Materials GOx immobilization Km app / mM Ref. PVA-g-P(4-VP) films Physical entrapment 19 1 Nafion film Covalent attachment with GA, BSA and Nafion 14.91 2 Chitosan matrix Covalent attachment with GA in a 5% (v/v) glycerol solution 14.2 3 NiO modified glassy carbon electrodes Co-deposition with NiO nanoparticles at 0.8 V for 15 min in buffer solution 2.7 4 Gold nanoparticles Thiol-Cystamine modification of Au with IO4oxidized GOx 4.3

Research in the field of aluminum batteries has focused heavily on electrodes made of carbonaceous materials. Still, the capacities reported for these multivalent systems remain stubbornly low. It is believed that a high structural quality of graphitic carbons and/or specific surface areas of >1000 m2 g‐1 are key factors to obtain optimal performance and cycling stability. Here an aluminum chloride battery is presented in which reduced graphene oxide (RGO) powder, dried under supercritical conditions, is used as the active cathode material and niobium foil as the current collector. With a specific surface area of just 364 m2 g‐1, the RGO enables a gravimetric capacity of 171 mAh g‐1 at 100 mA g‐1 and remarkable stability over a wide range of current densities (<15% decrease over 100 cycles in the interval 100–20000 mA g‐1). These properties, up to now achieved only with much larger surface area materials, result from the cathode's tailored mesoporosity. The 20 nm wide mesopores facilitate the movement of the chloroaluminate ions through the RGO, effectively minimizing the inactive mass content of the electrode. This more than compensates for the ordinary micropore volume of the graphene powder.

Hydroperoxyl intermediate is a vital component in the mechanism of electrochemical oxygen reduction reaction (ORR) and several other important chemical reactions. The selectivity and kinetics of ORR are controlled by the energetics of *OOH intermediate (* represents the active site). The present work integrates iron phthalocyanine (FePc) with sulfonic acid-functionalized multiwalled carbon nanotubes (MWCNTs-SO 3 H). The resulting composite (FePc@MWCNTs-SO 3 H) demonstrates significantly improved kinetics and higher four-electron selectivity for the electrochemical reduction of oxygen compared to its counterpart without functionalization (FePc@MWCNTs) in alkaline, neutral, and acidic media. Based on the in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) results and DFT calculations, it is proposed that sulfonate groups are involved in the water-assisted hydrogen-bonding interaction with the FeOOH intermediate. This interaction causes a substantial increase in selectivity and kinetics of ORR. Apart from the ORR, the findings of the current work strongly recommend that the functional groups on carbon support can be manipulated to get improved kinetics and selectivity of several important chemical transformations.