Synthesis of Spherical Carbon Nitride-Based Polymer Composites by Continuous Aerosol-Photopolymerization with Efficient Light Harvesting.
Synthesis of Spherical Carbon Nitride-Based Polymer Composites by Continuous Aerosol-Photopolymerization with Efficient Light Harvesting.
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DOI：
10.1021/acsami.6b07909
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发表时间：
2016-08
影响因子：
9.5
通讯作者：
Jalal Poostforooshan;Alireza Badiei;M. Kolahdouz;A. Weber
中科院分区：
文献类型：
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作者：
Jalal Poostforooshan;Alireza Badiei;M. Kolahdouz;A. Weber
在这里，我们报告了一种新颖、简便、可持续的方法，通过连续气溶胶光聚合工艺制备球形亚微米氮化碳基聚合物复合材料。在此基础上，采用喷雾干燥法制备球形介孔二氧化硅（SMS）纳米颗粒作为硬模板，通过纳米浇铸法制备球形介孔氮化碳（SMCN）纳米颗粒。除了实验表征外，还利用三维时域有限差分（FDTD）方法模拟了孔隙率对SMCN内部光吸收增强的影响，从而模拟了SMCN内部电子-空穴对的产生速率。为了制备氮化碳基聚合物复合材料，SMCN纳米颗粒在n-甲基二乙醇胺（MDEA）作为共引发剂存在下，在连续气溶胶基工艺中表现出优异的丙烯酸丁酯（PBuA）单体光聚合性能。在这种一锅合成中，SMCN纳米颗粒不仅可以作为光引发剂，同时还可以作为填料和模板。气溶胶在光反应器中的平均停留时间约为90 s。本文提出的气溶胶-光聚合工艺避免了溶剂和表面活性剂的使用，可在室温下操作，更重要的是适合于制备具有疏水聚合物的球形复合材料。此外，我们还模拟了SMCN纳米颗粒在气相过程中光照时的情况，它可以自由旋转。结果表明，由于SMCN纳米颗粒的旋转作用，孔（h(+)）密度在SMCN纳米颗粒的整个部分几乎均匀分布，从而实现了高效的光捕获和更均匀的光反应。将环境友好型SMCN、光聚合和气溶胶处理的突出特点相结合，可能为生产具有多功能性能的新型聚合物复合材料开辟新的途径，特别是在绿色化学方面。
Here we report a novel, facile, and sustainable approach for the preparation of spherical submicrometer carbon nitride-based polymer composites by a continuous aerosol-photopolymerization process. In this regard, spherical mesoporous carbon nitride (SMCN) nanoparticles were initially prepared via a nanocasting approach using spray-drying synthesized spherical mesoporous silica (SMS) nanoparticles as hard templates. In addition to experimental characterization, the effect of porosity on the light absorption enhancement and consequently the generation rate of electron-hole pairs inside the SMCN was simulated using a three-dimensional finite difference time-domain (FDTD) method. To produce the carbon nitride-based polymer composite, SMCN nanoparticles exhibit excellent performance in photopolymerization of butyl acrylate (PBuA) monomer in the presence of n-methyldiethanolamine (MDEA) as a co-initiator in a continuous aerosol-based process. In this one-pot synthesis, SMCN nanoparticles act not only as photoinitiators but at the same time as fillers and templates. The average aerosol residence time in the photoreactor is about 90 s. The presented aerosol-photopolymerization process avoids the need for solvent and surfactant, operates at room temperature, and, more importantly, is suitable to produce the spherical composite with hydrophobic polymers. Furthermore, we simulated the condition of SMCN nanoparticles during illumination in the gas phase process, which can freely rotate. The results demonstrated that the hole (h(+)) density is almost equally distributed in the whole part of the SMCN nanoparticles due to their rotation, leading to efficient light harvesting and more homogeneous photoreaction. The combination of the outstanding features of environmentally friendly SMCN, photopolymerization, and aerosol processing might open new avenues, especially in green chemistry, to produce novel polymer composites with multifunctional properties.