63 research outputs found
Charge transport through a single molecule of trans-1-bis-diazofluorene [60]fullerene
Fullerenes have attracted interest for their possible applications in various
electronic, biological, and optoelectronic devices. However, for efficient use
in such devices, a suitable anchoring group has to be employed that forms
well-defined and stable contacts with the electrodes. In this work, we propose
a novel fullerene tetramalonate derivate functionalized with trans-1
4,5-diazafluorene anchoring groups. The conductance of single-molecule
junctions, investigated in two different setups with the mechanically
controlled break junction technique, reveals the formation of molecular
junctions at three conductance levels. We attribute the conductance peaks to
three binding modes of the anchoring groups to the gold electrodes. Density
functional theory calculations confirm the existence of multiple binding
configurations and calculated transmission functions are consistent with
experimentally determined conductance values.Comment: 22 pages, 6 figure
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A diuranium carbide cluster stabilized inside a C80 fullerene cage.
Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing Ih(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@Ih(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@Ih(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@Ih(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses
Chronoamperometric Study of Ammonia Oxidation in a Direct Ammonia Alkaline Fuel Cell under the Influence of Microgravity
This is a study of the chronoamperometric performance of the electrochemical oxidation of ammonia in an alkaline fuel cell for space applications. Under microgravity the performance of a fuel cell is diminished by the absence of buoyancy since nitrogen gas is produced. The following catalysts were studied: platinum nanocubes of ca. 10nm, platinum nanocubes on carbon Vulcan ™ and platinum on carbon nanoonion support of ca. 10nm. These nanomaterials were studied in order to search for catalysts that may reduce or counter the loss of ammonia oxidation current densities performance under microgravity conditions. Chronoamperometries at potential values ranging from 0.2 V to 1.2V vs. cathode potential (breathing Air/300ml/min/82737 Pa) in 1.0 M NH4OH (30ml/min in anode) were done during over 30 parabolas in NASA’s C9 airplane The Weightless Wonder in January 2016 from Ellington Field Houston. The current densities at 15s in the chronoamperometry experiments showed diminishing values under microgravity and in some cases improvements of up to 92%, for Pt-carbon nanoonions, and over 70% for the three catalysts versus ground at potentials ranging from 0.2 to 0.4V after 5 minutes of chronoamperometric conditions. At higher potentials, 1.0V or higher, Pt nanocubes and Pt-carbon nanoonions showed enhancements of up to 32% and 24%, respectively. At these higher potentials we will have a contribution of oxygen evolution. The changes in current behavior are attributed to the sizes of the catalyst materials and the time needed for the N2 bubbles detachment from the Pt surface under microgravity conditions.This work was financially supported by the NASA-MIRO Center for Advanced Nanoscale Materials at the University of Puerto Rico-Río Piedras Campus Grant number NNX10AQ17A and NASA-EPSCoR grant number NNX14AN18A, Puerto Rico NASA Space Grant Consortium: NASA cooperative agreement NNX10AM80H, NASA Flight Opportunities Program Announcement of Flight Opportunities (AFO) NOCT110 call #5 and Ministerio de Economía y Competitividad (projects CTQ2013-44083-P and CTQ2013-48280-C3-3-R)
Diastereoselective Synthesis of C60/Steroid Conjugates
The design and synthesis of fullerene–steroid hybrids by using Prato’s protocol has afforded new fullerene derivatives endowed with epiandrosterone, an important naturally occurring steroid hormone. Since the formation of the pyrrolidine ring resulting from the 1,3-dipolar cyloaddition reaction takes place with generation of a new stereogenic center on the C2 of the five-membered ring, the reaction proceeds with formation of a diastereomeric mixture [compounds 6 and 7 in 70:30 ratio, 8 and 9 in 26:74 ratio (HPLC)] in which the formation of the major diasteroisomers 6 and 9 is consistent with an electrophilic attack of [60]fullerene on the Re face of the azomethine ylide directed by the steroidic unit. The chiroptical properties of these conjugates reveal typical Cotton effects in CD spectra that have been used to assign the absolute configuration of the new fulleropyrrolidines. The electrochemical study of the new compounds reveals the presence of four quasi-reversible reduction waves which are cathodically shifted in comparison with the parent C60, thus ascertaining the proposed structures.Financial support by the Ministerio de Ciencia e Innovación (MINECO) of Spain (CTQ2011-24652, CTQ2011-27253, PIB2010JP-00196, and CSD2007-00010 projects) and CAM (Madrisolar-2) is acknowledged; A.R. thanks UCM for financial support; M.S. is indebted to Programa del Grupo Santander 2012
Dye-sensitized Solar Cells
A dye-sensitized solar cell (DSSC) is a low-cost device for converting solar energy and possesses a large-area, flexible, colorful and lightweight devices. It is based on a semiconductor (TiO2) deposited on a layer of conductive ITO glass. The dye is placed over this semiconductor film, in contact with an electrolyte in order to close the circuit .
The crucial requirements for dye-sensitized solar cells are: (a) wide absorption spectrum; (b) the right anchor to the TiO2, for instance -COOH; (c) match the energy of the LUMO level of the photosensitizer with the Fermi level of the semiconductor and (d) the photosensitizer should be photostable, electrochemically and thermally.
Based in these requirements, we chose the porphyrins as electron donors in the dye, because of their superior light-harvesting ability in the visible región, connected to the anchor group by a platinum complex
Influence of Aggregation on Redox Potentials of Amphiphilic Cu(II) Complexes Modeled after Bleomycin Antibiotics
Synthesis of the Precursors for a New Covalent Organic Framework with Triangular Shaped Pores
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