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Electrochemically Triggered Chain Reactions for the Conversion of Furan Derivatives
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Hydrogenation and C-S bond activation pathways in thiophene and tetrahydrothiophene reactions on sulfur-passivated surfaces of Ru, Pt, and Re nanoparticles
Thiophene-H2 reactions proceed via sulfur removal and hydrogenation routes on dispersed metal nanoparticles that become decorated by refractory S-adlayers during catalysis. The identity and kinetic relevance of the required elementary steps are described here based on rates measured at S-chemical potentials set by H2S/H2 ratios similar to those prevalent during practical catalysis on Re, ReSx, Ru, and Pt catalysts. Free energies for S adatom formation (from H2S decomposition and H2 evolution) are strongly exothermic (< -50 kJ mol-1 on Pt(111) and < -150 kJ mol-1 on Re and Ru(0001)), but strong repulsions between S adatoms cause adsorption free energies to increase significantly with coverage on all three surfaces, preventing complete monolayer formation. These adlayers, composed of unreactive S-atoms (S') that cover 1/3–2/3 ML leave residual interstitial spaces (*) that bind S-atoms (S*), intermediates, and transition states reversibly, as required for catalytic turnovers. The number and binding properties of these interstices depend on the identity and chemical state of the nanoparticle bulk phase, which influences S'-binding and coverages and cause large differences in direct desulfurization and hydrogenation turnover rates (per exposed metal atom) on dispersed Re, ReSx, Ru, and Pt. The identity and kinetic relevance of elementary steps for desulfurization (to C4¬ hydrocarbons) and hydrogenation (to tetrahydrothiophene; THT) are similar among these catalysts; they involve the kinetically-relevant formation of a thiophene-derived intermediate (monohydrothiophene on Re and ReSx; dihydrothiophene on Ru and Pt) that either cleaves its C-S bond or “over-hydrogenates” to THT in one surface sojourn. THT then undergoes C-S bond cleavage in secondary reactions that correct such over-hydrogenation to form the more unsaturated species that cleave C-S bonds. THT/C4 product ratios are insensitive to H2S/H2 ratios and thiophene pressure, even though active interstitial spaces are covered by kinetically-detectable coverages of S* and thiophene; therefore, primary and secondary reactions must involve the same active surfaces. The observed increase in THT/C4 ratios with H2 pressure shows that THT formation transition states involve a larger number of H-atoms than for C-S cleavage. The requirement for bound species with intermediate unsaturation (between THT and thiophene) for C-S bond cleavage is reminiscent of the H-shuttling required in C-C and C-O hydrogenolysis, reactions that involve the partial dehydrogenation of alkanes and alkanols, respectively, to weaken such bonds and to increase the formation entropy of the relevant transition states via the evolution of H2(g). These mechanistic details challenge prevalent paradigms about different site requirements for hydrogenation and desulfurization pathways and about how metal-sulfur bond energies act as descriptors of reactivity; in fact, such binding energies merely act to define the refractory S-adlayers that enable the formation of weakly-binding interstices that reversibly bind intermediates and transition states, thus allowing catalytic turnovers.
Styrene Thermal Decomposition and Its Reaction with Acetylene under Shock Tube Pyrolysis Conditions: an Experimental and Kinetic Modeling Study
Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100-1730 K, nominal pressure of 20 bar, and reaction duration of similar to 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C14H12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C14H10 compounds are formed as a result of the following breakdown of the C14H12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C14H12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes.
Submonolayer Is Enough: Switching Reaction Channels on Pt/SiO 2 by Atomic Layer Deposition
The reaction mechanism of CO 2 with H 2 is studied on platinum nanoparticles supported on fumed silica. It is found that platinum nanoparticle size, reaction temperature, and metal oxide promoters play important roles in determining the reaction rate and the mechanism of forming surface carbonyl species. Metal oxide promoters consist of sub-monolayer titanium oxide or aluminum oxide overcoated onto the catalysts by atomic layer deposition (ALD). Furthermore, these alter the CO formation rate, influence the adsorption and desorption behavior, and switch the surface reaction channel from Eley-Rideal to Langmuir-Hinshelwood mechanism due to an enhancement of CO 2 affinity to the metal-metal oxide interface. At the temperatures relevant for catalytic turnover, ALD overcoating significantly increases catalytic activity in CO 2 hydrogenation to CH 4 and CO, while the identity of the oxide overcoat helps control product selectivity.
