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Reduced dimensionality and interlayer coupling in van der Waals materials gives rise to fundamentally different electronic , optical and many-body quantum properties in monolayers compared with the bulk. This layer-dependence permits the discovery of novel material properties in the monolayer regime. Ferromagnetic order in two-dimensional materials is a coveted property that would allow fundamental studies of spin behaviour in low dimensions and enable new spintronics applications. Recent studies have shown that for the bulk-ferromagnetic layered materials CrI (ref. ) and CrGeTe (ref. ), ferromagnetic order is maintained down to the ultrathin limit at low temperatures. Contrary to these observations, we report the emergence of strong ferromagnetic ordering for monolayer VSe, a material that is paramagnetic in the bulk. Importantly, the ferromagnetic ordering with a large magnetic moment persists to above room temperature, making VSe an attractive material for van der Waals spintronics applications.

Many proposed applications of graphene require the ability to tune its electronic structure at the nanoscale. Although charge transfer and field-effect doping can be applied to manipulate charge carrier concentrations, using them to achieve nanoscale control remains a challenge. An alternative approach is 'self-doping', in which extended defects are introduced into the graphene lattice. The controlled engineering of these defects represents a viable approach to creation and nanoscale control of one-dimensional charge distributions with widths of several atoms. However, the only experimentally realized extended defects so far have been the edges of graphene nanoribbons, which show dangling bonds that make them chemically unstable. Here, we report the realization of a one-dimensional topological defect in graphene, containing octagonal and pentagonal sp(2)-hybridized carbon rings embedded in a perfect graphene sheet. By doping the surrounding graphene lattice, the defect acts as a quasi-one-dimensional metallic wire. Such wires may form building blocks for atomic-scale, all-carbon electronics.

The prototypical photocatalyst TiO2 exists in different polymorphs, the most common forms are the anatase- and rutile-crystal structures. Generally, anatase is more active than rutile, but no consensus exists to explain this difference. Here we demonstrate that it is the bulk transport of excitons to the surface that contributes to the difference. Utilizing high –quality epitaxial TiO2 films of the two polymorphs we evaluate the photocatalytic activity as a function of TiO2-film thickness. For anatase the activity increases for films up to ~5 nm thick, while rutile films reach their maximum activity for ~2.5 nm films already. This shows that charge carriers excited deeper in the bulk contribute to surface reactions in anatase than in rutile. Furthermore, we measure surface orientation dependent activity on rutile single crystals. The pronounced orientation-dependent activity can also be correlated to anisotropic bulk charge carrier mobility, suggesting general importance of bulk charge diffusion for explaining photocatalytic anisotropies.

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Nitrogen doping-induced changes in the electronic properties, defect formation, and surface structure of TiO2 rutile(110) and anatase(101) single crystals were investigated. No band gap narrowing is observed, but N doping induces localized N 2p states within the band gap just above the valence band. N is present in a N(III) valence state, which facilitates the formation of oxygen vacancies and Ti 3d band gap states at elevated temperatures. The increased O vacancy formation triggers the 1 x 2 reconstruction of the rutile (110) surface. This thermal instability may degrade the catalyst during applications.

Surface defects strongly influence the surface chemistry of metal oxides, and a detailed picture of defect structures may help to understand reactivity and overall materials performance in many applications. We report first-principles calculations of step edges, the most common intrinsic defects on surfaces (and probably the predominant ones on nanoparticles). We have determined the structure, energetics, and chemistry of step edges on the (101) surface of TiO(2) anatase, an important photocatalytic material. Scanning tunnelling microscopy measurements of step-edge configurations and the contrast in atomically resolved images agree remarkably well with the theoretical predictions. Step-edge formation energies as well as the adsorption energies of water scale with the surface energy of the step facet, a trend that is expected to generally hold for metal oxide surfaces. Depending on the terrace/step configuration, this can lead to a situation where a step is less reactive than the flat terrace.

Titanium dioxide is the prototypical transition metal oxide photocatalyst. However, the larger than 3 eV bandgap of common bulk phases of TiO₂ limits its light absorption to UV light, making it inefficient for solar energy conversion. Attempts at increasing visible light activity by narrowing the bandgap of TiO₂ through doping have proven difficult, because of defect-induced charge trapping and recombination sites of photo-excited charge carriers. Here, we report the existence of a dopant-free, pure TiO₂ phase with a narrow bandgap. This new pure TiO₂ phase forms on the surface of rutile TiO₂(011) by oxidation of bulk titanium interstitials. We measure a bandgap of only ~2.1 eV for this new phase, matching it closely with the energy of visible light.