CN115282987B - 一种高效人工光合光催化材料及其制备方法 - Google Patents
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Abstract
一种高效人工光合光催化材料及其制备方法，属于光化学能转换、光催化降解领域。本发明要解决人工光合光催化复合材料的高质量制备以及如何有效提高光化学能转换效率的技术问题。本发明方法：一、分别将硫脲、二水合乙酸锌、四水合乙酸镉溶于乙二胺，搅拌溶解后转移到反应釜中加热反应，冷却至室温后取出离心、洗涤、干燥，得到Zn0.5Cd0.5S纳米棒；二、将二水合钨酸钠溶解于去离子水中后依次加入盐酸和草酸，水热反应，得到WO3纳米片；三、将步骤一制备的Zn0.5Cd0.5S纳米棒和步骤二制备的WO3纳米片分散在去离子水中，利用盐酸调节水溶液的pH值，使Zn0.5Cd0.5S和WO3表面分别带有异性电荷，通过静电吸附作用使二者形成复合材料，进一步在氮气中退火，得到稳定的Zn0.5Cd0.5S/WO3人工光合光催化复合材料。
Description
技术领域
本发明属于光化学能转换、光催化降解领域。
背景技术
受自然界光合作用的启发，近年来基于人工光合设计思路不断涌现的Z-Scheme光催化体系引起了人们的广泛关注。特别是全固态直接Z-Scheme光催化剂更是受到更多的青睐。原因在于其构成仅需由两种在费米能级和能带结构带边位置适配的还原光催化剂PS I和氧化光催化剂PSⅡ形成有效的界面接触，那么光生电子将在空间电荷区内建电场的作用下由PSⅡ的导带向PS I的价带形成Z型迁移路径，从而形成光生电子和空穴的有效分离。经由这一光生载流子传递过程，能够最大限度地保留两催化剂的氧化还原反应热力学驱动，若能够兼顾太阳光谱利用率选取窄带半导体材料作为其组分，则同时集成了光量子吸收效率优势和光生电荷分离效率优势，是当前新型太阳能转换材料的研究热点。
在已报道的众多直接Z-Scheme光催化剂当中，CdS/WO3无疑是其中备受瞩目的。因为两半导体组分均具有可见光吸收，光还原性质极佳的CdS材料还具有足够负的导带底还原电位，能够进行诸如光解水制氢、二氧化碳还原以及毒害重金属离子降解等反应，可处理解决关乎能源、环境等诸多问题。虽然CdS易受光腐蚀，但Z-Scheme光生电荷迁移路径下的CdS表面富电子，可有效避免因空穴聚集造成的光氧化腐蚀现象。而随着Zn1−xCdxS固溶体的出现，人们发现Zn1−xCdxS/WO3的调控空间更大，具有更佳的光催化还原优势。因为Zn1−xCdxS固溶体相较于CdS具有更高的费米能级和导带还原电位，在空间电荷区高势垒作用下，光生电荷具有更高的迁移动力学驱动，反应热力学方面同样具有更高的光还原势能，因而近年来备受关注。尽管受ZnS宽带隙影响，固溶体的光响应有所下降，太阳光谱利用率一定程度降低。在Zn1-xCdxS系列固溶体材料中，Zn0.5Cd0.5S带隙适中并且因其固溶量最大晶格缺陷相对最多，而适量的缺陷态在表面反应中却可充当表面活性位点增进材料的催化活性。因此多数基于Zn0.5Cd0.5S开展的光催化性能研究都无需担载表面助催化剂，是广受开发的新型光催化材料。
综上所述，本发明提出一种高效人工光合光催化材料及其制备方法，该方法将制备得到的Zn0.5Cd0.5S和WO3纳米材料通过静电吸附结合后退火的方法形成稳定的Zn0.5Cd0.5S/WO3异质结复合材料。该人工光合异质结光催化剂可有效协同太阳光吸收、光生电荷分离和表面化学反应三方面效率。而本发明提出的静电吸附异质结构建策略则考虑到尽可能多地制造催化剂二组分有效接触界面，用以增加异质结数量，后退火处理也进一步增进界面紧密结合程度，强化界面质量。常规的原位化学合成虽可提供高质量的界面结合但无法实现Zn0.5Cd0.5S与WO3之间可选择性的定向结合。本发明依据二者等电点差异通过调变溶液pH使Zn0.5Cd0.5S和WO3表面带有异性电荷，充分实现异质界面的紧密结合、同时屏蔽同质界面相互作用的影响。退火工艺的引入也可进一步提高界面间的接触及键合，是提升异质结质量的有效手段。
