A Study on the Stability of Carbon Nanoforms-Polyimidazolium Network Hybrids in the Conversion of CO(2) into Cyclic Carbonates: Increase in Catalytic Activity after Reuse

碳纳米结构-聚咪唑网络杂化物在二氧化碳转化为环状碳酸酯反应中的稳定性研究:重复使用后催化活性提高

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Abstract

Three different carbon nanoforms (CNFs), single-walled and multi-walled carbon nanotubes (SWCNTs, MWCNTs) and carbon nanohorns (CNHs), have been used as supports for the direct polymerization of variable amounts of a bis-vinylimidazolium salt. Transmission electron microscopy confirmed that all CNFs act as templates on the growth of the polymeric network, which perfectly covers the nanocarbons forming a cylindrical (SWCNTs, MWCNTs) or spherical (CNHs) coating. The stability of these hybrid materials was investigated in the conversion of CO(2) into cyclic carbonate under high temperature and CO(2) pressure. Compared with the homopolymerized monomer, nanotube-based materials display an improved catalytic activity. Beside the low catalytic loading (0.05-0.09 mol%) and the absence of Lewis acid co-catalysts, all the materials showed high TON values (up to 1154 for epichlorohydrin with SW-1:2). Interestingly, despite the loss of part of the polymeric coating for crumbling or peeling, the activity increases upon recycling of the materials, and this behaviour was ascribed to their change in morphology, which led to materials with higher surface areas and with more accessible catalytic sites. Transmission electron microscopy analysis, along with different experiments, have been carried out in order to elucidate these findings.

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