CN106824070B - 一种二硒化钨-氮掺杂石墨烯光催化吸附材料及其制备方法 - Google Patents
一种二硒化钨-氮掺杂石墨烯光催化吸附材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种二硒化钨‑氮掺杂石墨烯光催化吸附材料及其制备方法，属于光催化材料技术领域。其中二硒化钨属于间接能带隙半导体材料，且具有较高的光吸收系数，禁带宽度为1.35eV。石墨烯有极高的电子迁移率，可增强光催化材料的光生载流子的迁移率；并且具有较大的比表面积，增加了其吸附性能。而氮元素的掺杂可以改善光催化剂的光谱响应性，拓宽其吸光范围。提高了可见光催化剂对有机污染物的降解性能。在相同条件下二硒化钨‑氮掺杂石墨烯光催化吸附材料比二硒化钨及氮掺杂石墨烯表现出更高的光催化吸附性能。
Description
技术领域
本发明属于光催化材料技术领域，具体涉及一种二硒化钨-氮掺杂石墨烯光催化吸附材料及其制备方法和在有机污染物处理中的应用。
背景技术
近些年来，环境污染的现象也日渐加重。有机污染物尤其是有机染料废水成分复杂、种类多变，可生化性差，毒性大，有机污染物浓度高，难以用普通方法降解。为了解决染料废水处理的难点问题，光催化技术可以利用太阳光作为能源进行物质转化，可使有机物得到去除和降解。光催化技术的应用关键在于光催化剂的发展。在可见光下具有较高光催化活性并表现出优秀稳定性的催化剂，一直被认为是在太阳能转换和水污染物处理应用中最有前途的一种材料。目前为止，研究最多的光催化剂是TiO2，其具有光化学性质稳定、催化效率高、氧化能力强、无毒无害、价格便宜、无二次污染等优点，因而备受国内外关注，但由于TiO2的禁带宽度为3.2eV，光谱响应范围很窄，只对波长较短的紫外光有响应，局限了其应用范围。太阳能是目前全球关注最高的清洁能源，如何充分利用它就显得尤为重要，发展具有可见光催化活性的新型催化剂具有十分重要的意义。
二硒化钨，由二维Se—W—Se的层状结构构成，层内通过共价键结合，而层间通过范德华力结合。二硒化钨属于间接能带隙半导体材料，较高的光吸收系数，禁带的宽度为1.35eV，可充分利用太阳光，特别是可以利用可见光，大大增加了对太阳光的利用率。
石墨烯的电导率较高(15000cm2v-1s-1)，能够及时地将电子导出，从而降低了光生电子和空穴的复合几率，且其比表面积很大，可以作为载体，对光催化剂起到了很好的分散和提高光催化剂稳定性的作用；氮元素的掺杂拓宽了二硒化钨的光谱响应范围，提高了可见光催化剂对有机污染物的降解性能。本工作以制备的二硒化钨与氧化石墨烯和尿素为原料，制备复合材料，用于光催化处理有机废水。在相同条件下二硒化钨-氮掺杂石墨烯复合材料比二硒化钨表及氮掺杂石墨烯现出更高的光催化性能。其可用于有机污染物的光催化降解处理。
发明内容
本发明的目的是提供一种具有可见光响应的二硒化钨-氮掺杂石墨烯光催化吸附剂及其制备方法，通过该制备方法得到的二硒化钨-氮掺杂石墨烯光催化吸附材料具有吸附和可见光催化性能，可用于有机污染物的吸附和在可见光条件下催化降解有机污染物。
本发明所采用的技术方案是将二硒化钨，其化学组成式为WSe2，负载在氮掺杂的石墨烯上制得。具体包括如下步骤：
(1)将一定量的Na2WO4·2H2O和硒粉按一定的配比溶于一定体积去离子水中，再将氢源以及还原剂依次加入上述溶液中，通过磁力搅拌2-4小时，搅拌均匀后置于高压反应釜中，控制温度，反应一定时间，冷却到室温，洗涤，干燥，得到灰色的粉末状物质，经一定质量分数的氢氧化钠溶液处理并洗涤干燥后得到二硒化钨(化学组成式为WSe2)；
(2)称取一定量的氧化石墨，分散于一定量去离子水中，超声分散2-4h并离心20-40min得到一定浓度的透明棕色溶液，即氧化石墨稀分散液。
(3)将氧化石墨烯分别与尿素和二硒化钨按一定的质量比加料，将一定质量的尿素、二硒化钨溶于一定浓度一定体积的氧化石墨烯分散液中，将此分散液搅拌0.5-2h后，转移至水热合成反应釜，在一定温度下反应一定时间，冷却后将得到的黑色固体，用蒸馏水洗涤，置于真空干燥箱干燥，得到二硒化钨-氮掺杂石墨烯。
上述步骤(1)中，氢源为盐酸(质量分数为36.5％)，还原剂为水合肼(80％)。
具体的，步骤(1)中，高压反应釜中的混合溶液保持温度在120-200℃下密闭反应24-48h。
具体的，步骤(1)中，Na2WO4·2H2O和硒粉按照WSe2的组成称量配料。
上述步骤(2)中，所述超声波的强度为60-100W。
具体的，步骤(2)中，所述氧化石墨烯分散液浓度为0.5-1.0g/L.
