CN113797940A - 一种硒化钴石墨氮化碳复合材料及其制备方法和应用 - Google Patents
一种硒化钴石墨氮化碳复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域，具体涉及一种硒化钴石墨氮化碳复合材料及其制备方法和应用。通过水热形成Co0.85Se，煅烧形成石墨氮化碳(g‑C3N4)；将Co0.85Se和g‑C3N4分散到去离子水中，然后做超声处理，洗涤、干燥，最后通过煅烧得到Co0.85Se/g‑C3N4复合材料。本发明通过简单水热超声煅烧合成了硒化钴石墨氮化碳复合光催化材料，制备原材料价格低廉，不含贵金属和污染环境的重金属，用于可见光下高效光催化分解水制氢气，而氢气是高热能、无污染、可再生的能源。
Description
技术领域
本发明属于光催化材料技术领域，具体涉及一种硒化钴石墨氮化碳复合材料及其制备方法以及在可见光下光催化分解水产氢的作用。
背景技术
当今世界能源短缺与环境问题日益严峻，开发清洁能源迫在眉睫。氢能是一种非常好的清洁能源，在消耗的过程中不会产生任何污染物质，能量密度高，是理想的选择。但是目前情况是工业上制氢技术远远达不到理想要求，不仅能耗高，而且效率低。发展光催化技术利用太阳能将水分解产生氢气是一种清洁可持续制氢的重要途径，因此探索和制备高效产氢的光催化剂显得尤为重要。
在利用半导体光催化分解水过程中，当能量大于其禁带宽度的光照射时，会产生光生电子空穴对，光生电子具有还原性，光生空穴具有氧化性。当某一材料的导价带电势分别比H+/H2 (0 V vs. NHE)负，比H2O/O2的氧化电位(1.23 V)正时，H2O分子就会被电子还原成H2，被空穴氧化成O2。但是实际中单一组分光催化材料产氢效率低，原因在于电子和空穴的分离效率低。使用贵金属负载被认为是提高光生电子空穴分离效率的有效方法之一。
但是在实际合成制备时大都存在着一些问题，比如原料使用稀有且昂贵的贵金属、合成过程条件严格复杂、产生污染环境的物质等。中国专利CN106268874A公开了一种Ag/g-C3N4复合薄膜及其制备方法和应用，原料成本高。类似的研究还有利用Au、Pt和Pd等贵金属作为助催化剂来提高光催化性能。当然也有很多研究针对非贵金属助催化剂的改性。中国专利CN107715859A公开了一种石墨烯钙钛矿复合型光催化制氢催化剂的制备方法，称取硝酸盐、钛酸四丁酯和络合剂溶解在乙醇中，加入石墨烯，搅拌至变为干凝胶，然后焙烧除去有机物再真空煅烧制得到，该制备过程复杂，比如石墨烯制备条件较困难；中国专利CN108927222A公开了一种CdS-PAN/石墨烯复合纳米纤维的制备方法，制备复杂，反应条件苛刻，且涉及到重金属硫化物CdS，对环境有污染。此外，目前大多数半导体催化剂都只在紫外光下有活性，可见光不响应，而太阳光的主要部分是可见光，所以太阳光利用效率很低。
发明内容
针对现有技术的不足，本发明的目的在于提供一种硒化钴石墨氮化碳复合材料复合材料、及其制备方法以及在光催化分解水产氢上的作用。该制备方法实验条件较简便，主要通过水热超声煅烧的方法即可，而且制备过程中没有污染环境的重金属等物质，所用原料价格低廉易得。
为达此目的，本发明采用以下技术方案：
一种用于可见光下光催化产氢的硒化钴石墨氮化碳复合材料的制备方法，包括以下步骤：
(1)将一定量的四水合乙酸钴和亚硒酸钠加入到乙二醇溶剂中，再搅拌5分钟；
(2)将溶液置于水热反应，再进行冷却，洗涤和干燥处理，得到Co0.85Se样品；
(3)将尿素放入陶瓷坩埚中并放入马弗炉在空气条件下煅烧制备石墨氮化碳g-C3N4；
(4)分别称取一定量的步骤(2)和步骤(3)制得的样品分散到去离子水中做超声处理，然后洗涤、干燥；
(5)将步骤(4)所得样品在马弗炉中做煅烧处理，制备得到Co0.85Se/g-C3N4复合材料。
所述步骤(1)四水合乙酸钴和亚硒酸钠中的钴和硒元素摩尔之比为1:2，硒元素过量。
步骤(2)所述水热温度为200 ℃，反应时间为24 h，干燥为烘箱60 ℃条件。
步骤(3)所述煅烧温度为550 ℃，保温时间为4 h，升温速率为5 ℃/min。
