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

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.

Graphitic carbon nitride and polymers: a mutual combination for advanced properties

“…8a). 160 Spherical mesoporous g-C 3 N 4 (SMCN) was initially prepared with mesoporous silica nanoparticles as template (Fig. 8b), then monomer was continuously added via the gas phase and polymerized in proximity of g-C 3 N 4 via photoinitiation under UV light irradiation.…”

Designer hydrogenated wrinkled yolk@shell TiO2 architectures towards advanced visible light photocatalysts for selective alcohol oxidation

“…Based on these premises, and following research endeavours from our groups, [37][38][39][40][41][42] herein we report an unprecedented strategy for the rational design of advanced yolk@hydrogenated wrinkled shell titania (Y@HWS-TiO 2 ) nanoarchitectures as selective and efficient visible light photonanocatalysts for the selective oxidation of alcohols at room temperature.…”

Condensation‐Controlled Toposelective Vapor Deposition in Nano‐ and Microcavities: Theory, Methods, Applications, and Related Technologies

“…[32] When a process has simultaneous mass transfer (equilibration) and fixation, superconformality can be reached only under specific conditions. [143,204] Self-limiting growth is not typical in VD. ALD is a powerful method because it introduced self-saturating surface reactions.…”