The molecular mechanism of precursor evolution in the synthesis of colloidal group II-VI semiconductor nanocrystals was studied using 1H, 13C, and 31P NMR spectroscopy and mass spectrometry. Tri-n-butylphosphine chalcogenides (TBPE; E = S, Se, Te) react with an oleic acid complex of cadmium or zinc (M-OA; M = Zn, Cd) in a noncoordinating solvent (octadecene (ODE), n-nonane-d20, or n-decane-d22), affording ME nanocrystals, tri-n-butylphosphine oxide (TBPO), and oleic acid anhydride ((OA)2O). Likewise, the reaction between trialkylphosphine selenide and cadmium n-octadecylphosphonic acid complex (Cd-ODPA) in tri-n-octylphosphine oxide (TOPO) produces CdSe nanocrystals, trialkylphosphine oxide, and anhydrides of n-octadecylphosphonic acid. The disappearance of tri-n-octylphosphine selenide in the presence of Cd-OA and Cd-ODPA can be fit to a single-exponential decay (kobs = (1.30 +/- 0.08) x 10-3 s-1, Cd-ODPA, 260 degrees C, and kobs = (1.51 +/- 0.04) x 10-3 s-1, Cd-OA, 117 degrees C). The reaction approaches completion at 70-80% conversion of TOPSe under anhydrous conditions and 100% conversion in the presence of added water. Activation parameters for the reaction between TBPSe and Cd-OA in n-nonane-d20 were determined from the temperature dependence of the TBPSe decay over the range of 358-400 K (deltaH++ = 62.0 +/- 2.8 kJ.mol-1, deltaS++ = -145 +/- 8 J.mol-1.K-1). A reaction mechanism is proposed where trialkylphsophine chalcogenides deoxygenate the oleic acid or phosphonic acid surfactant to generate trialkylphosphine oxide and oleic or phosphonic acid anhydride products. Results from kinetics experiments suggest that cleavage of the phosphorus chalcogenide double bond (TOP=E) proceeds by the nucleophilic attack of phosphonate or oleate on a (TOP=E)-M complex, generating the initial M-E bond.

This paper reports the enhancement of long-term oxidation of copper at room temperature by a graphene coating. Previous studies showed that graphene is an effective anticorrosion barrier against short-term thermal and electrochemical oxidation of metals. Here, we show that a graphene coating can, on the contrary, accelerate long-term oxidation of an underlying copper substrate in ambient atmosphere at room temperature. After 6 months of exposure in air, both Raman spectroscopy and energy-dispersive X-ray spectroscopy indicated that graphene-coated copper foil had a higher degree of oxidation than uncoated foil, although X-ray photoelectron spectroscopy showed that the surface concentration of Cu(2+) was higher for the uncoated sample. In addition, we observed that the oxidation of graphene-coated copper foil was not homogeneous and occurred within micrometer-sized domains. The corrosion enhancement effect of graphene was attributed to its ability to promote electrochemical corrosion of copper.

The intrinsic wettability of graphitic materials, such as graphene and graphite, can be readily obscured by airborne hydrocarbon within 5-20 min of ambient air exposure. We report a convenient method to effectively preserve a freshly prepared graphitic surface simply through a water treatment technique. This approach significantly inhibits the hydrocarbon adsorption rate by a factor of ca. 20×, thus maintaining the intrinsic wetting behavior for many hours upon air exposure. Follow-up characterization shows that a nanometer-thick ice-like water forms on the graphitic surface, which remains stabilized at room temperature for at least 2-3 h and thus significantly decreases the adsorption of airborne hydrocarbon on the graphitic surface. This method has potential implications in minimizing hydrocarbon contamination during manufacturing, characterization, processing, and storage of graphene/graphite-based devices. As an example, we show that a water-treated graphite electrode maintains a high level of electrochemical activity in air for up to 1 day.

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The radiation of an electric dipole emitter can be drastically enhanced if the emitter is placed in the nano-gap of a metallic dipole antenna. By assuming that only surface plasmon polaritons (SPPs) are excited on the antenna, we build up an intuitive pure-SPP model that is able to comprehensively predict the electromagnetic features of the antenna radiation, such as the total or radiative emission rate and the far-field radiation pattern. With the model we can distinguish the respective contributions from SPPs and from other surface waves to the antenna radiation. It is found that for antennas with long arms that support higher-order resonances, SPPs provide a dominant contribution to the antenna radiation, while for other cases, the contribution of surface waves other than SPPs should be considered. The model reveals an intuitive picture that the enhancement of the antenna radiation is due to surface waves that are resonantly excited on the two antenna arms and that are further coupled into the nano-gap or scattered into free space. From the model we can derive a phase-matching condition that predicts the antenna resonance and the resultant enhanced radiation. The model is helpful for a physical understanding and intuitive design of antenna devices. R esonant optical nano-antennas are intensively studied in recent years due to their superior properties of generating strong electromagnetic field under far-field illuminations 1-6 and reciprocally, enhancing the radiation of emitters such as molecules or quantum dots in the vicinity of antennas [7][8][9][10][11][12][13][14][15][16][17][18][19] . Plasmonic nanoantennas are widely used in enhanced Raman scattering spectroscopy [20][21][22][23] , nonlinear optical control [24][25][26][27] , and single-emitter fluorescence enhancement [9][10][11][15][16][17][18]28 . Much experimental and theoretical work has been devoted to achieve an understanding of the underlying physics of resonant nano-antennas for guiding the design of relevant devices. For a simple single-wire nano-antenna, it is described as a Fabry-Pérot resonator of surface plasmon polaritons (SPPs) 4,5,12,19 for predicting the resonance frequency. The single-wire nano-antenna is also treated as an equivalent circuit composed of resistors, inductors and capacitors [29][30][31] , and radiation or scattering features such as the resonance frequency and the extinction spectrum can be predicted. Resonant dipole antennas, which are made of two metallic nano-wires separated by a nano-gap 1 , can achieve a much stronger enhancement effect than the single-wire antenna. Concepts of impedance and resistance are proposed for dipole antennas [32][33][34][35] for reproducing quantities such as the resonance frequency, the quantum efficiency and the enhancement of field. The dipole antennas are also modelled as one-dimensional micro-cavities 34,36 , and the enhancement effect is attributed to the resonance of SPPs. In previous literatures, it is commonly believed that the enhancement effect of the antenna radiation or th...