Platinized spherical supramolecular nanoassemblies of a porphyrin: facile synthesis and excellent catalytic recyclability†,Physical Chemistry Chemical Physics

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Platinized spherical supramolecular nanoassemblies of a porphyrin: facile synthesis and excellent catalytic recyclability†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-02-23 00:00:00 , DOI: 10.1039/c8cp00173a
Guangwei Geng _{1,

2,

3,

4,

5} , Zhongju Wang _{1,

2,

3,

4,

5} , Penglei Chen _{1,

2,

3,

4,

5} , Bo Guan _{1,

2,

3,

4,

5} , Changchun Yang _{6,

7,

8,

9} , Minghua Liu _{1,

2,

3,

4,

5}

Affiliation

Porphyrin-based supramolecular nanoassemblies of a spherical morphology have been attracting broad interest owing to their wide application possibilities in numerous fields of paramount significance. Most of the existing assembly protocols, however, either suffer from the requirement of elaborately-designed yet tediously-synthesized ad hoc porphyrins, the use of surfactant templates, or accurate consideration of the experimental parameters etc. The initiation of a facile surfactant-free fabrication protocol performable under ambient conditions using commercial porphyrins as building blocks is strongly desired. We herein report that a commercial metal-free porphyrins, 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (TPPNH2), could be facilely organized to form well-defined discrete spherical nanoassemblies at room temperature by means of a simple reprecipitation method. We further find that the as-manufactured TPPNH2 nanospheres could work as photocatalysts towards the reduction of potassium tetrachloroplatinate(II), leading to their self-platinization and the production of platinum/porphyrin nanosphere nanocomposites, wherein ultrathin Pt nanoparticles of a size of ca. 3 nm are immobilized on the porphyrin nanospheres. Significantly, by taking the advantage of their easy sedimentation from aqueous suspensions, we show that the as-produced composites could serve as qualified heterogeneous nanocatalysts in terms of their excellent catalytic stability and recyclability towards the reduction of 4-nitrophenol, where the catalytic reactivity exhibits only trivial changes even after the reactions have been repeated 8 times continuously. Taking into account the general concerns of porphyrins- and Pt-based nanostructures, this might provide a facile method for the construction of spherical porphyrin nanostructures with self-platinization capability. Meanwhile, considering the high cost and scarcity of Pt, our nanocomposites with excellent stability and recyclability likely have a bright future of potential uses.

中文翻译：

卟啉的镀铂球形超分子纳米组件：易于合成和出色的催化可回收性†

球形形态的基于卟啉的超分子纳米组装件由于在许多最重要的领域中的广泛应用而引起了广泛的兴趣。大部分的现有的组件的协议，然而，无论是从精心设计的要求尚未遭受繁琐合成特设卟啉，使用表面活性剂的模板，或实验参数的准确的考虑等。强烈希望启动一种在环境条件下使用商业卟啉作为结构单元的无表面活性剂的容易制备的方案。我们在此报告，可以在室温下通过简单的方法轻松地组织商品化的无金属卟啉，5,10,15,20-四（4-氨基苯基）卟啉（TPPNH2）再沉淀法。我们进一步发现，所制造的TPPNH2纳米球可以作为光催化剂来减少四氯铂酸钾（II），从而使其自铂化并产生铂/卟啉纳米球纳米复合材料，其中尺寸为ca的超薄Pt纳米颗粒。3 nm固定在卟啉纳米球上。重要的是，通过利用它们从水性悬浮液中易于沉淀的优势，我们表明，所生产的复合物可以作为合格的多相纳米催化剂，因为它们具有出色的催化稳定性和对还原4-硝基苯酚的可回收性，在该反应中表现出催化活性。即使反应已连续重复8次，也只有很小的变化。考虑到基于卟啉和Pt的纳米结构的普遍关注，这可能为构建具有自铂化能力的球形卟啉纳米结构提供一种简便的方法。同时，考虑到Pt的高成本和稀缺性，我们的具有优异稳定性和可回收性的纳米复合材料可能具有广阔的应用前景。

更新日期：2018-02-23

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