Encouraged by the unusual free N-H bond tolerance and excellent chemo-and regioselectivities observed in the Giese reaction described above, we sought to investigate the influence of different CDs catalysts on the reactivity. As previously discussed, dopants may contribute to shifting the band positions of CDs, either by altering the carbon core structure or by acting as surface polarity regulators in the form of alkyl ammonium cations. By replacing secondary amine (1,4,7,10-tetraazacyclododecane) in the synthesis of CD-1 with a tertiary amine (1,4-diazabicyclo [2.2.2] octane, DABCO), we obtained another highly fluorescent CD catalyst, CD-2 (fig. ). Photoluminescent studies revealed the two catalysts exhibited almost identical PL spectra under 400 nm excitation (fig. ). Elemental analysis confirmed the C, H, N, and O contents in CD-1 and CD-2 were almost the same (table ). The primary structural difference was the different binding energy of N atoms, as shown by X-ray photoelectron spectroscopy (XPS) (fig. ). A significant proportion of N atoms in CD-2 existed in the form of ammonium cations, likely resulting from alkylation of the tertiary amines during the hydrothermal carbonization process, as anticipated. Such resulted cation-rich core/surface structure would naturally lead to an additional work potential during electron transfer (ref 10). Consequently, compared to CD-1, the redox window of CD-2 photocatalyst shifted to a much more oxidative region, with E 1 2 ⁄ red = 1.55v and E 1 2