烯分散液的体积比为10:1。
步骤3反应的条件为：在冰水浴中边搅拌边反应时间不少于7h。
步骤3冰水浴温度范围是0-5℃。
本发明一种片层状三相复合光催化材料的制备方法具有如下优点：
1.以石墨烯为基材，利用纳米铂的表面等离子共振效应和聚吡咯优异的导电和对可见光的捕获性能，成功地得到了三相复合光催化材料GO/PtNPs/PPy。
2.制备过程对设备要求低、且反应条件温和，合成工艺简单易于实现。
3.采用该方法制备的层状三相复合光催化材料具有高的可见光捕获能力、电子和空穴分离、传输效果好、光催化降解性能高。
4.为制备其它基于石墨烯的多相光催化材料提供了可靠的层状三相复合光催化材料参考依据。
附图说明
图1为本发明中石墨烯、纳米铂、聚吡咯三种单体和复合材料GO/PtNPs/PPy的紫外可见漫反射图；
图2为本发明中石墨烯、纳米铂、聚吡咯三种单体和复合材料GO/PtNPs/PPy的红外光谱图；
图3为本发明中制备的光催化材料GO/PtNPs/PPy的能谱图(EDX)；
图4(a)为本发明对比例1中制备的GO/PtNPs/PPy光催化材料的SEM图；
图4(b)为本发明对比例2中制备的GO/PtNPs/PPy光催化材料的SEM图；
图4(c)为本发明对比例3中制备的GO/PtNPs/PPy光催化材料的SEM图；
图4(d)为本发明实施例1中制备的GO/PtNPs/PPy光催化材料的SEM图；
图4(e)为本发明实施例2中制备的GO/PtNPs/PPy光催化材料的SEM图；
图4(f)为本发明实施例3中制备的GO/PtNPs/PPy光催化材料的SEM图；
图5(a)为本发明对比例1中制备的GO/PtNPs/PPy光催化材料对亚甲基蓝溶液的光催化降解效率图；
图5(b)为本发明对比例2中制备的GO/PtNPs/PPy光催化材料对亚甲基蓝溶液的光催化降解效率图；
图5(c)为本发明对比例3中制备的GO/PtNPs/PPy光催化材料对亚甲基蓝溶液的光催化降解效率图；
图5(d)为本发明实施例1中制备的GO/PtNPs/PPy光催化材料对亚甲基蓝溶液的光催化降解效率图；
图5(e)为本发明实施例2中制备的GO/PtNPs/PPy光催化材料对亚甲基蓝溶液的光催化降解效率图。
图5(f)为本发明实施例3中制备的GO/PtNPs/PPy光催化材料对亚甲基蓝溶液的光催化降解效率图。
具体实施方式
下面结合附图和具体实施例对本发明进一步说明。
对比例1
取5mL通过超声剥离制备的2.5g/L石墨烯分散和一定体积事先超声处理30min的5mM的K2PtCl6溶液混合均匀，然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂(GO/PtNPs)复合材料，所述K2PtCl6和NaBH4溶液体积为15mL；取1g木质素磺酸钠加入100mL蒸馏水中，在冰水浴中搅拌10min，将上述制得的GO/PtNPs复合材料分散于此溶液后，分别逐滴加入0.2mL的吡咯和50mL 0.2892M的FeCl3溶液。在冰水浴条件下边搅拌边反应7h后过滤、洗涤,放置于烘箱内在60℃的条件下烘干12h后即得三相石墨烯/纳米铂/聚吡咯(GO/PtNPs/PPy)复合光催化材料。
由上述方法制备的GO/PtNPs/PPy光催化材料标记为a。
对比例2
取5mL通过超声剥离制备的2.5g/L石墨烯分散液和一定体积事先超声处理30min的5mM的K2PtCl6溶液混合均匀，然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂(GO/PtNPs)复合材料，所述K2PtCl6和NaBH4溶液体积为15mL；取1g木质素磺酸钠加入100mL蒸馏水中，在冰水浴中搅拌10min，将上述制得的GO/PtNPs复合材料分散于此溶液后，分别逐滴加入0.6mL的吡咯和50mL 0.2892M的FeCl3溶液。在冰水浴条件下边搅拌边反应7h后过滤、洗涤,放置于烘箱内在60℃的条件下烘干12h后即得三相石墨烯/纳米铂/聚吡咯(GO/PtNPs/PPy)复合光催化材料。
由上述方法制备的GO/PtNPs/PPy光催化材料标记为b。
对比例3
取5mL通过超声剥离制备的2.5g/L石墨烯分散液和一定体积事先超声处理30min的5mM的K2PtCl6溶液混合均匀，然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂(GO/PtNPs)复合材料，所述K2PtCl6和NaBH4溶液体积为15mL；取1g木质素磺酸钠加入100mL蒸馏水中，在冰水浴中搅拌10min，将上述制得的GO/PtNPs复合材料分散于此溶液后，分别逐滴加入1.0mL的吡咯和50mL 0.2892M的FeCl3溶液。在冰水浴条件下边搅拌边反应7h后过滤、洗涤,放置于烘箱内在60℃的条件下烘干12h后即得三相石墨烯/纳米铂/聚吡咯(GO/PtNPs/PPy)复合光催化材料。
