The effects of five types of oxygen-containing functional groups (–COOH, –COC–, –OH, –CHO, and –OCH3) on graphene quantum dots (GQDs) are investigated using time-dependent density functional theory (TD-DFT).

The effects of four heteroatoms (B, N, P, and S) with three doping patterns on graphene quantum dots (GQDs) are systematically investigated using time-dependent density functional theory (TD-DFT). The absorption spectra and HOMO-LUMO gaps are quantitatively analyzed to study the correlations between the optical properties and heteroatom doping of doped GQDs. Heteroatom doping can endow GQDs with various new optical and structural properties, depending on the dopants and doping configurations. Compared with the absorption spectra of pristine GQD, both N and S surface doping demonstrate a slight blue shift, whereas B and P doping lead to a blue shift for edge-doped GQDs with heteroatoms in a pentatomic ring. The absorption process is investigated along with excited state analysis, which includes the density of state, natural transition orbital, and charge difference density. The results indicate that large radius atoms assist charge transfer in the excited state and play an important role in recombining the electron density distribution in the doped GQDs.

Controllable designing of heteroatom-doped carbon catalysts provides an insightful strategy for boosting the performance and kinetics of the oxygen reduction/evolution reaction (ORR/OER). However, the role of oxygen species is usually omitted. Herein, a facile oxygen engineering strategy is proposed to tune the oxygen species in N-doped porous carbon nanofibers (NPCNFs-O) via a facile electrospinning method, in which βcyclodextrin acts as the pore inducer and oxygen regulator. Benefitting from the large specific surface area and synergistic effect of N,O codoping, the NPCNF-O catalyst exhibits superior ORR (E 1/2 = 0.85 V vs reversible hydrogen electrode (RHE)) and OER (E j = 10 = 1.556 V vs RHE) activities with excellent stability. Both experimental and theoretical calculations verify the crucial role of carboxyl groups, which regulate the local charge density and reduce the reaction energy barrier for enhancing the oxygen electrocatalytic activity. Moreover, a rechargeable zinc−air battery using NPCNF-O as the air cathode demonstrates a maximum power density of 125.1 mW cm −2 and long-term durability. Importantly, NPCNF-O can be served as an integrated freestanding electrode for portable zinc−air batteries. The work brings brilliant fundamental insights for constructing efficient metal-free carbon material catalysts for future energy conversion and storage systems.

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BC3, BCO2, and BC2O show different behaviours in tuning the electronic and optical properties of boron-doped graphene quantum dots.

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