上述步骤(3)中，所述氧化石墨烯与尿素的质量比为1:20-1:40，氧化石墨烯与二硒化钨的质量比为1:0.2-1:2。
具体的，步骤(3)中，高压反应釜中的混合溶液保持温度在120-200℃下密闭反应8-14小时。
具体的，步骤(3)中，所述干燥温度为20-40℃.
上述二硒化钨-氮掺杂石墨烯复合材料制备方法制备的光催化剂可应用于光催化降解有机污染物，其光催化性能比二硒化钨及氮掺杂石墨烯更优越。
本发明的有益效果在于该制备方法得到的二硒化钨-氮掺杂石墨烯复合材料具有吸附和可见光催化性能，可见光响应频率范围宽，光吸收系数高，对有机污染物具有优异的吸附性能，可用于可见光下有机污染物尤其是有机染料的吸附和光催化降解处理。通过实验结果可知，其对亚甲基蓝的去除效果较好。
附图说明
图1为实施例1制备的二硒化钨-氮掺杂石墨烯(WSe2/g-C3N4)光催化吸附材料对亚甲基蓝的去除效果。
具体实施方式
下面通过实施例具体说明本发明，但本发明不受下述实施例的限定。
实施例1
本发明二硒化钨-氮掺杂石墨烯光催化吸附剂的制备方法，具体步骤如下：
1)二硒化钨材料的制备
将0.1649g Na2WO4·2H2O、0.07896g硒粉溶于60mL去离子水中，再将15mL盐酸(质量分数为36.5％)、5mL水合肼(80％)依次加入上述溶液，充分搅拌，搅拌均匀后；倒入高压反应釜密闭，将温度控制在200℃下持续加热24h，反应结束后，自然冷却到室温，将所得的产物蒸馏水洗涤数次，105℃真空干燥，得到灰色粉末，再将其溶于质量分数为40％的NaOH溶液中反应掉多余的硒粉，洗涤烘干，其化学式组成为WSe2。
2)氧化石墨烯分散液的制备
将0.25g氧化石墨溶于250mL去离子水水中，超声分散4h，然后连续离心20min，取上层透明棕色溶液，即得1.0g/L的氧化石墨烯分散液。
3)二硒化钨-氮掺杂石墨烯光催化吸附剂的制备
将氧化石墨烯与尿素以1:40的质量比，称取4.0g尿素溶于100mL1.0g/L氧化石墨烯分散液，然后按氧化石墨烯与二硒化钨以1:2的质量比，取0.2g二硒化钨加入上述溶液，磁力搅拌2h。待其与完全混合均匀后，放入高压反应釜中，保持温度为120℃，恒温14h。自然冷却后去除上清液，过滤，用蒸馏水洗涤，于20℃下真空干燥，得到光催化吸附材料。
实施例2
本发明二硒化钨-氮掺杂石墨烯光催化吸附剂的制备方法，具体步骤如下：
1)二硒化钨材料的制备
将0.8247g Na2WO4·2H2O、0.3948g硒粉溶于35mL去离子水中，再将35mL盐酸(质量分数为36.5％)、10mL水合肼(80％)依次加入上述溶液中，充分搅拌，搅拌均匀后；倒入高压反应釜密闭，将温度控制在120℃下持续加热48h，反应结束后，自然冷却到室温，将所得的产物用蒸馏水洗涤数次，105℃真空干燥，得到灰色粉末，再将其溶于质量分数为40％的NaOH溶液中反应掉多余的硒粉，洗涤烘干，其化学式组成为WSe2。
2)氧化石墨烯分散液的制备
将0.25g氧化石墨溶于500mL蒸馏水中，超声分散2h，然后连续离心40min，取上层透明棕色溶液，即得0.5g/L的氧化石墨烯分散液。
3)二硒化钨-氮掺杂石墨烯光催化吸附剂的制备