由上述方法制备的GO/PtNPs/PPy光催化材料标记为c。
实施例1
取5mL通过超声剥离制备的2.5g/L石墨烯分散液和一定体积事先超声处理30min的5mM的K2PtCl6溶液混合均匀，然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂(GO/PtNPs)复合材料，所述K2PtCl6和NaBH4溶液体积为25mL；取1g木质素磺酸钠加入100mL蒸馏水中，在冰水浴中搅拌10min，将上述制得的GO/PtNPs复合材料分散于此溶液后，分别逐滴加入0.6mL的吡咯和50mL 0.2892M的FeCl3溶液。在冰水浴条件下边搅拌边反应7h后过滤、洗涤,放置于烘箱内在60℃的条件下烘干12h后即得三相石墨烯/纳米铂/聚吡咯(GO/PtNPs/PPy)复合光催化材料。
由上述方法制备的GO/PtNPs/PPy光催化材料标记为d。
实施例2
取5mL通过超声剥离制备的2.5g/L石墨烯分散液和一定体积事先超声处理30min的5mM的K2PtCl6溶液混合均匀，然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂(GO/PtNPs)复合材料，所述K2PtCl6和NaBH4溶液体积为25mL；取1g木质素磺酸钠加入100mL蒸馏水中，在冰水浴中搅拌10min，将上述制得的GO/PtNPs复合材料分散于此溶液后，分别逐滴加入1.0mL的吡咯和50mL 0.2892M的FeCl3溶液。在冰水浴条件下边搅拌边反应7h后过滤、洗涤,放置于烘箱内在60℃的条件下烘干12h后即得三相石墨烯/纳米铂/聚吡咯(GO/PtNPs/PPy)复合光催化材料。
由上述方法制备的GO/PtNPs/PPy光催化材料标记为e。
实施例3
取5mL通过超声剥离制备的2.5g/L石墨烯分散液和一定体积事先超声处理30min的5mM的K2PtCl6溶液混合均匀，然后逐滴加入与K2PtCl6溶液相同体积的200mM NaBH4溶液反应后制得石墨烯/纳米铂(GO/PtNPs)复合材料，所述K2PtCl6和NaBH4溶液体积为35mL；取1g木质素磺酸钠加入100mL蒸馏水中，在冰水浴中搅拌10min，将上述制得的GO/PtNPs复合材料分散于此溶液后，分别逐滴加入1.0mL的吡咯和50mL 0.2892M的FeCl3溶液。在冰水浴条件下边搅拌边反应7h后过滤、洗涤,放置于烘箱内在60℃的条件下烘干12h后即得三相石墨烯/纳米铂/聚吡咯(GO/PtNPs/PPy)复合光催化材料。
由上述方法制备的GO/PtNPs/PPy光催化材料标记为f。
图1为所制备的GO/PtNPs/PPy复合光催化材料的紫外漫反射图。由图1可知，与各单体相比较，复合材料对可见光的有着显著提高的吸收能力，将在可见光下展示更强的光催化性能。
图2为本发明中石墨烯、聚吡咯两种单体和复合材料GO/PtNPs/PPy的红外光谱图。通过对比GO、PPy和复合材料的红外光谱图，可以看出复合材料在3402.2，2341.4，2358.8，1451.0，1184.2，1045.3，669.3cm-1处有强烈吸收峰，与GO和PPy的特征峰基本一致。进一步证明了GO和PPy成功地负载于GO/PtNPs/PPy复合光催化材料中。
图3为所制备的GO/PtNPs/PPy复合光催化材料的能谱图(EDX)。由图3可知，纳米铂分散较均匀，PPy也负载于GO表面。同时，复合材料的能谱图(EDX)还显示，复合材料中包含Pt、Cl、O、N、C等元素的含量。(其中含量较为丰富的Au元素是因为在做电镜时因为喷金所引入的，与本次实验无关)。进一步证明通过该制备方法成功地制备了GO/PtNPs/PPy复合光催化材料。
