The coadsorption of potassium and co on the pt(111) crystal surface: A TDS,HREELS and UPS study

The interaction of CO with a potassium covered Pt(111) surface is investigated using thermal desorption (TDS), high resolution electron energy loss (HREELS) and ultraviolet photoelectron (UPS) spectroscopies. When submonolayer amounts of potassium are preadsorbed, the adsorption energy of CO increases from 25 to 36 kcal/mole, while substantial shifts in the site occupancy from the linear to the bridged site are observed. The CO stretching vibrational frequencies are shown to decrease continuously with either increasing potassium coverage or decreasing CO coverage. A minimum CO stretching frequency of 1400 cm^?1 is observed, indicative of a CO bond order of 1.5. The work function decreases by up to 4.5 eV at submonolayer potassium coverages, but then increases by 1.5 eV upon CO co-adsorption. The results indicate that the large adsorption energy, vibrational frequency and work function changes are due to molecular CO adsorption with a substantial charge donation from potassium through the platinum substrate and into the 2π¹_CO orbital.     

Nachweis und colorimetrische Bestimmungsmethoden des Molybd?ns

Ohne Zusammenfassung     

Structure and bonding issues at the interface between gold and self-assembled conjugated dithiol monolayers

Organic thiols have received extensive attention recently because of their relative stability and ease of examination compared to other potential molecular electronic materials. In this work, scanning probe microscopy (SPM) is used to study (i) the structural properties of self-assembled monolayers (SAMs) containing conjugated dithiols and (ii) the formation of the upper molecule-metal interface on dithiol SAMs. The top gold film is deposited either by thermal evaporation or by nano-transfer printing (nTP). Generally, the utility of thermal evaporation is limited because of Au diffusion through the SAMs. However, several dithiol SAMs are identified in this work that bond well to Au overlayers and act as satisfactory diffusion barriers. Coassembly of conjugated dithiols and alkanemonothiols is suggested as a route to obtain dithiols that are denser packed and more vertical (than is obtained from pure dithiol routes). High-yield nTP is demonstrated on coassembled SAMs. Advantages and limitations of different Au deposition and transfer techniques are compared on a variety of length scales.     

Instability,intermixing and electronic structure at the epitaxial LaAlO3/SrTiO3(001) heterojunction

The question of stability against diffusional mixing at the prototypical LaAlO₃/SrTiO₃(001) interface is explored using a multi-faceted experimental and theoretical approach. We combine analytical methods with a range of sensitivities to elemental concentrations and spatial separations to investigate interfaces grown using on-axis pulsed laser deposition. We also employ computational modeling based on the density function theory as well as classical force fields to explore the energetic stability of a wide variety of intermixed atomic configurations relative to the idealized, atomically abrupt model. Statistical analysis of the calculated energies for the various configurations is used to elucidate the relative thermodynamic stability of intermixed and abrupt configurations. We find that on both experimental and theoretical fronts, the tendency toward intermixing is very strong. We have also measured and calculated key electronic properties such as potential energy gradients and valence band discontinuity at the interface. We find no measurable electric field in either the LaAlO₃ or SrTiO₃, and that the valence band offset is near zero, partitioning the band discontinuity almost entirely to the conduction band edge. Significantly, we find it is not possible to account for these electronic properties theoretically without including extensive intermixing in our physical model of the interface. The atomic configurations which give the greatest electrostatic stability are those that eliminate the interface dipole by intermixing, calling into question the conventional explanation for conductivity at this interface—electronic reconstruction. Rather, evidence is presented for La indiffusion and doping of the SrTiO₃ below the interface as being the cause of the observed conductivity.     

Potassium and potassium oxide monolayers on the platinum (111) and stepped (755) crystal surfaces: A LEED,AES, and TDS study

The adsorption of potassium and the coadsorption of potassium and oxygen on the Pt(111) and stepped Pt(755) crystal surfaces were studied by AES, LEED, and TDS. Pure potassium adlayers were found by LEED to be hexagonally ordered on Pt(111) at coverages of θ = _K0.9–;1. The monolayer coverage was 5.4 × 10¹⁴K atoms/cm² (0.36 times the atomic density of the Pt(111) surface). Orientational reordering of the adlayers, similar to the behavior of noble gas phase transitions on metals, was observed. The heat of desorption of K decreased, due to depolarization effects, from 60 kcal/mole at θ_K <0.1, to 25 kcal/mole at θ_K = 1 on both Pt(111) and Pt(755). Exposure to oxygen thermally stabilizes a potassium monolayer, increasing the heat of desorption from 25 to 50 kcal/mole. Both potassium and oxygen were found to desorb simultaneously indicating strong interactions in the adsorbed overlayer. LEED results on Pt(111) further indicate that a planar K₂O layer may be formed by annealing coadsorbed potassium and oxygen to 750 K.     

Microwave- and nitronium ion-enabled rapid and direct production of highly conductive low-oxygen graphene

Currently the preferred method for large-scale production of solution-processable graphene is via a nonconductive graphene oxide (GO) pathway, which uncontrollably cuts sheets into small pieces and/or introduces nanometer-sized holes in the basal plane. These structural changes significantly decrease some of graphene's remarkable electrical and mechanical properties. Here, we report an unprecedented fast and scalable approach to avoid these problems and directly produce large, highly conductive graphene sheets. This approach intentionally excludes KMnO(4) from Hummers' methods and exploits aromatic oxidation by nitronium ions combined with the unique properties of microwave heating. This combination promotes rapid and simultaneous oxidation of multiple non-neighboring carbon atoms across an entire graphene sheet, thereby producing only a minimum concentration of oxygen moieties sufficient to enable the separation of graphene sheets. Thus, separated graphene sheets, which are referred to as microwave-enabled low-oxygen graphene, are thermally stable and highly conductive without requiring further reduction. Even in the absence of polymeric or surfactant stabilizers, concentrated dispersions of graphene with clean and well-separated graphene sheets can be obtained in both aqueous and organic solvents. This rapid and scalable approach produces high-quality graphene sheets of low oxygen content, enabling a broad spectrum of applications via low-cost solution processing.