CN111036292B - 卟啉稳定的贵金属纳米颗粒催化剂及其应用 - Google Patents
卟啉稳定的贵金属纳米颗粒催化剂及其应用 Download PDFInfo
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Abstract
本发明提供了一种贵金属纳米颗粒催化剂及其在催化氨硼烷水解产氢中的应用。此催化剂的合成方法是以四氯化铂、硝酸铑和三氯化钌为原料,四羟基四苯基卟啉(THPP)为稳定剂,在去离子水中充分搅拌混合二者,随后在还原剂的作用下,贵金属离子被还原成原子。贵金属原子与四羟基四苯基卟啉上的羟基上的氢和大环上的内氢形成氢键,从而使金属纳米颗粒得以稳定在卟啉分子上。因卟啉本身良好的电荷转移动力和电子介质特点,所以由其所稳定的纳米颗粒表现出优良的催化性能。
Description
技术领域
本发明属于功能材料领域,涉及一种卟啉稳定金纳米颗粒催化剂制备方法及其应用。
背景技术
由于能源消耗的增加和地球上人口的增长,如今迫切需要清洁和多样化的能源。氢由于其高能量容量,无污染和可再生的性质等而被认为是非常有前景的能源载体。在可利用的与能源有关的策略中,氢燃料电池由于其清洁生产的电力具有零排放或高效率的低排放而备受关注。因此,需要合适的材料以确保燃料电池的安全和可控的方式存储和产生氢。
迄今为止,已有许多关于金属纳米颗粒催化剂(包括贵金属/非贵金属及其复合物)的制备和优化的报道,证明了在液相化学氢化物中脱氢的优异催化活性。研究发现催化剂的催化活性很大程度上取决于金属纳米颗粒和载体以及它们之间的相互作用。超小型纳米颗粒的高表面能可能导致热力学不稳定和团聚,从而导致催化性能下降。因此,稳定纳米颗粒分散的纳米颗粒催化剂非常重要。由于金属纳米颗粒与支撑物之间的强烈相互作用,结构良好的支撑物可以实现纳米颗粒的稳定而不聚集。关于这一点,研究人员付出了巨大的努力来使用适当的支持物来固定纳米颗粒,例如活性炭,石墨烯,MOF,MOF衍生的纳米材料和多孔有机笼(POC)。而四羟基四苯基卟啉本身结构很稳定,能与贵金属原子结合形成氢键的位点很多,能够起到很好的分散贵金属纳米粒子的效果;并且卟啉本身具有优良的光化学性能,能够促进电子转移从而提升催化剂的催化性能。
发明内容
基于上述背景,本发明的目的是提供一种卟啉稳定的贵金属纳米颗粒的制备方法及其应用。
本发明的所述的卟啉稳定的贵金属纳米颗粒催化剂,以乙醇将四羟基四苯基卟啉溶解得到卟啉的乙醇溶液和溶于去离子水的贵金属盐溶液为原料,在去离子水中均匀混合后,将硼氢化钠溶液滴加到混合溶液中,利用硼氢化钠的还原性将混合溶液中的贵金属离子还原成原子,贵金属原子与四羟基四苯基卟啉分子羟基上的氢和卟啉大环中的内氢形成氢键,从而将贵金属纳米颗粒吸附到卟啉分子上。因卟啉在溶液中是均匀分散的,从而得到均匀分散的贵金属纳米颗粒。测试表明贵金属纳米催化剂具有良好的催化氨硼烷水解产氢的性能。
所述的卟啉稳定的贵金属纳米颗粒催化剂的制备方法,包括以下制备步骤:
(1)四羟基四苯基卟啉溶解于溶剂中,在冰浴环境下搅拌至均匀;再把贵金属盐溶液分别缓慢加入上述卟啉溶液中,在冰浴环境下搅拌至均匀混合;
(2)将硼氢化钠溶液缓慢加入到步骤(1)的混合溶液中,在冰浴环境下反应1-5小时,反应结束后,即可得到卟啉稳定的贵金属纳米颗粒溶液。、
四羟基四苯基卟啉、贵金属和硼氢化钠的物质的量的比为1:1-4:10-40。
进一步优选为四羟基四苯基卟啉、贵金属和硼氢化钠的物质的量的比为1:4:40。
所述的步骤(1)中所述溶剂包括乙醇、或甲醇。
所述的步骤(1)中所述的贵金属溶液采用滴加的方式加入到溶液中,其中滴加速度为2-10min/mL。