步骤(4)所述过程中，所用的Co0.85Se的质量是g-C3N4质量的5-15%，超声分散时间为8h，超声功率为400 W。
步骤(5)所述的煅烧温度为320 ℃，保温时间为2 h，升温速率为3 ℃/min。
应用：所述的硒化钴石墨氮化碳复合材料在可见光催化分解水制氢气上的应用。
本发明提出先水热形成硒化钴，煅烧合成石墨氮化碳，然后通过将一定量的两种材料分散到水中超声，洗涤干燥，最后放入马弗炉中煅烧形成复合物样品。
硒化钴石墨氮化碳复合光催化材料的光催化活性是通过氙灯加420nm截止滤光片获得可见光照射，以三乙醇胺为牺牲剂对水光催化分解进行测试的。
硒化钴石墨氮化碳复合光催化材料性能的表征方法：用X射线衍射（XRD）光谱分析产物物质组成及结构情况。用紫外可见漫反射(UV-Vis-DRS)光谱仪分析复合材料的最大光吸收波长。
本发明的优点在于：该方案复合材料制备条件较为简单，主要通过水热煅烧超声的方法，所用原料成本价格低，并且在制备过程中不会产生污染环境的物质。
与现有技术相比，本发明的有益效果为：
本发明通过简单水热煅烧和超声的方法合成硒化钴石墨氮化碳复合光催化材料，制备所需要的原材料价格便宜，不含贵金属和污染环境的重金属。在性能方面，光响应范围宽，可用于可见光下光催化高效分解水制取氢气，与大多数只能在紫外光下响应的催化剂相比，具有高的太阳能利用效率，充分利用太阳能中占高比例的可见光。而制得氢气是高热能、无污染、可再生的能源。
Co0.85Se/g-C3N4复合材料高产氢活性的作用原理：g-C3N4和Co0.85Se的功函数分别为5.60eV和5.70eV，前者的费米能级高于后者。当两者形成靠近形成界面时，g-C3N4上的电子就会转移到Co0.85Se上直至两者费米能级持平，形成肖特基结，那么Co0.85Se的作用就类似于贵金属Pt。光照下g-C3N4受激发，大量光生电子会从g-C3N4迁移到上Co0.85Se参与到产氢反应，实现了光生电子、空穴的有效分离，导致光催化活性提高。而单一组分g-C3N4和Co0.85Se在光照射时产生的光生电子和空穴极易复合，电子不能参与反应，从而导致产氢活性很低。
附图说明
图1为实施例1合成方法所制得Co0.85Se产物的XRD谱图。
图2为实施例1合成方法所制得12%Co0.85Se/g-C3N4和g-C3N4产物的XRD谱图。
图3为实施例1合成方法所制得12%Co0.85Se/g-C3N4产物的UV-Vis-DRS谱图。
图4为实施例1所得催化剂制氢效果图。
图5为实施例1合成方法所制得Co0.85Se和g-C3N4产物的功函数图。
图6为实施例1可见光光催化水分解的反应器示意图。
图7为实施例1光解水反应装置图。
具体实施方式
下面结合实施例进一步说明本发明，该实例只用于说明本发明，并不限制本发明。
实施例一
将152mg四水合乙酸钴和210mg亚硒酸钠溶于30ml的乙二醇溶剂中，再搅拌5分钟后将混合物转移到不锈钢高压釜中，密封并保持在200 ℃下24 h，冷却至室温，将生成物洗涤并在60℃烘箱中干燥，得到Co0.85Se。石墨氮化碳（g-C3N4）由10 g尿素放入30 ml坩埚在马弗炉中550℃煅烧4 h制得，煅烧过程中的升温速率为5 ℃/min。再将6 mg Co0.85Se和50 mgg-C3N4溶于5 ml去离子水中超声8 h，超声功率为400 W，洗涤干燥后放在马弗炉中空气条件下320 ℃煅烧2 h，煅烧过程中的升温速率为3 ℃/min，得到12% Co0.85Se/g-C3N4的目标产物。使用相同的方法，获得了一系列不同比例含量的复合材料。
从Co0.85Se的XRD图（如图1）可以看出用这种方法合成的Co0.85Se与其标准卡片的峰吻合，不含有其它杂质。从12% Co0.85Se/g-C3N4复合材料的XRD图（图2），可以看出用上述方案方法合成的Co0.85Se/g-C3N4复合材料中的Co0.85Se的峰也与标准卡片吻合，在2θ=13°和27°处的两个峰归属于g-C3N4，峰较高，纯相g-C3N4的峰基本吻合。12% Co0.85Se/g-C3N4复合材料的紫外可见漫反射光谱图如图3所示，根据谱图可知该复合材料的最大吸收波长在435nm左右，可见光响应，证明了该材料在可见光下有产氢活性。