scholarly journals Mechanistic Study on Facet-Dependent Deposition of Metal Nanoparticles on Decahedral-Shaped Anatase Titania Photocatalyst Particles

Catalysts ◽  
2018 ◽  
Vol 8 (11) ◽  
pp. 542 ◽  
Author(s):  
Kenta Kobayashi ◽  
Mai Takashima ◽  
Mai Takase ◽  
Bunsho Ohtani
Keyword(s):  
Mechanistic Study ◽  
Phase Reaction ◽  
Surface Charges ◽  
Platinum Nanoparticle ◽  
Nanoparticle Deposition ◽  
Selective Reaction ◽  
Anatase Titania ◽  
Deposition Density ◽  
Titania Photocatalyst ◽  
Source Materials

Facet-selective gold or platinum-nanoparticle deposition on decahedral-shaped anatase titania particles (DAPs) exposing {001} and {101} facets via photodeposition (PD) from metal-complex sources was reexamined using DAPs prepared with gas-phase reaction of titanium (IV) chloride and oxygen by quantitatively evaluating the area deposition density on {001} and {101} and comparing with the results of deposition from colloidal metal particles in the dark (CDD) or under photoirradiation (CDL). The observed facet selectivity, more or less {101} preferable, depended mainly on pH of the reaction suspensions and was almost non-selective at low pH regardless of the deposition method, PD or CDL, and the metal-source materials. Based on the results, the present authors propose that facet selectivity is attributable to surface charges (zeta potential) depending on the kind of facets, {001} and {101}, and pH of the reaction mixture and that this concept can explain the observed facet selectivity and possibly the reported facet selectivity without taking into account facet-selective reaction of photoexcited electrons and positive holes on {101} and {001} facets, respectively.

ChemInform Abstract: A MECHANISTIC STUDY OF THE ION-MOLECULE GAS-PHASE REACTION: CH3+ + CH4 → CH3CH2+ + H2

1982 ◽  
Vol 13 (44) ◽  
Author(s):  
R. A. POIRIER ◽  
E. CONSTANTIN ◽  
J. CH. ABBE ◽  
M. R. PETERSON ◽  
I. G. CSIZMADIA
Keyword(s):  
Gas Phase ◽  
Mechanistic Study ◽  
Phase Reaction ◽  
Gas Phase Reaction

A mechanistic study of the ion—molecule gas-phase reaction: CH+3 + CH4 → CH3CH+2 + H2

1982 ◽  
Vol 88 (3-4) ◽  
pp. 343-355 ◽  
Author(s):  
Raymond A. Poirier ◽  
Emilia Constantin ◽  
Jean Ch. Abbé ◽  
Michael R. Peterson ◽  
Imre G. Csizmadia
Keyword(s):  
Gas Phase ◽  
Mechanistic Study ◽  
Phase Reaction ◽  
Gas Phase Reaction

scholarly journals Computational mechanistic study of the unimolecular dissociation of ethyl hydroperoxide and its bimolecular reactions with atmospheric species

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Mansour H. Almatarneh ◽  
Asmaa Alnajajrah ◽  
Mohammednoor Altarawneh ◽  
Yuming Zhao ◽  
Mohammad A. Halim
Keyword(s):  
Activation Energy ◽  
Density Functional ◽  
Computational Study ◽  
Basis Sets ◽  
Mechanistic Study ◽  
Intrinsic Reaction Coordinate ◽  
Unimolecular Dissociation ◽  
Phase Reaction ◽  
Atmospheric Species ◽  
Solvation Models

Abstract A detailed computational study of the atmospheric reaction of the simplest Criegee intermediate CH2OO with methane has been performed using the density functional theory (DFT) method and high-level calculations. Solvation models were utilized to address the effect of water molecules on prominent reaction steps and their associated energies. The structures of all proposed mechanisms were optimized using B3LYP functional with several basis sets: 6-31G(d), 6-31G (2df,p), 6-311++G(3df,3pd) and at M06-2X/6-31G(d) and APFD/6-31G(d) levels of theory. Furthermore, all structures were optimized at the B3LYP/6-311++G(3df,3pd) level of theory. The intrinsic reaction coordinate (IRC) analysis was performed for characterizing the transition states on the potential energy surfaces. Fifteen different mechanistic pathways were studied for the reaction of Criegee intermediate with methane. Both thermodynamic functions (ΔH and ΔG), and activation parameters (activation energies Ea, enthalpies of activation ΔHǂ, and Gibbs energies of activation ΔGǂ) were calculated for all pathways investigated. The individual mechanisms for pathways A1, A2, B1, and B2, comprise two key steps: (i) the formation of ethyl hydroperoxide (EHP) accompanying with the hydrogen transfer from the alkanes to the terminal oxygen atom of CIs, and (ii) a following unimolecular dissociation of EHP. Pathways from C1 → H1 involve the bimolecular reaction of EHP with different atmospheric species. The photochemical reaction of methane with EHP (pathway E1) was found to be the most plausible reaction mechanism, exhibiting an overall activation energy of 7 kJ mol−1, which was estimated in vacuum at the B3LYP/6-311++G(3df,3pd) level of theory. All of the reactions were found to be strongly exothermic, expect the case of the sulfur dioxide-involved pathway that is predicted to be endothermic. The solvent effect plays an important role in the reaction of EHP with ammonia (pathway F1). Compared with the gas phase reaction, the overall activation energy for the solution phase reaction is decreased by 162 and 140 kJ mol−1 according to calculations done with the SMD and PCM solvation models, respectively.

