First-Principles Microkinetic Modeling Unravelling the Performance of Edge-Decorated Nanocarbons for Hydrogen...

The doping of graphitic and nanocarbon structures with nonmetal atoms allows for the tuning of surface electronic properties and the generation of new active sites, which can then be exploited for several catalytic applications. In this work, we investigate the direct conversion of methane into H₂ and C₂H over Klein-type zigzag graphene edges doped with nitrogen, boron, phosphorus and silicon. We combine Density Functional Theory (DFT) and microkinetic modeling to systematically investigate the reaction network and determine the most efficient edge decoration. Among the four edge-decorated nanocarbons (EDNCs) investigated, N-EDNC presented an outstanding performance for H₂ production at temperatures over 900 K, followed by P-EDNC, Si-EDNC and B-EDNC. The DFT and microkinetic analysis of the enhanced desorption rate of atomic hydrogen reveal the presence of an Eley-Rideal mechanism, in which P-EDNC showed higher activity for H₂ production in this scenario. Coke deposition resistance in the temperature range between 900 and 1500 K was evaluated, and we compared the selectivity toward H₂ and C₂H₄ production. The N-EDNC and P-EDNC active sites showed strong resistance to carbon poisoning, whereas Si-EDNC showed higher propensity to regenerate its active sites at temperatures over 1100 K. This work shows that decorated EDNCs are promising metal-free catalysts for methane conversion into H₂ and short-length alkenes.