A Replacement Reaction Enabled Interdigitated Metal/Solid Electrolyte Architecture for Battery Cycling at 20 mA cm-2 and 20 mAh cm-2
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Mechanisms of the Cu(I)-Catalyzed Intermolecular Photocycloaddition Reaction Revealed by Optical and X-ray Transient Absorption Spectroscopies
The [2 + 2] photocycloaddition provides a simple, single-step route to cyclobutane moieties that would otherwise be disfavored or impossible due to ring strain and/or steric interactions. We have used a combination of optical and X-ray transient absorption spectroscopies to elucidate the mechanism of the Cu(I)-catalyzed intermolecular photocycloaddition reaction using norbornene and cyclohexene as model substrates. We find that for norbornene the reaction proceeds through an initial metal-to-ligand charge transfer (MLCT) state that persists for 18 ns before the metal returns to the monovalent oxidation state. The Cu K-edge spectrum continues to evolve until ~5 μs and then remains unchanged for the 50 μs duration of the measurement, reflecting product formation and ligand dissociation. We hypothesize that the MLCT transition and reverse electron transfer serve to sensitize the triplet excited state of one of the norbornene ligands, which then dimerizes with the other to give the product. For the case of cyclohexene, however, we do not observe a charge transfer state following photoexcitation and instead find evidence for an increase in the metal–ligand bond strength that persists for several ns before product formation occurs. This is consistent with a mechanism in which ligand photoisomerization is the initial step, which was first proposed by Salomon and Kochi in 1974 to explain the stereoselectivity of the reaction. Furthermore, our investigation reveals how this photocatalytic reaction may be directed along strikingly disparate trajectories by only very minor changes to the structure of the substrate.
Study of the ${{^{25}}}$Mg(d,p)${{^{26}}}$Mg reaction to constrain the ${{^{25}}}$Al(p,${\gamma }$)${{^{26}}}$Si resonant reaction rates in nova burning conditions
The rate of the 25 Al( p,γ) 26 Si reaction is one of the few key remaining nuclear uncertainties required for predicting the production of the cosmic γ-ray emitter 26 Al in explosive burning in novae. This reaction rate is dominated by three key resonances (J π = 0 + , 1 + and 3 + ) in 26 Si. Only the 3 + resonance strength has been directly constrained by experiment. A high resolution measurement of the 25 Mg(d, p) reaction was used to determine spectroscopic factors for analog states in the mirror nucleus, 26 Mg. A first spectroscopic factor value is reported for the 0 + state at 6.256 MeV, and a strict upper limit is set on the value for the 1 + state at 5.691 MeV, that is incompatible with an earlier ( 4 He, 3 He) study. These results are used to estimate proton partial widths, and resonance strengths of analog states in 26 Si contributing to the 25 Al( p,γ) 26 Si reaction rate in nova burning conditions.
The {sup 136}Xe + {sup 198}Pt Reaction: a Detailed Re-examination
We extend previous measurements of the transfer product yields in the reaction of E-c.m. = 450 MeV Xe-136 with Pt-198 by measurements of the product yields using Gammasphere. By recording events occurring in beam bursts and in between beam bursts, we are able to extend the number of measured product yields from 78 to 171 nuclides. Our new data span a much wider range of Z and A than observed in previous work and when compared to theoretical predictions, these new measurements provide a more stringent and thorough test of models of multi-nucleon transfer (MNT) reactions.
