RESUMEN
The lack of low-temperature (<200 °C) and easy-to-handle vapor deposition precursors for cadmium has been a limitation for cadmium chalcogenide ALD. Here, the cadmium amidinate system is presented as a scaffold for vapor deposition precursor design because the alkyl groups can be altered to change the properties of the precursor. Thus, the molecular structure affects the precursor stability at elevated temperature, onset of volatility, and reactivity. Cadmium bis-N,N-diisopropylacetamidinate (1) was synthesized and evaluated for its thermal stability, volatility, and reactivity-properties relevant to ALD precursors. Compounds 2, cadmium bis-N,N-diisopropyltertertiarybutylamidinate, and 3, cadmium bis-N,N-diisopropylbutylamidinate, are analogous to 1 and were synthesized by substituting the alkyl group on the bridging carbon during amidinate synthesis. All three compounds are volatile under reduced pressure, and thermal stability studies showed 1 and 3 to be stable at 100 °C in solution for days to weeks, while 2 decomposed at 100 °C within 24 h. Solution phase reactivity studies show 1 to be reactive with thiols at room temperature in a stoichiometric manner. No reactivity with either bis-silyl sulfides or alkyl sulfides was observed up to 110 °C over more than 3 days. Overall, the cadmium amidinate compounds presented here show potential as precursors in ALD/CVD processing, which can contribute to research critical for semiconductor processing.
RESUMEN
The chemical and electronic interactions of organometallic species with metal oxide support materials are of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe3)IrMe2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph3C]+), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.
RESUMEN
Crystalline tungsten disulfide (WS2) has been prepared from the reaction of bis(cyclopentadienyl)tungsten dihydride with sulfur at room temperature and ambient pressure in organic solvents. WS2 was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, resonance Raman spectroscopy, transmission electron microscopy, and X-ray absorption spectroscopy, and the resulting WS2 is highly crystalline by X-ray diffraction. The low-temperature synthesis is hypothesized to be a result of highly mobile surface W-Cp groups that are able to facilitate crystallization.
RESUMEN
Five different first-row transition metal precursors (V(III), Cr(III), Mn(II), Co(II), Ni(II)) were successfully incorporated into a catechol porous organic polymer (POP) and characterized using ATR-IR and XAS analysis. The resulting metallated POPs were then evaluated for catalytic alkyne hydrogenation using high-throughput screening techniques. All POPs were unexpectedly found to be active and selective catalysts for alkyne semihydrogenation. Three of the metallated POPs (V, Cr, Mn) are the first of their kind to be active single-site hydrogenation catalysts. These results highlight the advantages of using a POP platform to develop new catalysts which are otherwise difficult to achieve through traditional heterogeneous and homogeneous routes.
RESUMEN
Control over the oxidation state and crystalline phase of thin-film iron oxides was achieved by low-temperature atomic layer deposition (ALD), utilizing a novel iron precursor, bis(2,4-methylpentadienyl)iron. This low-temperature (T = 120 °C) route to conformal deposition of crystalline Fe3O4 or α-Fe2O3 thin films is determined by the choice of oxygen source selected for the second surface half-reaction. The approach employs ozone to produce fully oxidized α-Fe2O3 or a milder oxidant, H2O2, to generate the Fe(2+)/Fe(3+) spinel, Fe3O4. Both processes show self-limiting surface reactions and deposition rates of at least 0.6 Å/cycle, a significantly high growth rate at such mild conditions. We utilized this process to prepare conformal iron oxide thin films on a porous framework, for which α-Fe2O3 is active for photocatalytic water splitting.