所述的贵金属盐溶液包括铂、钌、或铑的卤化物盐溶液、或硝酸盐溶液。
所述的贵金属盐溶液包括四氯化铂、三氯化钌、或硝酸铑的水溶液中的任意一种。
贵金属溶液滴加完成后,需搅拌10-30mins再滴加硼氢化钠溶液,其中硼氢化钠溶液滴加速度为2-10min/mL。
本发明的技术方案将所述的卟啉稳定的钯纳米颗粒催化剂在硼氢化钠还原对硝基苯酚中的应用。
所述的卟啉稳定的钯纳米颗粒催化剂在催化硼氢化钠还原对硝基苯酚中的步骤如下:
步骤一:将氨硼烷溶解于去离子水中;
步骤二:将卟啉稳定的贵金属纳米颗粒催化剂溶液置于反应器中,加入搅拌子,并将反应器密封,打开搅拌器搅拌;
步骤三:用注射器吸取步骤一中氨硼烷溶液,迅速注入到步骤二的反应器中,同时开始计时;
步骤四:每间隔10-60s记录对应时间下的氢气体积。
所述的卟啉稳定的贵金属纳米颗粒催化剂在反应体系中的物质的量是氨硼烷的1-8‰。
本发明所合成的贵金属纳米纳米颗粒具有相对均匀、粒径窄的分布,且颗粒形貌良好。
附图说明
图1是实施例1制备的铑纳米颗粒催化剂的透射电镜图。
图2是实施例1制备的铑纳米颗粒催化剂的粒径分布统计图。
图3是实施例2制备的铑纳米颗粒催化剂催化氨硼烷水解产氢的反应时间与生成氢气的体积的关系图。
图4是实施例3制备的铂纳米颗粒催化剂的透射电镜图。
图5是实施例3制备的铂纳米颗粒催化剂的粒径分布统计图。
图6是实施例4制备的铂纳米颗粒催化剂催化氨硼烷水解产氢的反应时间与生成氢气的体积的关系图。
图7是实施例5制备的钌纳米颗粒催化剂的透射电镜图。
图8是实施例5制备的钌纳米颗粒催化剂的粒径分布统计图。
图9是实施例6制备的钌纳米颗粒催化剂催化氨硼烷水解产氢的反应时间与生成氢气的体积的关系图。
具体实施方式
实施例1
本发明采用的制备方案包括以下步骤
步骤一:将5.0×10-3mmol的卟啉溶解于乙醇(8mL)中,搅拌至完全溶解;
步骤二:将2.0×10-2mmol的硝酸铑溶液溶解于去离子水(1mL)中,3min/mL滴加速度滴加到步骤一所得的溶液中,在冰浴环境下搅拌均匀;
步骤三:将2.0×10-1mmol的硼氢化钠溶解于1mL去离子水中,3min/mL滴加速度滴加步骤三所得的冰浴混合溶液中,反应2小时。即可得到卟啉稳定的铑纳米颗粒(RhNP@THPP)催化剂。
图1是本发明制备的新型催化剂的透射电镜图,从图1可以看出铑纳米颗粒呈均匀的球形,粒径小且分散性良好。
图2是本发明制备的新型催化剂的粒径分布统计图,从图2可以看出铑纳米颗粒的粒径主要分布在2.3-2.7nm之间,平均粒径为2.53nm。
实施例2
根据实施例1制备的铑纳米颗粒催化剂在催化氨硼烷(NH3BH3)水解产氢反应的具体步骤如下:
步骤一:将适量的氨硼烷溶解于去离子水中配成0.5mol/L的溶液;
步骤二:将含有4×10-3mmol铑纳米颗粒的卟啉稳定的铂纳米颗粒催化剂溶液置于反应器中,加入搅拌子,并将反应器密封,打开搅拌器搅拌;
步骤三:用注射器吸取步骤一中氨硼烷溶液1mL,迅速注射到步骤2的反应器中,同时开始计时;
步骤四:记录对应时间下的氢气体积。
图3是本发明制备的新型催化剂催化氨硼烷水解产氢的反应时间与生成氢气的体积的关系图。从图中可以看出,反应在1.75mins内就可结束。
实施例3
本发明采用的制备方案包括以下步骤
步骤一:将5.0×10-3mmol的卟啉溶解于乙醇(8mL)中,搅拌至完全溶解;
步骤二:将2.0×10-2mmol的四氯化铂溶解于去离子水(1mL)中,3min/mL滴加速度滴加到步骤一所得的溶液中,在冰浴环境下搅拌均匀;
步骤三:将2.0×10-1mmol的硼氢化钠溶解于1mL去离子水中,3min/mL滴加速度滴加步骤三所得的冰浴混合溶液中,反应2小时。即可得到卟啉稳定的铂纳米颗粒(PtNP@THPP)催化剂。
