CN113398998B - Zr-MOF@CdS光催化剂及其制备方法和在光催化水分解制氢中的应用 - Google Patents
Zr-MOF@CdS光催化剂及其制备方法和在光催化水分解制氢中的应用 Download PDFInfo
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Abstract
本发明涉及Zr‑MOF@CdS光催化剂及其制备方法和在光催化水分解制氢中的应用。本发明首先通过溶剂热法制备Zr‑MOF晶体，然后将硫代乙醇酸作为分子链接剂，通过溶剂热法形成硫醇官能化的Zr‑MOF，最后通过回流的方法，利用S2‑交换过程，在Zr‑MOF上生长CdS，得到了一种高稳定性、高活性的光催化剂Zr‑MOF@CdS。将催化剂超声分散于乳酸的水溶液中，用Pt作为助催化剂，向溶液中通入氮气除去氧气，在可见光下(λ≥420nm)进行催化反应，可以实现在可见光下高效催化水分解制氢。
Description
技术领域
本发明属于催化制氢领域，尤其涉及Zr-MOF@CdS光催化剂及其在光催化水分解制氢反应中的应用。
背景技术
光催化裂解水制氢是一种将太阳能转化为可再生氢能的绿色技术，并且这种技术在降低化石燃料消耗和保护环境方面有很大帮助，因此引起了人们的极大关注。介孔Zr-MOF以其高稳定性、高比表面积、高结晶性等特点，加上其类半导体行为，在包括光催化等多个领域得到广泛应用。近年来，人们对基于半导体的光催化产氢进行了大量研究。在已经使用的各种半导体中，硫化镉由于其良好的可见光吸收能力和合适的导带位置而非常受欢迎，足以驱动氢气生成反应。然而，CdS的光腐蚀性、不稳定性、光致电子-空穴对的快速复合以及有限的表面催化中心限制了纯CdS的应用。如何获得活性高、稳定性好的催化材料是目前研发的重点，利用不同方法改性的CdS被广泛用于催化领域研究中。
发明内容
本发明的目的是通过回流的方法将Zr-MOF与CdS复合，得到一种新型材料Zr-MOF@CdS。该材料在催化水分解制氢中具有良好的应用前景。
为实现上述目的，本发明采用的技术方案是：Zr-MOF@CdS光催化剂，按质量比，Zr-MOF:CdS＝10:9。
Zr-MOF@CdS光催化剂的制备方法，包括如下步骤：
1)将适量Zr-MOF晶体溶于DMF中，加入硫代乙醇酸，进行溶剂热反应，得硫醇官能化的Zr-MOF；
2)于硫醇官能化的Zr-MOF中，加入镉源和硫源，进行回流反应，所得反应物离心，固体用无水乙醇洗涤，真空干燥，得目标产物。
优选的，上述的制备方法，步骤1)中，所述Zr-MOF晶体的制备方法包括如下步骤：将适量ZrCl4(四氯化锆)、H2TADIBA(4,4′-(2H-1,2,4-三唑-3,5-二基)二苯甲酸)和CF3COOH(三氟乙酸)加入DMF中，超声均匀，在120℃下溶剂热反应48h，得Zr-MOF晶体。
优选的，上述的制备方法，步骤1)中，所述溶剂热反应是，于60℃下加热12h。
优选的，上述的制备方法，步骤2)中，所述镉源来源于Cd(CH3COO)2·2H2O。
优选的，上述的制备方法，步骤2)中，所述硫源来源于硫代乙酰胺(TAA)。
优选的，上述的制备方法，步骤2)中，所述回流反应是，于80℃下回流反应2-2.25h。
本发明提供的Zr-MOF@CdS光催化剂作为催化剂在光催化水分解制氢中的应用。
优选的，方法如下：将Zr-MOF@CdS光催化剂超声分散于溶有牺牲剂的水溶液中，用Pt作为助催化剂，向溶液中通入氮气除去氧气，在可见光下进行催化反应。
优选的，所述牺牲剂为乳酸。
本发明的有益效果是：本发明利用简单的溶剂热法得到Zr-MOF，将硫代乙醇酸作为分子链接剂，利用溶剂热法得到硫醇官能化的Zr-MOF，通过回流法，利用S2-交换过程在Zr-MOF表面原位沉积CdS纳米颗粒，制备得到了一种具有良好光催化活性的催化剂Zr-MOF@CdS，该催化剂可以实现在可见光下高效催化水分解制氢。
附图说明
图1是CdS纳米颗粒，Zr-MOF晶体与Zr-MOF@CdS复合物的固体紫外-可见漫反射光谱图。
图2是Zr-MOF@CdS复合物的扫描电子显微镜图(a)和高分辨透射电子显微镜图(b)。
图3是可见光下(λ≥420nm)Zr-MOF@CdS复合物催化水分解制氢示意图。
图4是可见光下(λ≥420nm)CdS,Zr-MOF,Zr-MOF@CdS催化水分解产氢对比图。
具体实施方式
实施例1
(一)制备Zr-MOF晶体：
将29.1mg ZrCl4和40mg H2TADIBA溶于装有7.5mL DMF溶液的玻璃小瓶中，超声20min。然后，加入100uL三氟乙酸，密封，在120℃下静置48h。产物经离心分离，用DMF反复洗涤，最后60℃真空干燥12h，得Zr-MOF晶体。
