Transient photoinduced phenomena in graphitic carbon nitride as measured at nanoseconds resolution by step-scan FTIR

Transient FTIR measurements were performed on graphitic carbon nitride using a step-scan method, facilitating temporal resolution of a few nanoseconds. Variations in the location and the intensity of specific peaks and emerging of new peaks were observed during the first 170 nanoseconds after excitation. A comparison was made between graphitic carbon nitride prepared at two temperatures: 510 degrees C and 650 degrees C. The material prepared at 650 degrees C revealed very strong non-specific absorption beginning 35 nanoseconds after excitation and lasting for 20 nanoseconds. This phenomenon, termed IR-blackening was observed neither in g-C3N4 prepared at 510 degrees C nor in g-C3N4 prepared at 650 degrees C that was exposed to hole scavengers (ethanol and benzyl alcohol). In contrast, exposure of material prepared at 650 degrees C to an electron scavenger (methyl viologen) hardly alter the IR-blackening phenomenon. The results were explained by a mechanism, predicting higher reductive activity for materials having imperfect heptazine polymerization, as indeed was found in the photocatalytic degradation of 4-nitrophenol.