Pyrolysis of folic acid: Identification of gaseous/volatile products and structural evolution of N-doped graphitic carbon

Abstract

Folic acid (FA) is a low-cost and suitable source for producing different N-doped carbon materials by pyrolysis. However, the pyrolytic steps of FA are not entirely understood, particularly above 350 °C, which hampers the intelligent design of tailor-made carbon materials by a one-pot route. In this work, the pyrolytic decomposition steps of FA were investigated by simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (TGA-DSC). The released gaseous/volatile products were probed by coupling TGA to infrared spectroscopy and mass spectrometry (TGA-FTIR-MS). Considering the thermal analysis data, FA was pyrolysed in a furnace at 350, 430, 570, 800, and 1000 °C, and the products were analysed by X-ray diffractometry (XRD), vibrational spectroscopy, and X-ray photoelectron spectroscopy. In situ high-temperature X-ray diffractometry (HT-XRD) experiments were also conducted under the nitrogen atmosphere. According to the data set, insights about FA decomposition steps could be proposed, including gaseous/volatile products released during the process and the structural evolution of N-doped graphitic carbon. The formation of carbonaceous material initiated between 200 and 350 °C through polymerisation/condensation reactions, and this step was marked by the release of 2-pyrrolidone and aniline. The graphitisation was enhanced above 350 °C, increasing graphitic nitrogen while the amide groups vanished. The process was accompanied by deoxygenation (i.e., CO and CO₂ release) and denitrogenation (e.g., NH₃, HNCO, and HCN) reactions. In the 570–800 °C range, the N-enrichment of carbon material (N-pyridine, N-pyrrole/Csp²-N in 5,7-membered rings, and nitrile) could occur by the reaction of released NH₃ over the char surface. Graphitic-like structures containing mainly N-graphite and N-pyridine were obtained above 800 °C. The original data about the thermal decomposition steps of FA allow for optimising the synthesis of N-doped carbon materials suitable for applications in adsorption, sensing, catalysis, and energy storage.