Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis

X-ray photoelectron spectroscopy (XPS) was used to investigate the fate of nitrogen functional forms present in a lignite and its chars, chars derived from the model compounds acridine, carbazole and polyacrylonitrile (PAN). Four different peaks have been found in the XPS patterns, corresponding to at least five different nitrogen functional forms, all being aromatic moieties. The XPS patterns of the synthetic chars were recorded for identification purposes. The distribution of nitrogen functional forms changes with increasing severity of the pyrolysis conditions. Under mild pyrolysis conditions, firstly unstable functionalities like pyridones, protonated pyridinic-N and N-oxides of pyridinic-N are converted to pyridinic-N and secondly pyrrolic-N is converted to pyridinic-N during condensation of the carbon matrix. During the condensation process, nitrogen atoms are incorporated in the graphene layers replacing carbon atoms. After severe pyrolysis all nitrogen is eventually present in 6-membered rings located at the edges of the graphene layers as pyridinic-N or in the interior as quaternary-N. Upon exposure to the ambient, N-oxides of pyridinic-N can be formed. During pyrolysis, differences in nitrogen distribution of the char precursors have diminished. It is presumed that the remaining small differences in the nitrogen distribution of the chars cannot significantly influence the formation of nitrogen oxides during combustion of the chars.