(二)Zr-MOF@CdS的制备方法如下：
将70mg Zr-MOF晶体溶于装有5mL DMF的玻璃小瓶中，超声10min，然后加入100uL的硫代乙醇酸，密封，在60℃下溶剂热反应12h。产物经离心分离，用无水乙醇反复洗涤，真空干燥，得硫醇官能化的Zr-MOF。
将所得硫醇化官能化的Zr-MOF与120mg Cd(CH3COO)2·2H2O溶于装有20mL无水乙醇的圆底烧瓶中，在80℃下回流2h，随后，加入33.6mg硫代乙酰胺(TAA)并保持回流15min。通过离心收集固体物，用无水乙醇洗涤两次，并在60℃下干燥12h，得Zr-MOF@CdS复合物。
(三)CdS的制备：
将42mg Cd(CH3COO)2·2H2O加入装有20mL无水乙醇的圆底烧瓶中，在80℃下回流2h，随后，加入11.8mg硫代乙酰胺(TAA)并保持回流2h。通过离心收集产物固体物，用无水乙醇洗涤两次，并在60℃下干燥12h，得到CdS纳米颗粒。
(四)检测结果
图1是CdS纳米颗粒，Zr-MOF晶体与Zr-MOF@CdS复合物的固体紫外-可见漫反射光谱图。从图1中可以看出，Zr-MOF在可见光区域无吸收，Zr-MOF@CdS表现出较强的可见光响应能力，说明Zr-MOF与CdS复合后，可见光的吸收范围明显拓宽。
图2是Zr-MOF@CdS复合物的扫描电子显微镜图(a)和高分辨透射电子显微镜图(b)。由图2中(a)可以看出，Zr-MOF@CdS复合物是一种多面体结构，CdS纳米颗粒均匀的分散在Zr-MOF表面，并与Zr-MOF紧密结合。如图2中(b)可以看出，所测的晶格条纹之间的距离约为0.33nm，对应于立方相CdS的(111)晶面。
实施例2Zr-MOF@CdS光催化剂催化水分解制氢
方法如下：该反应在石英反应器中进行，以300W氙灯作为光源模拟太阳光。将催化剂Zr-MOF@CdS(30mg)超声分散于100mL浓度为1.2M乳酸的水溶液中，然后加入400uL0.01mol·L-1的氯铂酸溶液，向反应体系中通入高纯氮气30分钟以除去氧气，然后在可见光(λ≥420nm)照射下反应6h。在反应过程中采用气相色谱法每30分钟检测一次生成氢气的量。参比实验中，分别以CdS和Zr-MOF代替Zr-MOF@CdS作为催化剂。
图3是可见光下Zr-MOF@CdS光催化剂催化水分解制氢示意图。实验结果如图4，当Zr-MOF作催化剂时，由于其对可见光无响应，因此6h产氢量为零。当CdS作催化剂时，由于光催化过程中光生载流子严重复合，6h产氢量仅为2.45mmol·g-1；而Zr-MOF@CdS作催化剂时，催化活性显著提高，产氢量随着反应时间的增加线性上升，反应6h未见活性衰减，6h产氢总量高达11.17mmol·g-1。由此可见，当CdS与Zr-MOF复合形成异质结后，由于电子-空穴对的分离效率提高，光生载流子的迁移速率加快，使CdS催化水分解放氢活性提高了约4.5倍。Zr-MOF@CdS的催化活性高、稳定性好、制备方法简单，在光催化水分解制氢领域具有良好的应用前景。
Claims (8)
1.Zr-MOF@CdS光催化剂的制备方法，其特征在于，所述Zr-MOF@CdS光催化剂，按质量比，Zr-MOF : CdS = 10 : 9，制备方法包括如下步骤：
1）将适量ZrCl4、H2TADIBA和CF3COOH加入DMF中，超声均匀，在120 ℃下溶剂热反应48h，得Zr-MOF晶体；
2）将适量Zr-MOF晶体溶于DMF中，加入硫代乙醇酸，进行溶剂热反应，得硫醇官能化的Zr-MOF；
3）于硫醇官能化的Zr-MOF中，加入镉源和硫源，进行回流反应，所得反应物离心，所得固体用无水乙醇洗涤，真空干燥，得目标产物。
2.根据权利要求1所述的制备方法，其特征在于，步骤2）中，所述溶剂热反应是，于60℃下加热12 h。
3.根据权利要求1所述的制备方法，其特征在于，步骤3）中，所述镉源来源于Cd(CH3COO)2·2H2O。
4.根据权利要求1所述的制备方法，其特征在于，步骤3）中，所述硫源来源于硫代乙酰胺。
5.根据权利要求1所述的制备方法，其特征在于，步骤3）中，所述回流反应是，于80 ℃下回流反应2-2.25 h。
6.按照权利要求1所述的方法制备的Zr-MOF@CdS光催化剂作为催化剂在光催化水分解制氢中的应用。
7.根据权利要求6所述的应用，其特征在于，方法如下：将Zr-MOF@CdS光催化剂超声分散于溶有牺牲剂的水溶液中，用Pt作为助催化剂，向溶液中通入氮气除去氧气，在可见光下进行催化反应。
8.根据权利要求7所述的应用，其特征在于，所述牺牲剂为乳酸。
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