发明内容
本发明涉及解决人工光合异质结催化剂的高质量合成制备以实现催化剂性能的优化提升的问题，从而提出一种异质结复合材料合成新策略，为解决上述问题，本发明中一种高效人工光合光催化材料及其制备方法是通过下述步骤完成的。
步骤一、分别将硫脲、二水合乙酸锌、四水合乙酸镉溶于乙二胺并搅拌溶解，将溶液转移到聚四氟乙烯内衬的反应釜中加热，冷却后洗涤于真空干燥箱内干燥，得到Zn0.5Cd0.5S。
步骤二、将二水合钨酸钠溶解于去离子水中，加入盐酸，搅拌后加入草酸，继续搅拌，将溶液转移到聚四氟乙烯内衬的反应釜中，水热处理，将产物洗涤后干燥，得到WO3。
步骤三、将步骤一制备的Zn0.5Cd0.5S和步骤二制备的WO3分散在去离子水中，调节溶液的pH值，剧烈搅拌，将产物干燥后在氮气中退火，得到Zn0.5Cd0.5S/WO3。
进一步限定，步骤一中将0.71~2.13 g硫脲，1.10~3.30 g二水合乙酸锌和1.33~3.99 g乙酸镉加入50 mL乙二胺。
进一步限定，步骤一中搅拌溶解时间为60 min。
进一步限定，步骤一在烘箱内120~180 ℃下保温16~24 h，在真空干燥箱内60 ℃下保温12 h。
进一步限定，步骤二将1.815~4.444 g二水合钨酸钠、8~12 mL盐酸、0.45~1.35 g草酸加入50 mL去离子水中。
进一步限定，步骤二中搅拌时间为3 h。
进一步限定，步骤二在60 ℃下真空干燥12 h。
进一步限定，步骤三将20~120 mg WO3和200 mg Zn0.5Cd0.5S加入去离子水中。
进一步限定，步骤三使用10M HCl溶液调节pH至3.5。
进一步限定，步骤三中剧烈搅拌12~18 h，在氮气中退火2 h，退火温度为380 ℃。
本发明方法制备的人工光合异质结构催化剂为Zn0.5Cd0.5S纳米棒与WO3纳米片层良好耦合形成的Zn0.5Cd0.5S/WO3复合材料，本发明提供了一种新型的复合材料制备技术，以达到异质界面紧密接触，从而使光生载流子在界面内建电场作用下实现在空间电荷区的有效分离，最终实现光催化性能的有效提升。
附图说明
图1是Zn0.5Cd0.5S(ZCS)、WO3、40wt%-Zn0.5Cd0.5S/WO3(ZCSW40) 及标准PDF卡片的XRD图谱；图2是各组分Zn0.5Cd0.5S/WO3(ZCSW)的XRD图谱；图3是ZCS 纳米棒的扫描电镜照片；图4是WO3纳米片的扫描电镜照片；图5是ZCSW40的透射电镜照片；图6是ZCSW40的选区高分辨透射电镜照片；图7是各试样的紫外-可见吸收光谱、内插图为换算得到的带隙值；图8是各试样的光致发光光谱；图9是各试样对重铬酸钾指示剂溶液的光催化还原降解情况、内插图为ZCSW40试样的三次循环稳定性测试；图10是各试样的降解速率对比。
具体实施方式
实施例1：本实施例使用Zn0.5Cd0.5S纳米棒是按下述步骤进行的：将40mmol硫脲(NH2CSNH2)，10mmol乙酸锌[Zn(CH3COO)2·2H2O]和10mmol乙酸镉[Cd(CH3COO)2·4H2O]溶于50 ml乙二胺(NH2CSNH2)并搅拌1 h，将混合物溶液转移至反应釜中，在160 ℃加热反应24 h后冷却至室温。用无水乙醇和去离子水分别洗涤3遍，并在真空条件下60 ℃干燥12 h。
本实施中一种高效人工光合催化剂Zn0.5Cd0.5S/WO3及其制备方法是通过下述步骤完成的。
步骤一、将40 mmol硫脲，10 mmol乙酸锌和10 mmol乙酸镉溶于50 mL乙二胺，搅拌1h后，将获得的混合物转移至高压釜中并在160 ℃下加热反应24 h。冷却至室温，用无水乙醇和去离子水分别洗涤3遍，并在60 ℃下真空干燥12 h，获得Zn0.5Cd0.5S纳米棒粉末。