从所得光催化剂制氢效果图（图4）可以看出，Co0.85Se与g-C3N4复合后与纯g-C3N4相比光催化分解水制氢活性有很大的提升，当Co0.85Se的质量比为12%时活性最高，可见光下产氢活性为226 µmol·g-1h-1，远远高于单一组分g-C3N4的产氢活性（8µmol·g-1h-1）。卡尔文探针测试（图5）表明g-C3N4和Co0.85Se的功函数分别为5.60eV和5.70eV，前者的费米能级高于后者。当两者形成靠近形成界面时，g-C3N4上的电子就会转移到Co0.85Se上直至两者费米能级持平，形成肖特基结，那么Co0.85Se的作用就类似于贵金属Pt。光照下g-C3N4受激发，大量光生电子会从g-C3N4迁移到上Co0.85Se参与到产氢反应，实现了光生电子、空穴的有效分离，导致光催化活性提高。而单一组分g-C3N4和Co0.85Se在光照射时产生的光生电子和空穴极易复合，电子不能参与反应，从而导致产氢活性很低。
应用例1
光催化分解水实验，具体步骤如下：
所制备的一系列二元复合材料样品的光催化水分解活性测试所用的反应装置如图6所示，具体的操作步骤如下：将20 mg的催化剂放在反应器（如图6）中，随后再加入90 ml去离子水和10 ml三乙醇胺（三乙醇胺作为牺牲试剂）。
然后将反应器用真空封脂连接到光解水反应系统中，外接温度为5 ℃的循环冷凝水，用反应装置图7的真空泵对体系进行抽真空处理，保证体系不含有氮气和氧气。最后用300 W的氙灯光源照射，每隔1 h进一次样，使用氩气作为载气将反应得到的气体送到GC-2014C气相色谱检测产生的氢气量。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (10)
1.一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，将硒化钴Co0.85Se和石墨氮化碳g-C3N4分散到去离子水中超声处理，洗涤、干燥，最后通过煅烧得到Co0.85Se/g-C3N4复合材料。
2.根据权利要求1所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，所述石墨氮化碳g-C3N4具体制备包括以下步骤：
(1)将尿素放入陶瓷坩埚中，然后将坩埚放在马弗炉中煅烧，制得g-C3N4。
3.根据权利要求2所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，石墨氮化碳g-C3N4的制备过程中，煅烧温度为550℃，煅烧时间为4 h，升温速率为5 ℃/min。
4.根据权利要求1所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，所述硒化钴Co0.85Se具体制备包括以下步骤：
(1)将一定量的四水合乙酸钴和亚硒酸钠加入到乙二醇溶剂中，再搅拌5分钟；
(2)将溶液进行水热反应，再进行冷却，洗涤和干燥处理，研磨得到样品。
5.根据权利要求4所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，步骤(1) 四水合乙酸钴和亚硒酸钠中的钴、硒元素的摩尔比为1:2。
6.根据权利要求4所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，步骤(2)中水热温度为200℃，反应时间为24 h，干燥处理温度为60 ℃。
7.根据权利要求1所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，加入的Co0.85Se的质量是g-C3N4质量的5-15%，超声时间为8 h，超声功率为400 W。
8.根据权利要求1所述的一种硒化钴石墨氮化碳复合材料的制备方法，其特征在于，煅烧时间为2 h，升温速率为3 ℃/min，煅烧温度为320 ℃。
9.一种如权利要求1-8任一项所述制备方法获得的硒化钴石墨氮化碳复合材料。
10.一种如权利要求9所述的硒化钴石墨氮化碳复合材料在可见光催化分解水制氢气上的应用。
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