Electronic interactions and stability issues at the copper-graphene interface in air and in alkaline solution under electrochemical control

A micro-electrochemical cell is sealed with a polymer-free single-layer graphene (SLG) membrane to monitor the stability of Cu nanoparticles (NPs) attached to SLG, as well as the interfacial electronic interactions between Cu NPs and SLG both in air and in a mildly alkaline aqueous solution under electrochemical control. A combination of techniques, including in-situ Kelvin probe force microscopy (KPFM) and ex-situ electron microscopy, are applied. When Cu NPs are metallic at cathodic potentials, there is a relatively bias-independent offset in the SLG work function due to charge transfer at the Cu-SLG contact. When Cu NPs are oxidized at anodic potentials, on the other hand, the work function of SLG also depends on the applied bias in a quasi-linear fashion due to electrochemical gating, in addition to charge transfer at the CuOx-SLG contact. Furthermore, Cu NPs were found to oxidize and detach from SLG when kept under anodic potentials for a few hours, whereas they remain adhered to SLG at cathodic potentials. This is attributed to water intercalation at the CuO-SLG interface associated with the enhanced hydrophilicity of positively polarized graphene, as supported by the absence of Cu detachment following oxidation by galvanic corrosion in air

Insights into the Growth of Ternary WSSe Nanotubes in an Atmospheric CVD Reactor

The synthesis of complex new nanostructures is challenging but also bears the potential for observing new physiochemical properties and offers unique applications in the long run. High-temperature synthesis of ternary WSe2xS2(1-x) (denoted as WSSe) nanotubes in a pure phase and in substantial quantities is particularly challenging, requiring a unique reactor design and control over several parameters, simultaneously. Here, the growth of WSSe nanotubes with the composition 0 ≤ x < 1 from W18O49 nanowhiskers in an atmospheric chemical vapor deposition (CVD) flow reactor is investigated. The oxide precursor powder is found to be heavily agglomerated, with long nanowhiskers decorating the outer surface of the agglomerates and their core being enriched with oxide microcrystallites. The reaction kinetics with respect to the chalcogen vapors varies substantially between the two kinds of oxide morphologies. Insights into the chemical reactivity and diffusion kinetics of S and Se within W18O49 nanowhishkers and the micro-oxide crystallites were gained through detailed microscopic, spectroscopic analysis of the reaction products and also through density functional theory (DFT) calculations. For safety reasons, the reaction duration was limited to half an hour each. Under these circumstances, the reaction was completed for some 50% of the nanotubes and the other half remained with thick oxide core producing new WOx@WSSe core-shell nanotubes. Furthermore, the selenium reacted rather slowly with the WOx nanowhiskers, whereas the more ionic and smaller sulfur atoms were shown to diffuse and react faster. The yield of the combined hollow and core-shell nanotubes on the periphery of the agglomerated oxide was very high, approaching 100% in parts of the reactor boat. The nanotubes were found to be very thin (∼80% with a diamete