CN114870900A - 一类Pt配位的锆基MOFs光催化材料的合成和应用 - Google Patents
一类Pt配位的锆基MOFs光催化材料的合成和应用 Download PDFInfo
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Abstract
本发明涉及一类Pt配位的锆基MOFs光催化材料的合成和应用,所述配位Pt是利用具有对称性结构的卟啉有机配体将其锚定。本发明采用的卟啉有机配体为5,10,15,20‑四(4‑羧基苯基)卟啉铂,其制备工艺成熟,适用于商业生产。采用水热法将具有优异的金属锚定作用的四羧基苯基卟啉铂(PtTCPP)与ZrCl4分别与甲酸和苯甲酸等混合反应得到不同形貌锆基MOFs(Zr‑MOFs),其中,Zr‑MOFs‑S的析氢性能最好。
Description
技术领域
本发明涉及光催化析氢技术领域,具体涉及一类Pt配位的锆基MOFs光催化材料的合成和应用。
背景技术
通过光催化水分解制氢反应将太阳能转换和存储在作为中间能量载体的H2的化学键中具有重要意义。尽管已开发出多种光催化剂,包括分子催化剂和无机半导体,以实现高效的光催化制氢,但实现催化剂的回收和改善可见光转化率仍具有挑战性。太阳能包含约5%的紫外线,42%~43%的可见光(400-700nm)和52%~55%的红外光(>700nm)。金属有机框架材料由于其独特的功能已成为一种有前途的光催化制氢催化剂,它可以将多种光敏剂和助催化剂合并在一起,增强光吸收能力并改善电子-空穴分离,从而增强光催化性能。
为了对MOFs的纳米空间进行特定功能设计,可以将光敏剂(例如卟啉)引入框架中,从而产生自敏化的MOFs。众所周知,卟啉是具有氧化还原活性的光敏剂,它们大多数具有吸收对应于Soret带和Q带的可见光的能力,并显示出三重态激发态的超长寿命。例如,Rh,Pd和Pt作为金属中心配位的卟啉在室温下的三重态寿命通常约为数十至数百微秒(μs)。此外,助催化剂例如金属(M)或金属纳米粒子(MNPs)封装到MOFs的配位间隙中可以提高电子-空穴分离能力,在MOFs和MNPs的界面处会形成肖特基势垒,光生电子可能从MOFs的LUMO转移到M或MNPs,从而增强电子-空穴的分离,进而提高光催化性能。如果实现自敏化MOFs与掺入的助催化剂之间的协同催化作用,助催化剂均匀地位于MOFs内部,则可以提高催化性能。
为了有效地分解水,光催化剂在水中应具有高稳定性。据报道,由高电荷金属阳离子(例如Cr3+,Zr4+和Hf4+)和羧酸盐构成的MOFs在水甚至酸性或碱性水溶液中具有很高的稳定性,显示出光催化分解水的巨大潜力。将过渡金属-氧簇和羧酸盐配位使相应的MOFs具有亲水性,从而促进光催化水分解反应。因此,我们认为,基于IVA族金属Zr4+的MOFs利用受限配位空间将H2O富集成为有效的光解水的催化剂。
因此,合成一类Pt配位的锆基MOFs光催化材料并将其用于光催化析氢研究,是本领域技术人员研究的方向。
发明内容
本发明的目的在于合成一类单原子Pt基光催化材料,以实现优异的光催化析氢效果。
一类Pt配位的锆基MOFs光催化材料,包括如下步骤:
(1)以ZrCl4、H2O、DMF、甲酸为原料,通过搅拌使固体完全溶解得到混合溶液,在混合溶液中加入PtTCPP,通过水热法制备了Zr-MOFs-S;
(2)以ZrCl4、H2O、DMF、苯甲酸为原料,通过搅拌使固体完全溶解得到混合溶液,在混合溶液中加入PtTCPP,通过水热法制备了Zr-MOFs-C;
(3)以ZrCl4、DMF、苯甲酸、PtTCPP为原料,超声使固体溶解后加入反应釜中,通过水热法制备了Zr-MOFs-L。
其中,所述步骤(1)中,反应温度为120度,时间为24小时;
所述步骤(2)中,反应温度为120度,时间为24小时;