RESUMEN
An in situ microbalance and infrared spectroscopic study of alternating exposures to Me2Au(S2CNEt2) and ozone illuminates the organometallic chemistry that allows for the thermal atomic layer deposition (ALD) of gold. In situ quartz crystal microbalance (QCM) studies resolve the nucleation delay and island growth of Au on a freshly prepared aluminum oxide surface with single cycle resolution, revealing inhibition for 40 cycles prior to slow nucleation and film coalescence that extends over 300 cycles. In situ infrared spectroscopy informed by first-principles computation provides insight into the surface chemistry of the self-limiting half-reactions, which are consistent with an oxidized Au surface mechanism. X-ray diffraction of ALD-grown gold on silicon, silica, sapphire, and mica reveals consistent out-of-plane oriented crystalline film growth as well as epitaxially directed in-plane orientation on closely lattice-matched mica at a relatively low growth temperature of 180 °C. A more complete understanding of ALD gold nucleation, surface chemistry, and epitaxy will inform the next generation of low-temperature, nanoscale, textured depositions that are applicable to high surface area supports.
RESUMEN
The effect of Zr modification on the catalytic activity of Co/SiO2 was investigated for nonoxidative propane dehydrogenation. Isolated Zr on SiO2 surface sites were prepared by organometallic synthesis using Zr(O t Bu)4 as a precursor. The resulting Zr/SiO2 support was functionalized with Co2+ ions via strong electrostatic adsorption. Spectroscopic (diffuse reflectance infrared Fourier transform spectroscopy, UV-vis, electron paramagnetic resonance) and microscopic characterization (transmission electron microscopy, scanning transition electron microscopy) results are consistent with single-site cobalt that preferentially associates with the mono-dispersed Zr at a variety of loadings and Co/Zr ratios. The oxidation state of Co in the as-prepared Co/SiO2 and Co-Zr/SiO2 was both +2 with tetrahedral and octahedral geometries, respectively. In situ X-ray absorption near edge structure and extended X-ray absorption fine structure results confirmed that the oxidation state of Co remained as +2 under reaction condition for both Co/SiO2 and Co-Zr/SiO2 samples and both catalysts have tetrahedral Co2+ as the active catalyst. Despite similar Co coordination environments, the catalytic activity and selectivity was significantly improved by the Zr modification of the silica support versus Co/SiO2. This was attributed to the change in oxygen donor ability and Co-O bond strength of the ≡SiO-Zr-O sites of Co-Zr/SiO2 compared with the ≡SiO- ligands in Co/SiO2. These results show that tuning of the support SiO2 oxygen donation ability by use of an anchoring site (e.g., ≡SiO-Zr-O-) can be used to alter both rate and selectivity of propane dehydrogenation with single-site heterogeneous catalysts. These results also show some preference for Co2+ active sites to associate with ≡SiO-Zr-O- sites over ≡SiO-.
RESUMEN
Dimeric and monomeric supported single-site Fe(ii) pre-catalysts on SiO2 have been prepared via organometallic grafting and characterized with advanced spectroscopic techniques. Manipulation of the surface hydroxyl concentration on the support influences monomer/dimer formation. While both pre-catalysts are highly active in liquid-phase hydrogenation, the dimeric pre-catalyst is â¼3× faster than the monomer. Preliminary XAS experiments on the H2-activated samples suggest the active species are isolated Fe(ii) sites.
RESUMEN
Actively tunable optical transmission through artificial metamaterials holds great promise for next-generation nanophotonic devices and metasurfaces. Plasmonic nanostructures and phase change materials have been extensively studied to this end due to their respective strong interactions with light and tunable dielectric constants under external stimuli. Seamlessly integrating plasmonic components with phase change materials, as demonstrated in the present work, can facilitate phase change by plasmonically enabled light confinement and meanwhile make use of the high sensitivity of plasmon resonances to the variation of dielectric constant associated with the phase change. The hybrid platform here is composed of plasmonic indium-tin-oxide nanorod arrays (ITO-NRAs) conformally coated with an ultrathin layer of a prototypical phase change material, vanadium dioxide (VO2), which enables all-optical modulation of the infrared as well as the visible spectral ranges. The interplay between the intrinsic plasmonic nonlinearity of ITO-NRAs and the phase transition induced permittivity change of VO2 gives rise to spectral and temporal responses that cannot be achieved with individual material components alone.
