Chemistry of low-valent platinum dimers

Physical and chemical properties of low-valent platinum dimers, namely [Pt_2(P_2O_5H_2)4]^(4-) and Pt_2(µ-dppm)_2Cl_2, have been investigated using a variety of structural and spectroscopic techniques.

Platinum(II) d^8-d^8 dimers have been shown to exhibit much thermal and photochemical reactivity. Chapter 2 describes studies aimed at elucidating the excited state reduction potenetial of [Pt_2(P_2O_5H_2)4]^(4-), Pt_2, in organic media. By conducting excited state electron transfer studies using derivatized pyridiniums and benzophenones, the excited state reduction potential has been estimated to be ~2 V. The Pt_2 complex undergoes partial oxidation to form Pt(II,III) linear chains. Chapter 3 describes the structural and spectroscopic techniques used to determine the translational symmetries of these [Pt_2(P_2O_5H_2)4]^(4-) (X = Cl, Br), Pt_2X, chains. Pt_2Br has been found to be intermediate between (AAB)_n and (AABCCB)_n, while, Pt_2Cl is of (AABCCB)_n translational symmetry. Investigations into the electronic transitions of Pt_2Cl and Pt_2Br were conducted using high pressure techniques and are presented in Chapter 4. The Pt_2X electronic spectrum exhibits bands attributable to the reduced Pt2 complex and the oxidized Pt_2X_2 complex [Pt_2(P_2O_5H_2)4]^(4-) along with an intervalence charge-tranfer band characteristic of a mixed-valence solid.

Photophysical investigations of a new luminescent chromophore, Pt_2(µ-dppm)_2Cl_2, a d^9-d^9 dimer, and its analogs are described in Chapter 5. The absorption band directly responsible for the observed emission is believed to be very weak and, as of yet, unobserved. Attempts to determine the spin multiplicty and approximate energy of this unobserved transition are described in Chapter 6. Excited-state energy transfer studies indicate that this absorption band is a triplet transition at -13,000 cm^(-1). Although, the Pt_2(µ-dppm)_2Cl_2 excited state is non-luminescent in fluid solution, it has been shown to undergo thermal electron transfer to tetracyanoethylene and photoinduced electron transfer to methylviologen. These experiments are presented in Chapter 7. Preliminary studies, described in Chapter 8, of non-bridged d^9-d^9 platinum(I) dimers have shown that [Pt_2(CNCH_3)_6]^(2+) serves as a versatile precursor in the synthesis of new d^8-d^8 A-frame complexes.

Iridium and rhodium analogues of the Shilov cycle catalyst; and the investigation and applications of the Reduction-Coupled Oxo Activation (ROA) mechanistic motif towards alkane upgrading

This dissertation will cover several disparate topics, with the overarching theme centering on the investigation of organometallic C-H activation and hydrocarbon transformation and upgrading. Chapters 2 and 3 discuss iridium and rhodium analogues of the Shilov cycle catalyst for methane to methanol oxidation, and Chapter 4 on the recently discovered ROA mechanistic motif in catalysts for various alkane partial oxidation reactions. In addition, Chapter 5 discusses the mechanism of nickel pyridine bisoxazoline Negishi catalysts for asymmetric and stereoconvergent C-C coupling, and the appendices discuss smaller projects on rhodium H/D exchange catalysts and DFT method benchmarking.

The pyrolysis of n-butane

A study of the pyrolysis of n-butane was carried out using an all-gold tubular reactor. The initial rate of decomposition of the n-butane was of 1.50-order with respect to the partial pressure of the n-butane. A free radical mechanism, similar to that originally proposed by Rice, accounted satisfactorily for the distribution of products. Oxygen was rigorously excluded from the pyrolysis gases. The surfaces of the gold reactor had been acid-treated to remove oxide impurities. Some preliminary experiments were performed in the partial oxidation of n-butane.

