CN110302806A - 一种单层四元复合可见光催化材料及其制备方法 - Google Patents
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Abstract
本发明提供了一种单层四元复合可见光催化材料及其制备方法，所述复合可见光催化材料的化学式为BaxZn1‑xIn2S4，其中0<x<1。所述的光催化材料在可见光下具有较高的光催化产氢活性。
Description
技术领域
本发明属于光催化技术领域，具体涉及一种单层四元BaxZn1-xIn2S4复合可见光催化材料及其制备方法。
背景技术
煤炭燃烧为工业发展提供电能，同时为城市生活供暖。但是煤炭燃烧产生的废渣和废气严重污染环境，并造成了不可逆转的后果，如雾霾、水污染等。依赖传统化石能源不可避免的会造成环境污染，并且会导致能源危机。在现代科技发展过程中，清洁能源的发展日新月异，其中氢能是理想的清洁能源，氢气与氧气燃烧后释放能量并生成水，对环境是无污染的。
生产氢气的常用方法是电解水，但消耗的电能仍然需要用传统化石能源来提供，这违背了保护环境的初衷。近年来，利用太阳光将水分解生成氢气和氧气的研究受到广泛的关注。太阳光是取之不竭的巨大能源，水占地球面积的70%，因此利用太阳光将水分解为氢能具有巨大的科学价值。其中光催化剂的应用必不可少。
常用的光催化剂是TiO2，但TiO2只能响应紫外光，不能利用可见光，致使太阳光中大部分的光能不能被利用。国内外在开发可见光催化剂工作上进行了大量研究，但都没有达到令人满意的程度。
通过能级结构设计和大量实验，我们发现硫化物组成的复合半导体材料可以受可见光激发，使光催化剂发挥最大的催化效率。
发明内容
本发明的目的在于提供一种单层四元BaxZn1-xIn2S4复合可见光催化材料及其制备方法。
为实现上述目的，本发明采用如下技术方案：
一种单层四元复合可见光催化材料，其化学式为BaxZn1-xIn2S4，其中0<x<1。
一种单层四元BaxZn1-xIn2S4复合可见光催化材料的制备方法，包括以下步骤：
（1）称取硝酸钡x mmol(0<x<1)，醋酸锌1-x mmol、氯化铟2 mmol、硫代乙酰胺4.5 mmol先后加入到250 mL三口烧瓶中，加入10-20 mL丙酮和10-20 mL去离子水，持续超声0.5-1.5h，得到均一的混合溶液，向溶液中加入20 mL以四氢呋喃和N’N-二甲基甲酰胺为混合溶剂溶解的0.5 mmol双嵌段聚合物聚苯乙烯-聚丙烯酸混合液，再在溶液中溶解1 mmol邻苯二甲酸或间苯二甲酸，超声分散0.5 h；
（2）将溶液转移到100 mL聚四氟乙烯反应釜中，在聚四氟乙烯反应釜外套上微波专用安全保护套，将反应釜放入微波水热反应器中，设置微波功率为300 W，微波反应时间为1-8h，微波反应温度为130-220℃；
（3）反应结束后，将反应物倒入离心管中，超声分散30 min，将沉淀用蒸馏水和无水乙醇分别洗涤3次，9000 r/min离心分离得到固体粉末，固体粉末转入到装有100 mL无水乙醇的烧杯中，在烧杯底部通入0.1-1Mpa高压氮气，放入超声波反应器中超声2-3 h，超声频率为20～40kHz，9000 r/min离心分离得到固体粉末，60-80 ℃烘干24 h、研磨成粉，形成一种单层四元BaxZn1-xIn2S4复合可见光催化材料。
本发明的优点在于：本发明在较温和条件下制备了产物，使用高压氮气使块状材料被剥离成层状材料，表面活性剂（双嵌段聚合物聚苯乙烯-聚丙烯酸）有效保护材料的表面形态，微波加热方式提供了内部均一的热源和磁场，有利于材料纯度的提高。
三元材料ZnIn2S4已经被证实具有可见光催化活性，但还需要提高。掺杂元素Ba后形成了晶格缺陷，产生了更多的反应活性位，较三元催化剂提高了光催化活性。此外，Ba对反应物和产物的吸附脱附作用也可以影响催化剂的活性。
Ba 与Zn的总量是1，催化剂活性与用量相关，随着Ba用量的增加，活性是先增大后降低的变化趋势。
附图说明
图1为Ba0.2Zn0.8In2S4复合可见光催化材料的XRD图；
图2为Ba0.2Zn0.8In2S4复合可见光催化材料的电镜图。
具体实施方式
为让本发明的上述特征和优点能更明显易懂，下文特举实施例，作详细说明。本发明的方法如无特殊说明，均为本领域常规方法。
实施例1
一种单层四元Ba0.2Zn0.8In2S4复合可见光催化材料的制备方法，包括以下步骤：
（1）称取硝酸钡0.2 mmol，醋酸锌0.8 mmol、氯化铟2 mmol、硫代乙酰胺4.5 mmol先后加入到250 mL三口烧瓶中，加入10mL丙酮和10 mL去离子水，持续超声0.5h，得到均一的混合溶液，向溶液中加入20 mL以四氢呋喃和N’N-二甲基甲酰胺为混合溶剂溶解的0.5 mmol双嵌段聚合物聚苯乙烯-聚丙烯酸混合液，再在溶液中溶解1 mmol邻苯二甲酸，超声分散0.5 h；
（2）将溶液转移到100 mL聚四氟乙烯反应釜中，在聚四氟乙烯反应釜外套上微波专用安全保护套，将反应釜放入微波水热反应器中，设置微波功率为300 W，微波反应时间为3h，微波反应温度为150℃；
