In‐Situ Carbon Doping of TiO2 Nanotubes Via Anodization in Graphene Oxide Quantum Dot Containing Electrolyte and Carburization to TiOxCy Nanotubes

Anodic production of self‐organized titania nanotubes (TNTs) in an electrolyte enriched with graphene oxide quantum dots (GOQDs) is reported. The TNT‐GOQD composites grown under these conditions show in‐situ carbon doping, leading to the formation of anatase TiO₂ domains and to the reduction to substoichiometric oxide (TiO_x) and TiC. Surface science and electrochemical techniques are used in synergy to reveal that graphitic carbon is incorporated into TiO₂ upon anodic nanotube growth promoting the formation of oxygen vacancies and thus TiO₂ reduction. Upon annealing in ultrahigh vacuum, titanium oxycarbide (TiO_xC_y) is formed at temperatures ≥400 °C, where the material changes from a semiconductor to a semimetal. At the solid/liquid interface, the apparent electron donor density increases from as‐grown TNTs to as‐grown TNT‐GOQD composites due to the carbon doping, and the conductivity increases further with annealing temperature due to the increasing concentration of coordinatively unsaturated C atoms, crystallinity, and TiO₂ reduction. The materials synthesized and characterized in this study find application in different areas ranging from visible light photocatalysis and photo‐electrochemistry to use as Li‐ion battery anodes and electrocatalyst supports, because it is possible to gradually tune the density of states below the Fermi level, which can be referred to as band‐gap engineering.     

Water�CGas Shift and CO Methanation Reactions over Ni�CCeO2(111) Catalysts

X-ray and ultraviolet photoelectron spectroscopies were used to study the interaction of Ni atoms with CeO₂(111) surfaces. Upon adsorption on CeO₂(111) at 300 K, nickel remains in a metallic state. Heating to elevated temperatures (500?C800 K) leads to partial reduction of the ceria substrate with the formation of Ni²⁺ species that exists as NiO and/or Ce_1?xNi_xO_2?y. Interactions of nickel with the oxide substrate significantly reduce the density of occupied Ni 3d states near the Fermi level. The results of core-level photoemission and near-edge X-ray absorption fine structure point to weakly bound CO species on CeO₂(111) which are clearly distinguishable from the formation of chemisorbed carbonates. In the presence of Ni, a stronger interaction is observed with chemisorption of CO on the admetal. When the Ni is in contact with Ce⁺³ cations, CO dissociates on the surface at 300 K forming NiC_x compounds that may be involved in the formation of CH₄ at higher temperatures. At medium and large Ni coverages (>0.3 ML), the Ni/CeO₂(111) surfaces are able to catalyze the production of methane from CO and H₂, with an activity slightly higher than that of Ni(100) or Ni(111). On the other hand, at small coverages of Ni (<0.3 ML), the Ni/CeO₂(111) surfaces exhibit a very low activity for CO methanation but are very good catalysts for the water?Cgas shift reaction.     

Formation of a Quasi‐Free‐Standing Single Layer of Graphene and Hexagonal Boron Nitride on Pt(111) by a Single Molecular Precursor

It is shown that on Pt(111) it is possible to prepare hexagonal boron nitride (h‐BN) and graphene (G) in‐plane heterojunctions from a single molecular precursor, by thermal decomposition of dimethylamine borane (DMAB). Photoemission, near‐edge X‐ray absorption spectroscopy, low energy electron microscopy, and temperature programmed desorption measurements indicate that the layer fully covers the Pt(111) surface. Evidence of in‐plane layer continuity and weak interaction with Pt substrate has been established. The findings demonstrate that dehydrogenation and pyrolitic decomposition of DMAB is an efficient and easy method for obtaining a continuous almost freestanding layer mostly made of G, h‐BN with only a low percentage (<3%) of impurities (B and N‐doped G domains or C‐doped h‐BN or boron carbonitride, BCN at the boundaries) in the same 2D sheet on a metal substrate, such as Pt(111), paving the way for the advancement of next‐generation G‐like‐based electronics and novel spintronic devices.     

Single-atom Zn for boosting supercapacitor performance

Single-atom metal-incorporated carbon nanomaterials(CMs)have shown great potential towards broad catalytic applications.In this work,we show that N-doped porous...