Growth and magnetic properties of ferromagnetic Co nanorods filled inside carbon nanotubes towards nanoscale spintronics

We synthesize Co nanorod filled inside multi-walled CNTs (MWCNTs) by microwave plasma enhanced chemical vapor deposition (MPECVD) and utilize off-axis electron holography to observe the remanent states of the filled metal nanorod inside MWCNTs at room. The MWCNTs grew up to 100-110 nm in diameter and 1.5-1.7 μm in length. The typical bright-field transmission electron microscope (TEM) images revealed both Co/Pd multisegment nanorod and Co nanorod filled inside MWCNTs on the same substrate. We have also performed energy-dispersive X-ray spectrometer (EDS) measurements to characterize the composition of metal filled inside MWCNTs. Based on high-resolution TEM measurements, we observed the face-centered-cubic (fcc) Co filled inside MWCNT. The component of magnetic induction was then measured to be 1.2±0.1 T, which is lower than the expected saturation magnetization of fcc Co of 1.7 T. The partial oxidation of the ferromagnetic metal during the process and the magnetization direction may play an important role in the determination of the quality of the remanent states. © 2008 IEEE.

Analysis of in-cylinder hydrocarbons in a multi-cylinder gasoline HCCI engine using gas chromatography

Gasoline Homogeneous Charge Compression Ignition (HCCI) combustion has been studied widely in the past decade. However, in HCCI engines using negative valve overlap (NVO), there is still uncertainty as to whether the effect of pilot injection during NVO on the start of combustion is primarily due to heat release of the pilot fuel during NVO or whether it is due to pilot fuel reformation. This paper presents data taken on a 4-cylinder gasoline direct injection, spark ignition/HCCI engine with a dual cam system, capable of recompressing residual gas. Engine in-cylinder samples are extracted at various points during the engine cycle through a high-speed sampling system and directly analysed with a gas chromatograph and flame ionisation detector. Engine parameter sweeps are performed for different pilot injection timings and quantities at a medium load point. Results show that for lean engine running conditions, earlier pilot injection timing leads to partial oxidation of the injected pilot fuel during NVO, while the fraction of light hydrocarbons remains constant for all parameter variations investigated. The same applies for a variation in pilot fuel amount. Thus there is evidence that in lean conditions, pilot injection-related NVO effects are dominated by heat release rather than fuel reformation. © 2009 SAE International.

Liquid phase epitaxy of Al0.3Ga0.7As islands

Self-organized Al0.3Ga0.7As islands generated on the (100) facet are achieved by liquid phase epitaxy. Three particularly designed experimental conditions-partial oxidation, deficient solute and air quenching-result in defect-free nucleation. Micron-sized frustums and pyramids are observed by a scanning electron microscope. The sharp end of the tip has a radius of curvature less than 50 nm. It is proposed that such Al0.3Ga0.7As islands may be potentially serviceable in microscale and nanoscale fabrication and related spheres. (C) 2004 Elsevier B.V. All rights reserved.

Changing planar thin film growth into self-assembled island formation by adjusting experimental conditions

Illustrated in this paper are two examples of altering planar growth into self-assembled island formation by adapting experimental conditions. Partial oxidation, undersaturated solution and high temperature change Frank-Van der Merwe (FM) growth of Al0.3Ga0.7As in liquid phase epitaxy (LPE) into isolated island deposition. Low growth speed, high temperature and in situ annealing in molecular beam epitaxy (MBE) cause the origination of InAs/GaAs quantum dots (QDs) to happen while the film is still below critical thickness in Stranski-Krastanow (SK) mode. Sample morphologies are characterized by scanning electron microscopy (SEM) or atomic force microscopy (AFM). It is suggested that such achievements are of value not only to fundamental researches but also to spheres of device applications as well. (c) 2004 Elsevier B.V. All rights reserved.

Micro-fabricated Al0.3Ga0.7As pyramids for potential SPM applications

A novel technique of manufacturing Al0.3Ga0.7As pyramids by liquid phase epitaxy (LPE) for scanning probe microscopy (SPM) sensors is reported Four meticulously designed conditions-partial oxidation, deficient solute, air quenching and germanium doping result in defect-free homogeneous nucleation and subsequent pyramid formation. Micrometer-sized frustums and pyramids are detected by scanning electron microscopy (SEM). The sharp end of the microtip has a radius of curvature smaller than 50 nm. It is believed that such accomplishments would contribute not only to crystal growth theory, but also to miniature fabrication technology.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.