RESUMEN
Synchrotron characterization techniques provide some of the most powerful tools for the study of film structure and chemistry. The brilliance and tunability of the Advanced Photon Source allow access to scattering and spectroscopic techniques unavailable with in-house laboratory setups and provide the opportunity to probe various atomic layer deposition (ALD) processes in situ starting at the very first deposition cycle. Here, we present the design and implementation of a portable ALD instrument which possesses a modular reactor scheme that enables simple experimental switchover between various beamlines and characterization techniques. As first examples, we present in situ results for (1) X-ray surface scattering and reflectivity measurements of epitaxial ZnO ALD on sapphire, (2) grazing-incidence small angle scattering of MnO nucleation on silicon, and (3) grazing-incidence X-ray absorption spectroscopy of nucleation-regime Er2O3 ALD on amorphous ALD alumina and single crystalline sapphire.
RESUMEN
Atomic layer deposition (ALD) of indium sulfide (In2S3) films was achieved using a newly synthesized indium precursor and hydrogen sulfide. We obtain dense and adherent thin films free from halide and oxygen impurities. Self-limiting half-reactions are demonstrated at temperatures up to 225 °C, where oriented crystalline thin films are obtained without further annealing. Low-temperature growth of 0.89 Å/cycle is observed at 150 °C, while higher growth temperatures gradually reduce the per-cycle growth rate. Rutherford backscattering spectroscopy (RBS) together with depth-profiling Auger electron spectroscopy (AES) reveal a S/In ratio of 1.5 with no detectable carbon, nitrogen, halogen, or oxygen impurities. The resistivity of thin films prior to air exposure decreases with increasing deposition temperature, reaching <1 Ω·cm for films deposited at 225 °C. Hall measurements reveal n-type conductivity due to free electron concentrations up to 10(18) cm(-3) and mobilities of order 1 cm(2)/(V·s). The digital synthesis of In2S3 via ALD at temperatures up to 225 °C may allow high quality thin films to be leveraged in optoelectronic devices including photovoltaic absorbers, buffer layers, and intermediate band materials.
RESUMEN
The reduced heterobimetallic complex (THF)Zr(MesNP(i)Pr2)3CoN2 (1) has been examined along with a series of structurally similar reference compounds using X-ray absorption near edge structure (XANES) spectroscopy. Complex 1 has been shown to be highly reactive, often via one-electron pathways that might be expected for a d(1) Zr(III) complex. However, the presence of two strongly interacting metals in complex 1 renders the assignment of oxidation states ambiguous. Both Zr and Co K-edge XANES spectra reveal that the most accurate description of complex 1 is that of a Zr(IV)/Co(-I) zwitterion. Electronic structure calculations support this assignment.
RESUMEN
The structure of [(CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2- is [(3-CF3C6H4NCH2CH2)2NMe]2-) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF3N2NMe)Mo(CH2SiMe3)2] in [D6]benzene in the presence of five equivalents of 2-butyne led to diamagnetic [(CF3N2NMe)Mo(CHSiMe3)(eta(2)-MeC[triple bond]CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF3N2NMe)Mo(CH2SiMe3)2] with 2-butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by alpha-hydrogen abstraction in the Mo(VI) species to yield (initially) the Mo=CHSiMe3 species and tetramethylsilane.
