Heat treating nitrogen-doped multiwalled carbon nanotubes containing up to six different types of nitrogen functionalities transforms particular nitrogen functionalities into other types which are more catalytically active toward oxygen reduction reactions (ORR). In the first stage, the unstable pyrrolic functionalities transform into pyridinic functionalities followed by an immediate transition into quaternary center and valley nitrogen functionalities. By measuring the electrocatalytic oxidation reduction current for the different samples, we achieve information on the catalytic activity connected to each type of nitrogen functionality. Through this, we conclude that quaternary nitrogen valley sites, N-Q(valley), are the most active sites for ORR in N-CNTs. The number of electrons transferred in the ORR is determined from ring disk electrode and rotating ring disk electrode measurements. Our measurements indicate that the ORR processes proceed by a direct four-electron pathway for the N-Q(valley) and the pyridinic sites while it proceeds by an indirect two-electron pathway via hydrogen peroxide at the N-Q(center) sites. Our study gives both insights on the mechanism of ORR on different nitrogen functionalities in nitrogen-doped carbon nanostructures and it proposes how to treat samples to maximize the catalytic efficiency of such samples.

The electrocatalytic reduction of CO2 provides a sustainable way to mitigate CO2 emissions, as well as store intermittent electrical energy into chemicals. However, its slow kinetics and the lack of ability to control the products of the reaction inhibit its industrial applications. In addition, the immature mechanistic understanding of the reduction process makes it difficult to develop a selective, scalable, and stable electrocatalyst. Carbon‐based materials are widely considered as a stable and abundant alternative to metals for catalyzing some of the key electrochemical reactions, including the CO2 reduction reaction. In this context, recent research advances in the development of heterogeneous nanostructured carbon‐based catalysts for electrochemical reduction of CO2 are summarized. The leading factors for consideration in carbon‐based catalyst research are discussed by analyzing the main challenges faced by electrochemical reduction of CO2. Then the emerging metal‐free doped carbon and aromatic N‐heterocycle catalysts for electrochemical reduction of CO2 with an emphasis on the formation of multicarbon hydrocarbons and oxygenates are discussed. Following that, the recent progress in metal–nitrogen–carbon structures as an extension of carbon‐based catalysts is scrutinized. Finally, an outlook for the future development of catalysts as well as the whole electrochemical system for CO2 reduction is provided.

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The change of distance between individual graphene oxide sheets due to swelling is the key parameter to explain and predict permeation of multilayered graphene oxide (GO) membranes by various solvents and solutions. In situ synchrotron X-ray diffraction study shows that swelling properties of GO membranes are distinctly different compared to precursor graphite oxide powder samples. Intercalation of liquid dioxolane, acetonitrile, acetone, and chloroform into the GO membrane structure occurs with maximum one monolayer insertion (Type I), in contrast with insertion of 2-3 layers of these solvents into the graphite oxide structure. However, the structure of GO membranes expands in liquid DMSO and DMF solvents similarly to precursor graphite oxide (Type II). It can be expected that Type II solvents will permeate GO membranes significantly faster compared to Type I solvents. The membranes are found to be stable in aqueous solutions of acidic and neutral salts, but dissolve slowly in some basic solutions of certain concentrations, e.g. in NaOH, NaHCO3 and LiF. Some larger organic molecules, alkylamines and alkylammonium cations are found to intercalate and expand the lattice of GO membranes significantly, e.g. up to ∼35 Å in octadecylamine/methanol solution. Intercalation of solutes into the GO structure is one of the limiting factors for nano-filtration of certain molecules but it also allows modification of the inter-layer distance of GO membranes and tuning of their permeation properties. For example, GO membranes functionalized with alkylammonium cations are hydrophobized and they swell in non-polar solvents.