The carbonization procedure is a crucial step for polyacrylonitrile (PAN)-based precursors to be transformed into carbon materials. In this study, PAN and poly(acrylonitrile-co-itaconic acid)s (PAIs) with different contents of itaconic acid (IA) were prepared through free radical polymerization, and their carbonization behaviors were investigated at different thermal treatment temperatures. As confirmed by Fourier transform infrared spectroscopy analyses, functional groups containing heteroatoms practically disappeared above 600 °C, due to crosslinking, condensation, dehydrogenation, and gas-evolution reactions of the carbonization processes. Deconvolution of the carbon, oxygen and nitrogen peaks from X-ray photoelectron spectroscopy analyses revealed the development of ordered and doped graphitic carbons at elevated thermal treatment temperatures. The total yields of PAIs with excess amounts of IA (3 ~ 6 mol%) demonstrated a large carbon loss during the carbonization procedures. PAI with 1 ~ 2 mol% IA afforded carbon materials with a relatively high graphitic carbon content at 1200 °C, which is potentially important for electrical conductivity. Meanwhile, carbon materials prepared from PAI with 2 mol% IA at 1200 °C exhibited a relatively high content of pyridinic nitrogen, suggesting potentially superior catalytic activity. This study afforded technical guidelines on the structural elements of PAN-based precursors to prepare carbon materials with predesigned characteristics.

碳化过程是将基于聚丙烯腈（PAN）的前体转化为碳材料的关键步骤。在这项研究中，PAN和聚（丙烯腈共通过自由基聚合反应制备了衣康酸（IA）含量不同的衣康酸（PAIs），并研究了它们在不同热处理温度下的碳化行为。如通过傅立叶变换红外光谱分析所证实的，由于碳化过程的交联，缩合，脱氢和气体逸出反应，含有杂原子的官能团在600°C以上实际上消失了。通过X射线光电子能谱分析对碳，氧和氮峰进行解卷积揭示了在升高的热处理温度下有序和掺杂的石墨碳的发展。在碳化过程中，过量IA（3〜6 mol％）的PAI的总收率表现出很大的碳损失。IA为1〜2 mol％的PAI提供的碳材料在1200°C时具有相对较高的石墨碳含量，这对导电性可能具有重要意义。同时，在1200℃下由具有2mol％IA的PAI制备的碳材料显示出相对高的吡啶二氮含量，表明潜在地优异的催化活性。这项研究为基于PAN的前体的结构元素提供了技术指导，以制备具有预先设计特征的碳材料。