Reactions of NO 3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reaction
Rate coefficients for the reaction of NO3 radicals with a series of aromatic aldehydes were measured in a 7300 L simulation chamber at ambient temperature and pressure by relative and absolute methods. The rate coefficients for benzaldehyde (BA), ortho-tolualdehyde (O-TA), meta-tolualdehyde (M-TA), para-tolualdehyde (P-TA), 2,4-dimethyl benzaldehyde (2,4-DMBA), 2,5-dimethyl benzaldehyde (2,5-DMBA) and 3,5-dimethyl benzaldehyde (3,5-DMBA) were k 1 = 2.6 ± 0.3, k 2 = 8.7 ± 0.8, k 3 = 4.9 ± 0.5, k 4 = 4.9 ± 0.4, k 5 = 15.1 ± 1.3, k 6 = 12.8 ± 1.2 and k 7 = 6.2 ± 0.6, respectively, in the units of 10 -15 cm 3 molec. -1 s -1 at 298 ± 2 K. The rate coefficient k 13 for the reaction of the NO 3 radical with deuterated benzaldehyde (benzaldehyde-d1) was found to be half that of k 1 . The end product of the reaction in an excess of NO 2 was measured to be C 6 H 5 C(O)O 2 NO 2 . Furthermore, theoretical calculations of aldehydic bond energies and reaction pathways indicate that the NO 3 radical reacts primarily with aromatic aldehydes through the abstraction of an aldehydic hydrogen atom. The atmospheric implications of the measured rate coefficients are briefly discussed.
Impingement effect of service module reaction control system engine plumes. Results of service module reaction control system plume model force field application to an inflight Skylab mission proximity operation situation with the inflight Skylab response
Plume impingement effects of the service module reaction control system thruster firings were studied to determine if previous flight experience would support the current plume impingement model for the orbiter reaction control system engines. The orbiter reaction control system is used for rotational and translational maneuvers such as those required during rendezvous, braking, docking, and station keeping. Therefore, an understanding of the characteristics and effects of the plume force fields generated by the reaction control system thruster firings were examined to develop the procedures for orbiter/payload proximity operations.
Reaction rate and products for the reaction O/3P/ + H2CO
A study of reaction kinetics of O + H2CO in a discharge-flow system using mass spectrometric detection of reactants and products is presented. It was performed under both oxygen-atom-rich and formaldehyde-rich conditions over the 296 to 437 K range, showing that the global bimolecular rate constant is in agreement with other studies. This study differs from others in that the reaction products can be observed, and a substantial yield of a primary reaction product was measured with a mass spectral peak at m/e=44. This suggests that the global reaction rate probably consists of combination, as well as of simple abstraction. For the combination, one hypothesis is that triplet dioxymethylene is formed which polymerizes to triplet formic acid; the vibrationally excited triplet formic acid may decompose to form several sets of products, including HCO + OH and HCO2 + H.
Preliminary studies on NiAl/Nb2Be17 reaction and effectiveness of BeO as an interfacial reaction barrier
The interfacial reaction between NiAl and Nb2Be17 (used as a reinforcement for the alloy) was studied by measuring diffusion bonding of NiAl and Nb2Be17 plates in a hot press under a vacuum of 10 exp -5 atm. It was found that, after 2 hrs of hot pressing at 1373 K, the reaction between NiAl and Nb2Be17 was extensive. A 40 to 50-micron-thick reaction zone consisted of three distinct layers at the NiAl/Nb2Be17 interface: layer A next to Nb2Be17, layer B in the middle, and layer C next to NiAl. Results of analysis of the reaction layers using energy dispersive spectroscopy (EDS) were inconclusive because of the inabiliaty of EDS to detect Be.