RESUMEN
In the Buchwald-Hartwig reaction between HIPTBr (HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3 = hexaisopropylterphenyl) and (H2NCH2CH2)3N, it is possible to obtain a 65% isolated yield of (HIPTNHCH2CH2)2NCH2CH2NH2. A second coupling then can be carried out to yield a variety of "hybrid" ligands, (HIPTNHCH2CH2)2NCH2CH2NHAr, where Ar = 3,5-Me2C6H3, 3,5-(CF3)2C6H3, 3,5-(MeO)2C6H3, 3,5-Me2NC5H3, 3,5-Ph2NC5H3, 2,4,6-i-Pr3C6H2, or 2,4,6-Me3C6H2. The hybrid ligands may be attached to Mo to yield [hybrid]MoCl species. From the monochloride species, a variety of other species such as [hybrid]MoN, {[hybrid]MoN2}Na, and {[hybrid]Mo(NH3)}+ can be prepared. [Hybrid]MoN2 species were prepared through oxidation of {[hybrid]MoN2}Na species with ZnCl2, but they could not be isolated. [Hybrid]Mo=N-NH species could be observed as a consequence of the protonation of {[hybrid]MoN2}- species, but they too could not be isolated as a consequence of a facile decomposition to yield dihydrogen and [hybrid]MoN2 species. Attempts to reduce dinitrogen catalytically led to little or no ammonia being formed from dinitrogen. The fact that no ammonia was formed from dinitrogen in the case of Ar = 3,5-Me2C6H3, 3,5-(CF3)2C6H3, or 3,5-(MeO)2C6H3 could be attributed to a rapid decomposition of intermediate [hybrid]Mo=N-NH species in the catalytic reaction, a decomposition that was shown in separate studies to be accelerated dramatically by 2,6-lutidine, the conjugate base of the acid employed in the attempted catalytic reduction. X-ray structures of [(HIPTNHCH2CH2)2NCH2CH2N{3,5-(CF3)2C6H3}]MoCl and [(HIPTNHCH2CH2)2NCH2CH2N(3,5-Me2C6H3)]MoN2}Na(THF)2 are reported.
Asunto(s)
Etilenodiaminas/química , Molibdeno/química , Nitrógeno/química , Compuestos de Terfenilo/química , Amoníaco/química , Catálisis , Cristalografía por Rayos X , Ligandos , Espectroscopía de Resonancia Magnética , Conformación Molecular , Estructura Molecular , Oxidación-ReducciónRESUMEN
Three new tetramines, (ArNHCH(2)CH(2))(3)N, have been synthesized in which Ar = 3,5-(2,4,6-t-Bu(3)C(6)H(2))(2)C(6)H(3) (H(3)[HTBTN(3)N]), 3,5-(2,4,6-Me(3)C(6)H(2))(2)C(6)H(3) (H(3)[HMTN(3)N]), or 4-Br-3,5-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H(2) (H(3)[pBrHIPTN(3)N]). The diarylated tetramine, [3,5-(2,4,6-t-Bu(3)C(6)H(2))(2)C(6)H(3)NHCH(2)CH(2)](2)NCH(2)CH(2)NH(2), has also been isolated, and the "hybrid" tetramine [3,5-(2,4,6-t-Bu(3)C(6)H(2))(2)C(6)H(3)NHCH(2)CH(2)](2)NCH(2)CH(2)NH(4-t-BuC(6)H(4)) has been prepared from it. Monochloride complexes, [(TerNCH(2)CH(2))(3)N]MoCl, have been prepared, as well as a selection of intermediates that would be expected in a catalytic dinitrogen reduction such as [(TerNCH(2)CH(2))(3)N]Mo[triple bond]N and [[(TerNCH(2)CH(2))(3)N]Mo(NH(3))][BAr'(4)] (Ter = HTBT, HMT, or pBrHIPT and Ar' = 3,5-(CF(3))(2)C(6)H(3))). Intermediates that contain the new terphenyl-substituted ligands are then evaluated for their efficiency for the catalytic reduction of dinitrogen under conditions where analogous [HIPTN(3)N]Mo species give four turnovers to ammonia under "standard" conditions with an efficiency of approximately 65%. Only [pBrHIPTN(3)N]Mo compounds are efficient catalysts for dinitrogen reduction. The reasons are explored and discussed.