将氧化石墨烯与尿素以质量为1:20的比例，称取2.0g尿素溶于200mL0.5g/L氧化石墨烯分散液，然后按氧化石墨烯与二硒化钨以1:0.2的质量比，取0.02g二硒化钨加入上述溶液，磁力搅拌0.5h。待其完全混合均匀后，放入高压反应釜中，保持温度为200℃，恒温8h。自然冷却后去除上清液，过滤，用蒸馏水洗涤，于40℃下真空干燥，得到光催化吸附材料。
实施例3
实施例1得到的光催化吸附剂对有机染料的光催化降解效果实验
1)称取0.05g光催化剂放入50mL的试管内，然后加入50mL浓度为6.0×10-5mol/L的亚甲基蓝溶液，放入光化学反应器中(型号为JOYN-GHX-A)，打开搅拌，进行半个小时的暗反应，暗反应结束后，打开风扇与水龙头，打开氙灯，进行光催化反应。每隔十分钟取一次样，连续取六次，试验持续一个小时，将取出的混合液进行离心，离心结束后，用UV-752型可见分光光度计于亚甲基蓝最大吸收波长664nm处测其吸光度，计算亚甲基蓝的浓度。
2)亚甲基蓝的光降解率D按如下公式计算：
C0：初始浓度；Ct：在时间为t时的浓度。所得实验结果如图1所示。
从图1中可以看出二硒化钨和二硒化钨-氮掺杂石墨烯光催化吸附材料均可以在可见光下催化降解亚甲基蓝，随时间变化降解率逐渐增加，呈上升趋势。相同条件下二硒化钨-氮掺杂石墨烯光催化吸附材料对于亚甲基蓝的降解效率均明显高于单纯的二硒化钨纳米材料的降解效率。50min时二硒化钨-氮掺杂石墨烯光催化吸附材料对于亚甲基蓝的降解率超过90％，可以很好地处理有机染料废水。
Claims (3)
1.一种二硒化钨-氮掺杂石墨烯复合材料，其特征在于，包括如下原料：Na2WO4·2H2O、硒粉、36.5％的盐酸、80％的水合肼、氧化石墨、尿素；
制备方法包括以下步骤：
(1)将一定量的Na2WO4·2H2O和硒粉按WSe2的组成称量配料，溶于一定体积去离子水中，再将36.5％的盐酸以及80％的水合肼依次加入上述溶液中，通过磁力搅拌均匀后置于高压反应釜中，保持温度在120-200℃下密闭反应24-48小时，冷却到室温，洗涤，干燥，得到灰色的粉末状物质，经一定质量分数的氢氧化钠溶液处理并洗涤干燥后得到二硒化钨(化学组成式为WSe2)；
(2)称取一定量的氧化石墨，溶于一定量去离子水中，超声分散2-4h并离心20-40min得到一定浓度的棕色溶液，获得浓度为0.5-1.0g/L的氧化石墨稀分散液；
(3)将氧化石墨烯分别与尿素和二硒化钨按一定的质量比，将一定质量的尿素、二硒化钨溶于一定浓度一定体积的氧化石墨烯分散液中，将此混合液搅拌均匀后，至于高压反应釜中，控制温度120-200℃下密闭反应8-14小时，冷却后将得到的黑色固体，用蒸馏水洗涤数次，放入真空干燥箱干燥温度为20-40℃下真空干燥，得到最终产物；
所述氧化石墨烯与尿素的质量比为1:20-1:40，氧化石墨烯与二硒化钨的质量比为1:0.2-1:2。
2.含有权利要求1所述的二硒化钨-氮掺杂石墨烯复合材料的光催化吸附材料。
3.含有权利要求1所述的二硒化钨-氮掺杂石墨烯复合材料的光催化吸附材料在吸附降解有机化合物方面的应用。
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