Oligomerization reactions of ribonucleotides - The reaction of the 5'-phosphorimidazolide of nucleosides on montmorillonite and other minerals
The reaction of ImpA in the presence of Na(+)-montmorillonite 22A or Na(+)-Volclay in aqueous, pH 8 solution gives a 50-60 percent yield of dimers and trimers (pA)2 and (pA)3. The ratio of 3',5'-phosphodiester bond formation is twice as great as 2',5'-bond formation. The reaction requires the presence of Mg2+ and is inhibited by 0.4 M imidazole. N-methylimidazole enhances the rate of the reaction but does not cause major changes in yield or product composition. Higher yields were obtained when Li+- or Ca2+-montmorillonites were used in place of Na+-montmorillonite. Little or no phosphodiester bond formation was observed with Mg2+- or Al3+-montmorillonite. Montmorillonites other than 22A and Volclay exhibited litle or no catalysis. In addittion, little or no catalysis was exhibited in ferrugenous smectite, nontronite, allophane, imogolite or sepiolite. Oligomers were also formed by the reaction of ImpG, 2-methylImpG, ImpC and ImpU in the presence of Na+-montmorillonite. The pyrimidine nucleotides gave significantly lower yields of oligomers.
The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process
The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.
Microstructure and Mechanical Properties of Reaction-Formed Joints in Reaction Bonded Silicon Carbide Ceramics
A reaction-bonded silicon carbide (RB-SiC) ceramic material (Carborundum's Cerastar RB-SIC) has been joined using a reaction forming approach. Microstructure and mechanical properties of three types of reaction-formed joints (350 micron, 50-55 micron, and 20-25 micron thick) have been evaluated. Thick (approximately 350 micron) joints consist mainly of silicon with a small amount of silicon carbide. The flexural strength of thick joints is about 44 plus or minus 2 MPa, and fracture always occurs at the joints. The microscopic examination of fracture surfaces of specimens with thick joints tested at room temperature revealed the failure mode to be typically brittle. Thin joints (<50-55 micron) consist of silicon carbide and silicon phases. The room and high temperature flexural strengths of thin (<50-55 micron) reaction-formed joints have been found to be at least equal to that of the bulk Cerastar RB-SIC materials because the flexure bars fracture away from the joint regions. In this case, the fracture origins appear to be inhomogeneities inside the parent material. This was always found to be the case for thin joints tested at temperatures up to 1350C in air. This observation suggests that the strength of Cerastar RB-SIC material containing a thin joint is not limited by the joint strength but by the strength of the bulk (parent) materials.
Quantum Dynamics Scattering Study of AB+CDE Reactions: A Seven Dimensional Treatment for the H2+C2H Reaction
A time-dependent wave-packet approach is presented for the quantum dynamics study of the AB+CDE reaction system for zero total angular momentum. A seven-degree-of-freedom calculation is employed to study the chemical reaction of H2+C2H yields H + C2H2 by treating C2H as a linear molecule. Initial state selected reaction probabilities are presented for various initial ro-vibrational states. This study shows that vibrational excitation of H2 enhances the reaction probability, whereas the excitation of C2H has only a small effect on the reactivity. An integral cross section is also reported for the initial ground states of H2 and C2H. The theoretical and experimental results agree with each other very well when the calculated seven dimensional results are adjusted to account for the lower transition state barrier heights found in recent ab initio calculations.
Multiple Reaction Pathways for the Oxygen Evolution Reaction May Contribute to IrO 2 (110)’s High Activity
Density functional theory calculations in conjunction with statistical mechanical arguments are performed on the rutile IrO 2 (110) facet in order to characterize multiple reaction pathways on the surface at the highest active limit (the stoichiometric surface with all metal sites available) and at the lowest active limit (the oxygen-terminated surface). Alternative pathways to the oxygen evolution reaction (OER) are found, with multiple pathways determined at each step of the four proton-coupled electron transfer reaction. Of particular interest is the detailed characterization of a co-adsorption pathway utilizing neighboring, adsorbed O, OH species in order to evolve oxygen; activation energies of this pathway are <0.5 eV and therefore easily surmountable at the high operating potentials of OER. We also determined that surface Ir atoms can potentially participate in deprotonating an OOH* intermediate; the activation energy to this is 0.67 eV on the oxygen-terminated surface. These theoretical findings explain in part the high activity present in iridium oxide catalysts and also provide insight into the mechanistic pathways available on metal oxide catalysts, which may require the concerted interaction of nearest neighbor co-adsorbates to produce chemicals of interest.