Selective doping of pyridinic nitrogen in carbon materials has attracted attention due to its significant properties for various applications such as catalysts and electrodes. However, selective doping of pyridinic nitrogen together with controlling skeletal structure is challenging in the absence of catalysts. In this work, four precursors including four fused aromatic rings and pyridinic nitrogen were simply carbonized in the absence of catalysts in order to attain mass synthesis at low cost and a high percentage of pyridinic nitrogen in carbon materials with controlled edges. Among four precursors, dibenzo[f,h] quinoline (DQ) showed an extremely high percentage of pyridinic nitrogen (96 and 86%) after heat treatment at 923 and 973 K, respectively. Experimental spectroscopic analyses combined with calculated spectroscopic analyses using density functional theory calculations unveiled that the C-H next to the pyridinic nitrogen in DQ generated gulf edge structures with controlled pyridinic nitrogen after carbonization. By comparing the reactivities among the four precursors, three main factors required for maintaining the pyridinic nitrogen in carbon materials with controlled edges, such as (1) high thermal stability of the pyridinic nitrogen, (2) the presence of one pyridinic nitrogen in one ring, and (3) the formation of gulf edges including pyridinic nitrogen to protect the pyridinic nitrogen by the C-H groups on the gulf edges, were revealed.
Carbon dots (CDs) were synthesized from phloroglucinol (PG) by simple heat treatment at 220–230 °C in the atmosphere without catalysts and solvents. PG-CDs heated at 220–230 °C could be completely dissolved in environmentally friendly water and exhibited a photoluminescence (PL) peak at 485 nm with 85 nm of the full width at half maximum (FWHM). The water-soluble polymer-dot-like PG-CDs were estimated to be 1.6–3.2 nm in size, and exhibited a wide range of PL wavelength at 370–630 nm. Since the PG-CDs are water-soluble materials, PG-CDs could be homogeneously mixed with a polymer such as polyvinylpyrrolidone (PVP) in water as a solvent, and PG-CDs/PVP films were prepared. The films exhibited PL characteristics that convert ultraviolet light at 350 nm to visible light above 400 nm. Thus, using PG as the raw material which has widely been produced industrially, the water-soluble fluorescent PG-CDs/PVP films could be prepared at a low cost by environmentally friendly methods.