步骤二、将0.342 g二水合钨酸钠溶解于去离子水中并用盐酸调节pH值至1，在室温下磁力搅拌3 h后将0.169 g草酸加入上述溶液，继续搅拌30 min，将获得的混合物转移至反应釜，并在60 ℃下加热反应24 h。冷却至室温后用无水乙醇和离子水分别洗涤3遍，并在60 ℃真空干燥12 h，获得WO3纳米片粉末。
步骤三、使用10M盐酸溶液将去离子水调节至pH值为3.5，分别取用6个烧杯盛装该水溶液并依次加入20 mg、40 mg、60 mg、80 mg、100 mg、120 mg WO3纳米片，之后再分别加入200 mg的Zn0.5Cd0.5S纳米棒，持续搅拌14 h，将产物离心干燥后在氮气中380 ℃退火2 h。得到WO3与ZCS的质量比分别为10%、20%、30%、40%、50%、60%的Zn0.5Cd0.5S/WO3复合材料样品，分别命名为ZCSW10、ZCSW20、ZCSW30、ZCSW40、ZCSW50、ZCSW60。
光催化还原降解Cr(VI)反应采用300 W氙灯模拟太阳光光源。在100 mL的烧杯中放入10 mg的待测催化剂和30 mL浓度为40 mg/L的重铬酸钾指示剂溶液。将烧杯固定于光源前方距离5 cm处，降解反应过程中保持匀速的磁力搅拌。取相同的时间间隔对反应液进行吸光度检测，并计算出反应液浓度，以此做出降解率随光照时间的变化规律曲线，由此对样品的光催化活性进行分析评价，如图9所示。
从图10中可以看出，在光催化反应中ZCSW10~ZCSW60这6种复合材料光催化剂的性能均高于参比Zn0.5Cd0.5S和WO3催化剂。其中ZCSW40样品的降解速率最快，仅用时10分钟便降解了全部的重铬酸钾指示剂溶液（详见图9），降解速率达到了20.4 μmol·min-1·gcat -1，同时其也具有良好的循环稳定性，连续三次反应仍然保持93%以上的降解率，如图9插图所示。以上性能表现均说明了人工光合催化剂特有的光生电子迁移路径为空间电荷的分离创造了有利条件，不仅延长了光生电子的寿命，还有效增加了光生电子的反应热力学势能，宏观表现为材料光催化降解性能的显著提高。
Claims (8)
1.一种光催化降解Cr(VI)的高效人工光合光催化材料的制备方法，其特征在于所述制备方法是通过下述步骤完成的：
步骤一、将四水合醋酸镉、二水合醋酸锌和硫脲溶于乙二胺，超声震荡并以300rpm速率剧烈搅拌后，将溶液转移到具有聚四氟乙烯内衬的反应釜中加热，冷却至室温后多次洗涤并在真空干燥箱内干燥，得到Zn0.5Cd0.5S纳米棒；
步骤二、将二水合钨酸钠、盐酸、草酸依次加入到去离子水中，搅拌后水热处理并洗涤、干燥，得到WO3纳米片；
步骤三、将步骤一和步骤二获得的Zn0.5Cd0.5S以及WO3加入去离子水，用盐酸溶液调节pH值至3.5并剧烈搅拌12~18 h，将其离心干燥后在氮气中退火，退火时间为2 h，退火温度为380 ℃，得到Zn0.5Cd0.5S/WO3人工光合催化剂。
2.根据权利要求1所述的制备方法，其特征在于步骤一中将0.71~2.13 g硫脲，1.10~3.30 g二水合醋酸锌和1.33~3.99 g四水合醋酸镉加入50 mL乙二胺。
3.根据权利要求1所述的制备方法，其特征在于步骤一中搅拌时间为60 min。
4.根据权利要求1所述的制备方法，其特征在于步骤一中加热温度为120~180 ℃，加热时间为16~24 h，在真空干燥箱内60℃下保温12h。
5.根据权利要求1所述的制备方法，其特征在于步骤二中依次将1.815~4.444 g二水合钨酸钠、8~12 mL盐酸、0.45~1.35 g草酸加入50 mL去离子水中。
6.根据权利要求1所述的制备方法，其特征在于步骤二中搅拌时间为3 h。
7.根据权利要求1所述的制备方法，其特征在于步骤二在60 ℃下干燥12 h。
8.根据权利要求1所述的制备方法，其特征在于步骤三将20~120 mg WO3和200 mgZn0.5Cd0.5S加入去离子水中。
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