所述步骤(3)中,反应温度为120度,时间为24小时;
本发明还提供了单原子Pt光催化材料的应用,其特征在于,所述的单原子Pt光催化材料由权利要求1所述的方法制备得到;所述单原子Pt光催化材料适用于酸性条件下的光催化析氢应用,并表现出优异的效果。
与现有技术相比,本发明具有如下优点:
1、本发明提供的一类Pt配位的锆基MOFs光催化材料的制备方法,通过使用不同的有机酸使得锆基MOFs光催化材料具有不同的形貌特征,不同的形貌特征暴露出暴露不同的活性位点;卟啉有机配体Pt的加入一方面提供了活性位点Pt,另一方面卟啉结构锚定了金属Pt,避免了其在光催化制氢过程中脱落,保证其稳定性。
2、本发明制备一类Pt配位的锆基MOFs光催化材料中,Zr-MOFs-S的制氢效果最好。
附图说明
图1为实施1制备的Zr-MOFs-S的SEM图。
图2为实施2制备的Zr-MOFs-C的SEM图。
图3为实施2制备的Zr-MOFs-L的SEM图。
图4为实施1、2、3制备的锆基MOFs的XRD图。
图5为实施1、2、3制备的锆基MOFs的光催化析氢图。
具体实施方式
下面将结合附图及实施例对本发明作进一步说明。
实施例1:
Zr-MOFs-S光催化材料的制备方法,包括如下步骤:
将ZrCl4(50mg)、甲酸(1.2mL)、H2O(250μL)加入到10mLDMF中,使之充分溶解。然后,在上述溶液中进一步添加PtTCPP(50mg),在室温下保持磁力搅拌10min。将所得均匀溶液转移至25mL反应釜中,然后在120℃加热反应24h。待反应冷却后,离心得固体,并用乙醇和病痛洗涤数次,最后真空干燥得Zr-MOFs-S。
附图1SEM图可以看出制备Zr-MOFs-S的形貌呈现出椭圆状结构,与其余两种Pt配位的锆基MOFs光催化材料的形貌不同,附图4为Pt配位的锆基MOFs光催化材料的XRD图,可以看出从图中可以看出,块状的Zr-MOF-L催化剂在4.71°,6.57°,7.98°和9.28°处显示衍射峰。然而,随着形貌的改变,Zr-MOF-S和Zr-MOF-C的衍射峰开始消失或减弱,当然,不排除一些特征峰变成宽峰。总的来说,此类Pt配位的锆基MOFs。
将制备的Zr-MOFs-S光催化材料用于光催化析氢中,具体如下:
(1)光催化析氢体系的选择:在100mL光学反应容器中进行光催化制氢实验。称取5mg Zr-MOFs-S光催化材料,加入到50mL水溶液中,加入880.6mg抗坏血酸作为牺牲剂,然后将悬浮液搅拌并用氮气吹扫约20min以除去空气。
(2)光催化析氢仪器操作:使用全光谱的300W的Xe灯(带有420nm的截止滤光片),保持恒温冷却循环泵的测试温度为10℃,将(1)中光学反应容器固定在仪器上后,用Xe灯照射进行光催化制氢。使用热导检测器(TCD)通过气相色谱法(ShimadzuGC-2014C,氮气作为载气)测量氢气。通过再次添加牺牲剂以进行循环稳定性测试。每个周期的持续时间为5小时。
附图5为制备的Zr-MOFs-S材料的光催化析氢结果图,从结果图可以看出,在这类Pt配位的锆基MOFs光催化材料中,Zr-MOFs-S的制氢效果最好。
实施例2:
Zr-MOFs-C光催化材料的制备方法,包括如下步骤:
在磁力搅拌下将50mg ZrCl4、1.25g苯甲酸和1mL H2O充分溶解在10mL DMF溶液中,再将上述溶液中进一步加入50mg PtTCCP,并使之充分溶解。将所得均匀溶液转移至25mL反应釜中,然后在120℃加热24小时。通过离心收集橙色固体,并用乙醇和丙酮进一步纯化几次,干燥即可得Zr-MOFs-C。
附图2SEM图可以看出制备Zr-MOFs-C的形貌呈现出方块状结构,附图4为Pt配位的锆基MOFs光催化材料的XRD图。
将制备的Zr-MOFs-C光催化材料用于光催化析氢中,具体如下:
(1)光催化析氢体系的选择:在100mL光学反应容器中进行光催化制氢实验。称取5mg Zr-MOFs-C光催化材料,加入到50mL水溶液中,加入880.6mg抗坏血酸作为牺牲剂,然后将悬浮液搅拌并用氮气吹扫约20min以除去空气。
(2)光催化析氢仪器操作:使用全光谱的300W的Xe灯(带有420nm的截止滤光片),保持恒温冷却循环泵的测试温度为10℃,将(1)中光学反应容器固定在仪器上后,用Xe灯照射进行光催化制氢。使用热导检测器(TCD)通过气相色谱法(ShimadzuGC-2014C,氮气作为载气)测量氢气。通过再次添加牺牲剂以进行循环稳定性测试。每个周期的持续时间为5小时。
附图5为制备的Zr-MOFs-C材料的光催化析氢结果图。
实施例3:
Zr-MOFs-L光催化材料的制备方法,包括如下步骤:
将150mg ZrCl4,50mg PtTCPP和2g苯甲酸超声溶解在10mLDMF溶液中。将所得均匀溶液转移至25mL反应釜中,然后将混合物在120℃中加热24小时。冷却至室温后,离心收集橙红色固体,并用乙醇和丙酮纯化数次,干燥即可得Zr-MOFs-L。
附图3SEM图可以看出制备Zr-MOFs-L的形貌呈现出不规则长条结构,附图4为Pt配位的锆基MOFs光催化材料的XRD图。
将制备的Zr-MOFs-L光催化材料用于光催化析氢中,具体如下:
(1)光催化析氢体系的选择:在100mL光学反应容器中进行光催化制氢实验。称取5mg Zr-MOFs-L光催化材料,加入到50mL水溶液中,加入880.6mg抗坏血酸作为牺牲剂,然后将悬浮液搅拌并用氮气吹扫约20min以除去空气。
(2)光催化析氢仪器操作:使用全光谱的300W的Xe灯(带有420nm的截止滤光片),保持恒温冷却循环泵的测试温度为10℃,将(1)中光学反应容器固定在仪器上后,用Xe灯照射进行光催化制氢。使用热导检测器(TCD)通过气相色谱法(ShimadzuGC-2014C,氮气作为载气)测量氢气。通过再次添加牺牲剂以进行循环稳定性测试。每个周期的持续时间为5小时。
附图5为制备的Zr-MOFs-C材料的光催化析氢结果图。
最后需要说明的是,以上实施例仅用以说明本发明的技术方案而非限制技术方案,本领域的普通技术人员应当理解,那些对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,均应涵盖在本发明的权利要求范围当中。
Claims (5)
1.一类Pt配位的锆基MOFs光催化材料的制备方法,其特征在于,包括如下步骤:
(1)以ZrCl4、H2O、DMF、甲酸为原料,通过搅拌使固体完全溶解得到混合溶液,在混合溶液中加入PtTCPP,通过水热法制备了Zr-MOFs-S;
(2)以ZrCl4、H2O、DMF、苯甲酸为原料,通过搅拌使固体完全溶解得到混合溶液,在混合溶液中加入PtTCPP,通过水热法制备了Zr-MOFs-C;
(3)以ZrCl4、DMF、苯甲酸、PtTCPP为原料,超声使固体溶解后加入反应釜中,通过水热法制备了Zr-MOFs-L。
2.根据权利要求1所述的一类Pt配位的锆基MOFs光催化材料的制备方法,其特征在于,所述步骤(1)中,反应温度为120度,时间为24小时;
3.根据权利要求1所述的一类Pt配位的锆基MOFs光催化材料的制备方法,其特征在于,所述步骤(2)中,搅拌时间为10分钟,反应温度为120度,时间为24小时;
4.根据权利要求1所述的一种Pt配位的锆基MOFs光催化材料的制备方法,其特征在于,所述步骤(3)中,反应温度为120度,时间为24小时;
5.一类Pt配位的锆基MOFs光催化材料的制备方法,其特征在于,所述的Pt配位的锆基MOFs光催化材料由权利要求1所述的方法制备得到。
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