Kinetic and mechanistic study of the gas-phase reaction of ozone with γ-terpinene

2020 ◽  
pp. 118073
Author(s):  
Layal Fayad ◽  
Cécile Coeur ◽  
Thomas Fagniez ◽  
Xavier Secordel ◽  
Nicolas Houzel ◽  
...  
Keyword(s):  
Gas Phase ◽  
Mechanistic Study ◽  
Phase Reaction ◽  
Gas Phase Reaction

scholarly journals Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene

2020 ◽  
Author(s):  
Isaac Kwadjo Afreh ◽  
Bernard Aumont ◽  
Marie Camredon ◽  
Kelley Claire Barsanti
Keyword(s):  
Air Quality ◽  
Gas Phase ◽  
Measurement Model ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Mechanistic Study ◽  
Phase Reaction ◽  
Particle Phase ◽  
Atmospheric Conditions ◽  
Model Simulations

Abstract. Camphene, a dominant monoterpene emitted from both biogenic and pyrogenic sources, has been significantly understudied, particularly in regard to secondary organic aerosol (SOA) formation. When camphene represents a significant fraction of emissions, the lack of model parameterizations for camphene can result in inadequate representation of gas-phase chemistry and underprediction of SOA formation. In this work, the first mechanistic study of SOA formation from camphene was performed using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A). GECKO-A was used to generate gas-phase chemical mechanisms for camphene and two well-studied monoterpenes, α-pinene and limonene; and to predict SOA mass formation and composition based on gas/particle partitioning theory. The model simulations represented observed trends in published gas-phase reaction pathways and SOA yields well under chamber-relevant photooxidation and dark ozonolysis conditions. For photooxidation conditions, 70 % of the simulated α-pinene oxidation products remained in the gas phase compared to 50 % for limonene; supporting model predictions and observations of limonene having higher SOA yields than α-pinene under equivalent conditions. The top 10 simulated particle-phase products in the α-pinene and limonene simulations represented 37–50 % of the SOA mass formed and 6–27 % of the hydrocarbon mass reacted. To facilitate comparison of camphene with α-pinene and limonene, model simulations were run under idealized atmospheric conditions, wherein the gas-phase oxidant levels were controlled. Metrics for comparison included: gas-phase reactivity profiles, time-evolution of SOA mass and yields, and physicochemical property distributions of gas- and particle-phase products. The controlled-reactivity simulations demonstrated that: (1) in the early stages of oxidation, camphene is predicted to form very low volatility products, lower than α-pinene and limonene, which condense at low mass loadings; and (2) the final simulated SOA yield for camphene (46 %) was relatively high, in between α-pinene (25 %) and limonene (74 %). A 50 / 50 (α-pinene / limonene) mixture was then used as a surrogate to represent SOA formation from camphene; while simulated SOA mass and yield were well represented, the volatility distribution of the particle-phase products was not. To demonstrate the potential importance of including a parameterized representation of SOA formation by camphene in air quality models, SOA mass and yield were predicted for three wildland fire fuels based on measured monoterpene distributions, and published SOA parameterizations for α-pinene and limonene. Using the 50 / 50 surrogate mixture to represent camphene increased predicted SOA mass by 43–50 % for black spruce and by 56–108 % for Douglas fir. This first detailed modeling study of the gas-phase oxidation of camphene and subsequent SOA formation provides an opportunity for future measurement-model comparisons and lays the foundation for developing chemical mechanism and SOA parameterizations for camphene that are suitable for air quality modeling.

Plasma-Enhanced MOCVD of Superconducting Oxides

1993 ◽  
Vol 335 ◽  
Author(s):  
Kenji Ebihara ◽  
Tomoyuki Fujishima ◽  
Masanobu Shiga ◽  
Quanxi Jia
Keyword(s):  
Thin Films ◽  
Phase Reaction ◽  
Superconducting Transition ◽  
Superconducting Thin Film ◽  
High Tc ◽  
Rf Discharges ◽  
Excited Species ◽  
Thin Film Preparation ◽  
Plasma Enhancement ◽  
Source Materials

AbstractThe plasma-enhanced MOCVD is developed to prepare high-Tc oxide superconducting thin films. Plasmas generated by microwave and rf discharges decompose effectively the source materials ( β-diketonate chelates) into their elements and oxides. YBaCuO thin films were deposited on the MgO substrate of 500–650 °C at total pressure of 0.6–5 Torr with O2 contents less than 30%. The as-grown films produced by two kinds of plasma enhancement were porous and consisted of crystalline grains, but showed the superconducting transition after heating procedure at around 800 °C. It is shown that the inherent crystalline orientations of the as-grown films determine the crystal structure of the post-annealed films. The film of the metal atomic ratios of 0.91 for Ba/Y and 2.64 for Cu/Y showed the superconducting properties with Tc(zero) of 89 K and the critical current density (at 77 K) of 5×104 A/cm2. Spectroscopic analysis showed that the plasmas are composed of many excited species such as Y, Y+, Ba, Ba+, Cu, YO, BaO, CuO. Formation of the metal-oxides through the gas phase reaction is essential for the high-quality YBaCuO superconducting thin film preparation in the PEMOCVD.

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