Synthesis of Spherical Carbon Nitride-Based Polymer Composites by Continuous Aerosol-Photopolymerization with Efficient Light Harvesting

Jalal Poostforooshan; Alireza Badiei; Mohammadreza Kolahdouz; Alfred P Weber

doi:10.1021/acsami.6b07909

Synthesis of Spherical Carbon Nitride-Based Polymer Composites by Continuous Aerosol-Photopolymerization with Efficient Light Harvesting

ACS Appl Mater Interfaces. 2016 Aug 24;8(33):21731-41. doi: 10.1021/acsami.6b07909. Epub 2016 Aug 11.

Authors

Jalal Poostforooshan^{1

2}, Alireza Badiei¹, Mohammadreza Kolahdouz³, Alfred P Weber²

Affiliations

¹ School of Chemistry, College of Science, University of Tehran , Tehran, Iran.
² Institute of Particle Technology, Technical University of Clausthal , Clausthal-Zellerfeld, Germany.
³ School of Electrical and Computer Engineering, University of Tehran , Tehran, Iran.

PMID: 27483090
DOI: 10.1021/acsami.6b07909

Abstract

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.

Keywords: FDTD method; aerosol−photopolymerization; carbon nitride-based polymer composite; efficient light harvesting; spherical mesoporous carbon nitride.