Multiple electron and proton transfers in nanomaterials pose significant demands and challenges across the various fields such as renewable energy, chemical processes, biological applications, and photophysics. In this context, pH-responsive functional group-enriched carbon dots (C-Dots) emerge as superior proton-coupled electron transfer (PCET) agents owing to the presence of multiple functional groups (-COOH, -NH2, and -OH) on the surface and redox-active sites in the core. Here, we elucidate the 2e-/2H+ transfer ability of carboxyl-enriched C-Dots (C-Dot-COOH) and amine-enriched C-Dots (C-Dot-NH2) with molecular 2e-/2H+ acceptor (benzoquinone, BQ) as a function of pKa, facilitated by the formation of new O-H bonds. The ground state and excited state pKa values of different functional groups on the surface of C-Dots are determined using steady-state absorbance and photoluminescence (PL) spectroscopy. The optical spectroscopy and electrochemical studies are employed to comprehend the influence of the surface and core of C-Dots on the proton and electron transfer processes as a function of pH. The cyclic voltammetry analysis reveals a standard Nernstian shift in E1/2 per pH unit of 30 mV, indicating that the functionalized C-Dots hold promise as candidates for the 2e-/2H+ transfer process. The calculated bond dissociation free energy (BDFE) of the electroactive O-H/N-H bonds provides a more nuanced and detailed understanding of PCET thermodynamic landscapes. These findings underscore the potential of nanoscale functionalized C-Dots for facilitating multiple PCET reactions in future energy technologies.
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