Carbon-based materials are considered to be active for electrochemical oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2) production. Nevertheless, less attention is paid to the investigation of the influence of in-plane carbon lattice defect on the catalytic activity and selectivity toward ORR. In the present work, graphene precursors were prepared from oxo-functionalized graphene (oxo-G) and graphene oxide (GO) with H2O2 hydrothermal treatment, respectively. Statistical Raman spectroscopy (SRS) analysis demonstrated the increased in-plane carbon lattice defect density in the order of oxo-G, oxo-G/H2O2, GO, GO/H2O2. Furthermore, nitrogen-doped graphene materials were prepared through ammonium hydroxide hydrothermal treatment of those graphene precursors. Rotating ring-disk electrode (RRDE) results indicate that the nitrogen-doped graphene derived from oxo-G with lowest in-plane carbon lattice defects exhibited the highest H2O2 selectivity of >82% in 0.1 M KOH. Moreover, a high H2O2 production rate of 224.8 mmol gcatalyst –1 h–1 could be achieved at 0.2 VRHE in H-cell with faradaic efficiency of >43.6%. Our work provides insights for the design and synthesis of carbon-based electrocatalysts for H2O2 production.

Oxidative wet-chemical delamination of graphene from graphite is expected to become a scalable production method. However, the formation process of the intermediate stage-1 graphite sulfate by sulfuric acid intercalation and its subsequent oxidation are poorly understood and lattice defect formation must be avoided. Here, we demonstrate film formation of micrometer-sized graphene flakes with lattice defects down to 0.02% and visualize the carbon lattice by transmission electron microscopy at atomic resolution. Interestingly, we find that only well-ordered, highly crystalline graphite delaminates into oxo-functionalized graphene, whereas other graphite grades do not form a proper stage-1 intercalate and revert back to graphite upon hydrolysis. Ab initio molecular dynamics simulations show that ideal stacking and electronic oxidation of the graphite layers significantly reduce the friction of the moving sulfuric acid molecules, thereby facilitating intercalation. Furthermore, the evaluation of the stability of oxo-species in graphite sulfate supports an oxidation mechanism that obviates intercalation of the oxidant.

Potential biomedicinal applications of graphene oxide (GO), for example, as a carrier of biomolecules or a reagent for photothermal therapy and biosensing, are limited by its cytotoxicity and mutagenicity. It is believed that these properties are at least partially caused by GO-induced oxidative stress in cells. However, it is not known which chemical fragments of GO are responsible for this unfavorable effect. We generated four GOs containing variable redox-active groups on the surface, including Mn(2+), C-centered radicals, and endoperoxides (EPs). A comparison of the abilities of these materials to generate reactive oxygen species in human cervical cancer cells revealed that EPs play a crucial role in GO-induced oxidative stress. These data could be applied to the rational design of biocompatible nontoxic GOs for biomedical applications.

The preparation and performance of a new cathodic battery material consisting of a composite of poly(vinylferrocene) (PVFc) and reduced graphene oxide (rGO) is described. It shows the highest charge/discharge efficiency (at a rate of 100 A g−1) ever reported for ferrocene–polymer materials. The composite allows for specific capacities up to 0.21 mAh cm−2 (770 mC cm−2, 29 μm film thickness) at a specific capacity density of 114 mAh g−1 and less than 5% performance decay over 300 cycles. The composite material is binder free and the charge storing PVFc accounts for 88% of the total weight of the cathodic material. The superb performance is based on (i) perfect self‐assembling of oxidized PVFc on graphene oxide (GO) leading to PVFc@GO, (ii) its stepwise (n steps) transfer onto a current collector (CC) (PVFc@GO)n@CC (n = drop casting steps), and (iii) the efficient electrochemical transformation of GO into rGO in the composite using viologen as homogeneous electrocatalyst. The self‐assembling step is analyzed by zeta potential and atomic force microscopy (AFM) studies, demonstrating heavy ferrocene loading on GO and a mesoporous composite structure, respectively. Complete GO/rGO transition and quantitative ClO4 − ion breathing of the composite are found by electrochemical quartz crystal microbalance and by electrochemical AFM.