（3）反应结束后，将反应物倒入离心管中，超声分散30 min，将沉淀用蒸馏水和无水乙醇分别洗涤3次，9000 r/min离心分离得到固体粉末，固体粉末转入到装有100 mL无水乙醇的烧杯中，在烧杯底部通入1Mpa高压氮气，放入超声波反应器中超声2h，超声频率为40kHz，9000 r/min离心分离得到固体粉末，60℃烘干24 h、研磨成粉，形成一种单层四元Ba0.2Zn0.8In2S4复合可见光催化材料。
实施例2
一种单层四元Ba0.5Zn0.5In2S4复合可见光催化材料的制备方法，包括以下步骤：
（1）称取硝酸钡0.5 mmol，醋酸锌0.5 mmol、氯化铟2 mmol、硫代乙酰胺4.5 mmol先后加入到250 mL三口烧瓶中，加入15 mL丙酮和15 mL去离子水，持续超声1h，得到均一的混合溶液，向溶液中加入20 mL以四氢呋喃和N’N-二甲基甲酰胺为混合溶剂溶解的0.5 mmol双嵌段聚合物聚苯乙烯-聚丙烯酸混合液，再在溶液中溶解1 mmol邻苯二甲酸，超声分散0.5h；
（2）将溶液转移到100 mL聚四氟乙烯反应釜中，在聚四氟乙烯反应釜外套上微波专用安全保护套，将反应釜放入微波水热反应器中，设置微波功率为300 W，微波反应时间为5h，微波反应温度为200℃；
（3）反应结束后，将反应物倒入离心管中，超声分散30 min，将沉淀用蒸馏水和无水乙醇分别洗涤3次，9000 r/min离心分离得到固体粉末，固体粉末转入到装有100 mL无水乙醇的烧杯中，在烧杯底部通入0.5Mpa高压氮气，放入超声波反应器中超声3 h，超声频率为30kHz，9000 r/min离心分离得到固体粉末，70℃烘干24 h、研磨成粉，形成一种单层四元Ba0.5Zn0.5In2S4复合可见光催化材料。
实施例3
一种单层四元Ba0.9Zn0.1In2S4复合可见光催化材料的制备方法，包括以下步骤：
（1）称取硝酸钡0.9mmol，醋酸锌0.1mmol、氯化铟2 mmol、硫代乙酰胺4.5 mmol先后加入到250 mL三口烧瓶中，加入20 mL丙酮和20 mL去离子水，持续超声1.5 h，得到均一的混合溶液，向溶液中加入20 mL以四氢呋喃和N’N-二甲基甲酰胺为混合溶剂溶解的0.5 mmol双嵌段聚合物聚苯乙烯-聚丙烯酸混合液，再在溶液中溶解1 mmol间苯二甲酸，超声分散0.5 h；
（2）将溶液转移到100 mL聚四氟乙烯反应釜中，在聚四氟乙烯反应釜外套上微波专用安全保护套，将反应釜放入微波水热反应器中，设置微波功率为300 W，微波反应时间为8h，微波反应温度为220℃；
（3）反应结束后，将反应物倒入离心管中，超声分散30 min，将沉淀用蒸馏水和无水乙醇分别洗涤3次，9000 r/min离心分离得到固体粉末，固体粉末转入到装有100 mL无水乙醇的烧杯中，在烧杯底部通入0.1Mpa高压氮气，放入超声波反应器中超声3 h，超声频率为20kHz，9000 r/min离心分离得到固体粉末，80 ℃烘干24 h、研磨成粉，形成一种单层四元Ba0.9Zn0.1In2S4复合可见光催化材料。
在固定床反应器中，300W氙灯照射下，90毫升去离子水和10毫升甲醇组成混合液，加入0.1g实施例1中的催化剂，磁力搅拌，反应8小时停止。经气相色谱检测，氢气产量为(176 umol/g/h)。
图1是催化剂的XRD图，从图中峰的位置可以看出生成了目标产物，峰型尖锐，说明晶形完整。图2是样品的SEM图，从图中可以看出样品的微观形貌，样品为片状形貌。
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 (2)
1.一种单层四元复合可见光催化材料，其特征在于，所述复合可见光催化材料的化学式为BaxZn1-xIn2S4，其中0<x<1。
2.根据权利要求1所述的单层四元复合可见光催化材料的制备方法，其特征在于，包括以下步骤：
（1）称取硝酸钡x mmol，醋酸锌1-x mmol、氯化铟2 mmol、硫代乙酰胺4.5 mmol先后加入到250 mL三口烧瓶中，加入10-20 mL丙酮和10-20 mL去离子水，持续超声0.5-1.5 h，得到均一的混合溶液，向溶液中加入20 mL以四氢呋喃和N’N-二甲基甲酰胺为混合溶剂溶解的0.5 mmol双嵌段聚合物聚苯乙烯-聚丙烯酸混合液，再在溶液中溶解1 mmol邻苯二甲酸或间苯二甲酸，超声分散0.5 h；
（2）将溶液转移到100 mL聚四氟乙烯反应釜中，在聚四氟乙烯反应釜外套上微波专用安全保护套，将反应釜放入微波水热反应器中，设置微波功率为300 W，微波反应时间为1-8h，微波反应温度为130-220℃；
（3）反应结束后，将反应物倒入离心管中，超声分散30 min，将沉淀用蒸馏水和无水乙醇分别洗涤3次，9000 r/min离心分离得到固体粉末，固体粉末转入到装有100 mL无水乙醇的烧杯中，在烧杯底部通入0.1-1Mpa高压氮气，放入超声波反应器中超声2-3 h，超声频率为20～40kHz，9000 r/min离心分离得到固体粉末，60-80 ℃烘干24 h、研磨成粉，得到单层四元BaxZn1-xIn2S4复合可见光催化材料，其中0<x<1。
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