图4是本发明制备的新型催化剂的透射电镜图,从图4可以看出铂纳米颗粒呈均匀的球形,粒径小且分散性良好。
图5是本发明制备的新型催化剂的粒径分布统计图,从图5可以看出铂纳米颗粒的粒径主要分布在1.6-2.5nm之间,平均粒径为2.14nm。
实施例4
根据实施例3制备的铂纳米颗粒催化剂在催化氨硼烷(NH3BH3)水解产氢反应的具体步骤如下:
步骤一:将适量的氨硼烷溶解于去离子水中配成0.5mol/L的溶液;
步骤二:将含有4×10-3mmol铂纳米颗粒的卟啉稳定的铂纳米颗粒催化剂溶液置于反应器中,加入搅拌子,并将反应器密封,打开搅拌器搅拌;
步骤三:用注射器吸取步骤一中氨硼烷溶液1mL,迅速注射到步骤2的反应器中,同时开始计时;
步骤四:记录对应时间下的氢气体积。
图6是本发明制备的新型催化剂催化氨硼烷水解产氢的反应时间与生成氢气的体积的关系图。从图中可以看出,反应在5mins内就可结束。
实施例5
本发明采用的制备方案包括以下步骤
步骤一:将5.0×10-3mmol的卟啉溶解于乙醇(8mL)中,搅拌至完全溶解;
步骤二:将2.0×10-2mmol的三氯化钌溶解于去离子水(1mL)中,3min/mL滴加速度滴加到步骤一所得的溶液中,在冰浴环境下搅拌均匀;
步骤三:将2.0×10-1mmol的硼氢化钠溶解于1mL去离子水中,3min/mL滴加速度滴加步骤三所得的冰浴混合溶液中,反应2小时。即可得到卟啉稳定的钌纳米颗粒(RuNP@THPP)催化剂。
图7是本发明制备的新型催化剂的透射电镜图,从图7可以看出钌纳米颗粒呈均匀的球形,粒径小且分散性良好。
图8是本发明制备的新型催化剂的粒径分布统计图,从图8可以看出钌纳米颗粒的粒径主要分布在2.1-3.1nm之间,平均粒径为2.56nm。
实施例6
根据实施例3制备的钌纳米颗粒催化剂在催化氨硼烷(NH3BH3)水解产氢反应的具体步骤如下:
步骤一:将适量的氨硼烷溶解于去离子水中配成0.5mol/L的溶液;
步骤二:将含有4×10-3mmol钌纳米颗粒的卟啉稳定的钌纳米颗粒催化剂溶液置于反应器中,加入搅拌子,并将反应器密封,打开搅拌器搅拌;
步骤三:用注射器吸取步骤1中氨硼烷溶液1mL,迅速注射到步骤2的反应器中,同时开始计时;
步骤四:记录对应时间下的氢气体积。
图9是本发明制备的新型催化剂催化氨硼烷水解产氢的反应时间与生成氢气的体积的关系图。从图中可以看出,反应在4.5mins内就可结束。
Claims (5)
1.卟啉稳定的贵金属纳米颗粒催化剂在催化氨硼烷水解产氢上的应用,其特征在于,卟啉稳定的贵金属纳米颗粒制备方法包括以下步骤:
(1)四羟基四苯基卟啉溶解于溶剂中,在冰浴环境下搅拌至均匀;再把贵金属溶液分别缓慢加入上述卟啉溶液中,在冰浴环境下搅拌至均匀混合,所述的贵金属盐溶液为硝酸铑水溶液;
(2)将硼氢化钠溶液缓慢加入到步骤(1)的混合溶液中,在冰浴环境下反应1-5 小时,反应结束后,即可得到卟啉稳定的贵金属纳米颗粒溶液。
2.根据权利要求1 所述的应用,其特征在于,四羟基四苯基卟啉、贵金属和硼氢化钠的物质的量的比为1:1-4:10-40。
3.根据权利要求1 所述的应用,其特征在于,步骤(1)中所述溶剂包括乙醇、或甲醇。
4.根据权利要求 1 所述的应用,其特征在于,贵金属溶液滴加完成后,搅拌10-30mins,再滴加硼氢化钠溶液,其中硼氢化钠溶液滴加速度为2-10min/mL。
5.根据权利要求1所述的应用,其特征在于,水解产氢的反应体系中卟啉稳定的贵金属纳米颗粒催化剂的物质的量是氨硼烷的1-8‰。
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