Heterogeneous carbon gels: N-doped carbon xerogels from resorcinol and N-containing heterocyclic aldehydes

Direct, acid (HCl) initiated sol-gel polycondensation of resorcinol with pyrrole-2-carboxaldehyde or its derivative N-methyl-2-pyrrolecarboxaldehyde yields thermosetting phenolic organic gels with N-content of up to 8.4 wt %. After carbonization, sturdy monoliths of N-doped carbon xerogels with N-content of up to 8 wt % are produced. The morphology and porosity of the doped carbons can be tuned by the solvent composition and the amount of polymerization catalyst used. An increase in carbonization temperature from 600 to 1000 °C strongly affects the carbon gels' microporosity, resulting in a decrease in N2 adsorption capacity, but a significant increase in H2 adsorption capacity (at -196 °C). The growing H2 sorption capacity with the decreasing specific surface area (measured by N2) is related to the gradual shrinkage of the carbon xerogel matrix and narrowing of the small micropores. In addition, it is demonstrated that pyridine-based heterocyclic aldehydes, that is, 2- or 4-pyridinecarboxaldehyde, condensate with resorcinol in basic conditions (KOH, NH4OH). However, in this case, monoliths cannot be produced and powders/rigid solid precipitates are obtained instead. If NH4OH is used as a sol-gel polycondensation catalyst, N-doped foams are obtained as a final carbonaceous product.