Doping of porous carbons with sulfur and nitrogen markedly enhances their surface activity for formaldehyde removal

The surfaces of phosphoric acid activated carbon, referred to as CG, and steam activated one, referred to as SX, were modified through an introduction of S- and N- groups originated from thiourea. The prepared samples were used for formaldehyde removal at room temperature. Heating at 450, 600 and 950 °C altered both surface chemistry and porosity. The extents of these modifications depended on the type of carbon. Using thiourea as the modifier resulted in an incorporation of significant amounts of nitrogen and sulfur to the carbon matrices. Their speciation depended on the heat treatment conditions. The activity of samples heated at 450 °C was governed by amine groups of thiourea retained on the surface. A further heat treatment converted gradually amine nitrogen into pyridines/pyrroles and quaternary nitrogen, shifting the adsorption mechanism to rather specific interactions than a direct chemical reactivity. Carbons with few times less nitrogen than in their amine-modified counterparts, but in quaternary form and with the small amount of sulfur in thiophenic configurations, regardless the origin, worked as very efficient adsorbents of HCHO. Due to the modification of the carbon matrix electronic structure, resulting in a positive charge on carbon atoms in the vicinity of the heteroatoms incorporated to carbon rings, the density of specific adsorption centers on the surface in larger pores was significantly higher than that in ultramicropores. This markedly contributed to efficient utilization of pores/surface, where heteroatom can exist and where otherwise the dispersive adsorptions forces would be weak, for HCHO removal at ambient conditions.