Coal gasification fine ash (CGFA) is a carbon–mineral composite solid waste whose valorization is severely hindered by poor interfacial compatibility with organic media due to its highly polar surface. Here, we report a surface alkylation strategy using haloalkanes with variable chain lengths to systematically tune the surface chemistry and thermo-oxidative behavior of CGFA. Comprehensive spectroscopic characterizations (XPS, FTIR, and 13C NMR) confirm successful grafting of alkyl chains, which increases aliphatic C-H content from 24.8% to 43.9% while reducing polar carboxyl groups from 7.9% to 1.6%, with the mineral framework remaining intact. Thermogravimetric analysis reveals that alkylation lowers the onset decomposition temperature from 358 °C to 295 °C and enhances the maximum mass-loss rate. Kinetic analysis shows that grafted alkyl chains act as low-energy initiation sites, reducing the initial activation energy to 95 kJ/mol, while the later-stage oxidation becomes diffusion-limited. Notably, long straight-chain alkylation achieves the best performance, whereas branched chains are less effective due to steric hindrance and pore blockage. This work establishes a clear chain-length-dependent structure–thermal response relationship, positioning alkylated CGFA as a designable precursor for functional carbon materials, intelligent char-forming agents, and tunable components for energy or responsive material systems.
Jiao et al. (Fri,) studied this question.