Two-step mechanism for low-temperature oxidation of vacancies in graphene.

We study the oxidation of vacancies in graphene by ab initio atomistic thermodynamics to identify the dominant reaction mechanisms. Our calculations show that the low-temperature oxidation occurs via a two-step process: Vacancies are initially saturated by stable O groups, such as ether (C-O-C) and carbonyl (C=O). The etching is activated by a second step of additional O2 adsorption at the ether groups, forming larger O groups, such as lactone (C-O-C=O) and anhydride (O=C-O-C=O), that may desorb as CO2 just above room temperature. Our studies show that the partial pressure of oxygen is an important external parameter that affects the mechanisms of oxidation and that allows us to control the extent of etching.

A metal-free polymeric photocatalyst for hydrogen production from water under visible light.

The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.

Structural, electronic, and chemical properties of nanoporous carbon.

Nanoporous carbon (NPC) exhibits unexplained chemical properties, making it distinct from other graphenelike materials, such as graphite, fullerenes, or nanotubes. In this Letter, we analyze the properties of NPC in terms of its structural motifs, which are derived from defects in distorted graphene sheets. Our density-functional theory calculations show that these motifs can be present in high concentration (up to 1%). Some of them induce localized levels close to the Fermi level, therefore leading to local charging and controlling the material's chemical function, for example, as a catalyst.

An interfacial complex in ZnO and its influence on charge transport.

The segregation of native defects and Bi impurities to a high-angle grain boundary in ZnO is studied by first-principles calculations. It is found that the presence of Bi(Zn) increases the concentration of native defects of acceptor type in the grain boundary. This leads to the formation of a Bi(Zn)+V(Zn)+O(i) interfacial complex under O-rich conditions and exhibits a localized acceptor state. This state, which is different from that of the isolated impurity, gives the grain boundary p-type character and when embedded between n-type ZnO grains is consistent with the double Schottky barrier model for Bi-doped ZnO varistors.