如图4(a)-(f)所示，为本发明中所制备的GO/PtNPs/PPy复合光催化材料的SEM图，对比例1、对比例2、对比例3、实施例1、实施例2和实施例3中制备的GO/PtNPs/PPy复合光催化材料分别为a、b、c、d、e和f，由图4(a)可知，当5mM的K2PtCl6和200mM NaBH4溶液的用量都为15mL,使用0.2mL的吡咯时，得到的GO/PtNPs/PPy复合光催化材料a没有固定的形状，有团聚的聚吡咯分散在石墨烯的表面。由图4(b)可知，当5mM的K2PtCl6和200mM NaBH4溶液的用量都为15mL,使用0.6mL的吡咯时，得到的GO/PtNPs/PPy复合光催化材料b呈无规则的颗粒状，颗粒表面粗糙，且团聚明显。由图4(c)可知，当5mM的K2PtCl6和200mM NaBH4溶液的用量都为15mL,使用1.0mL的吡咯时，得到的GO/PtNPs/PPy复合光催化材料c呈卷曲的片状结构，纳米铂颗粒分散均匀，材料表面具有明显的孔隙结构；由图4(d)可知，当5mM的K2PtCl6和200mM NaBH4溶液的用量都为25mL,使用0.6mL的吡咯时，得到的GO/PtNPs/PPy复合光催化材料d呈骨节状结构，片层表面具有明显的孔隙结构；由图4(e)可知，当5mM的K2PtCl6和200mM NaBH4液的用量都为25mL,使用1.0mL的吡咯时，得到的GO/PtNPs/PPy复合光催化材料e呈片层状，但层与层之间堆积比较紧密，不利于有机污染物在催化剂表面的预吸附；由图4(f)可知，当5mM的K2PtCl6和200mM NaBH4溶液的用量都为35mL,使用1.0mL的吡咯时，得到的GO/PtNPs/PPy复合光催化材料e呈片层状，且有效地克服了层与层之间的紧密堆积，有利于有机污染物在催化剂表面的预吸附，增大了污染物与催化剂表面的碰撞机会，提高其光催化降解性能。由此可见，当5mM的K2PtCl6和200mM NaBH4溶液的用量为在15～35mL之间,且使用1.0mL的吡咯时，可得到片层状的GO/PtNPs/PPy复合光催化材料。
采用亚甲基蓝模拟环境污染物对GO/PtNPs/PPy复合光催化材料的光催化性能进行实验，具体实验方法如下：
移取100mL浓度为10mg/L的染料溶液于石英试管中，加入100mg采用本对比例和实施例中制备得到的复合光催化材料(a-e)，避光磁力搅拌30min后开启氙灯(300W,用滤波片过滤波长小于400nm的光)，通冷却水使反应体系温度控制在10℃左右，每隔30min取样，过滤去除GO/PtNPs/PPy复合光催化材料，在紫外-可见分光光度计上测定不同光照时间后亚甲基蓝溶液的吸光度值。
如图5(a)-(f)所示，为所制备的GO/PtNPs/PPy复合光催化材料对亚甲基蓝溶液的光催化降解效率图，对比例1、对比例2、对比例3、实施例1、实施例2、实施例3中制备的钒酸铋光催化材料分别为a、b、c、d、e和f，从图5中可以看出，随着光照时间的延长，制备的GO/PtNPs/PPy复合光催化材料a-d对亚甲基蓝溶液主要是表面吸附作用，几乎没有光催化降解作用，其对亚甲基蓝的降解率分别为7.88％，17.43％，21.70％和21.43％。而实施例2和3在210min内对亚甲基蓝的降解率分别为66.24％(图5e)和79.37％(图5f)，使得亚甲基蓝溶液在最大吸收波长λ＝664nm处的吸光度值都有显著的降低。其中，实施例3中制备的GO/PtNPs/PPy复合光催化材料的光催化性最好。
本发明的有益效果是：发明了一种具有优异的光催化活性的GO基复合光催化材料的制备方法，以氧化石墨烯(GO)作为载体，以纳米铂(PtNPs)和聚吡咯(PPy)作为光电传导介质，制备过程对设备要求低、且反应条件温和，合成工艺简单易于实现，成功地得到了光催化性能较高的三相复合光催化材料GO/PtNPs/PPy。
Claims (4)
1.一种片层状三相复合光催化材料的制备方法，其特征在于，该方法包括以下：
步骤1：取通过超声剥离制备的2.5 g/L石墨烯分散液和预先经过超声处理30 min的5mM 的K2PtCl6溶液混合均匀；所述K2PtCl6溶液为25-35 mL；
步骤2：然后逐滴加入与K2PtCl6溶液相同体积的200 mM NaBH4溶液反应后制得石墨烯/纳米铂复合材料；
步骤3：取木质素磺酸钠加入蒸馏水中，在冰水浴中搅拌10 min，得到木质素磺酸钠溶液；将步骤2制得的石墨烯/纳米铂复合材料分散于木质素磺酸钠溶液后，分别逐滴加入吡咯和0.2892 M的FeCl3溶液；在冰水浴条件下边搅拌边反应后过滤、洗涤和干燥后得石墨烯/纳米铂/聚吡咯三相复合光催化材料；
所述吡咯和FeCl3溶液的体积比为1.0 mL：50mL；所述FeCl3溶液与步骤1石墨烯分散液的体积比为10:1。
2.根据权利要求1所述的一种片层状三相复合光催化材料的制备方法，其特征在于，步骤3所述木质素磺酸钠与蒸馏水的比例为1g: 100 mL。
3.根据权利要求1所述的一种片层状三相复合光催化材料的制备方法，其特征在于，步骤3所述反应的条件为：在冰水浴中边搅拌边反应时间不少于7 h。
4.根据权利要求1所述的一种片层状三相复合光催化材料的制备方法，其特征在于，步骤3所述冰水浴温度范围是0-5℃。
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