Reaction intermediates of methanol synthesis and the water–gas-shift reaction on the ZnO(0001) surface

The polar Zn-ZnO(0001) surface is involved in the catalysis of methanol synthesis and the water–gas-shift reaction. We use density functional theory calculations to explore the favorable binding geometries and energies of adsorption of several molecular species relevant to these reactions, namely carbon monoxide (CO), carbon dioxide (CO₂), water (H₂O) and methanol (CH₃OH). We also consider several proposed reaction intermediates, including hydroxymethyl (CH₂OH), methoxyl (CH₃), formaldehyde (CH₂O), methyl (CH₃), methylene (CH₂), formic acid (HCOOH), formate (HCOO), formyl (HCO), hydroxyl (OH), oxygen (O) and hydrogen (H). For each, we identify the preferred binding geometry at a coverage of 1/4 monolayers (ML), and report calculated vibrational frequencies that could aid in the identification of these species in experiment. We further explore the effects on the binding energy when the adsorbate coverage is lowered to 1/9 and 1/16 ML.     

Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111)

The mechanism of ethanol decomposition on the Ni(111) surface has been investigated between 155 and 500 K. The sequence of bond scission steps which occur as ethanol undergoes dissociative reactions on this surface has been deduced using deuterium and ¹³C isotopic labels. Bond activation occurs in the order (1) OH, (2) CH₂ (methylene CH), (3) CC, (4) CH₃ (methyl CH). The products observed are CH₃CHO(g), CH₄(g), CO(g), H₂(g) and surface carbon, C(a). The latter species exhibits a carbidic AES lineshape in the temperature range 450 to 670 K, at which temperature it dissolves into the Ni bulk. Acetaldehyde, CH₃CHO, and methane, CH₄, desorb with the same threshold temperature (260–265 K), and the formation of both of these products is controlled by scission of the methylene CH bond (CH₂ group). The CH₃ group is cleaved from the intermediate surface CH₃CHO species to form CH₃(ads). H₂ exhibits a broad, doublet desorption peak from 300 to 450 K. The carbonoxygen bond in ethanol remains intact and CO ultimately desorbs in a single desorption limited process (T_p = 430 K). A small fraction of CO(a) species undergo exchange with the carbidic surface carbon in a minor process observed above 440 K.     

A cavity ring-down analyzer for measuring atmospheric levels of methane, carbon dioxide, and water vapor

Researchers investigating global climate change need measurements of greenhouse gases with extreme precision and accuracy to enable the development and benchmarking of better climate models. Existing atmospheric monitors based on non-dispersive infrared (NDIR) sensors have known problems – they are non-linear, sensitive to water vapor concentration, and susceptible to drift. Many cannot easily be simultaneously calibrated across different sites to the level of accuracy required for use in atmospheric studies. We present results from field trials by Pennsylvania State University and the National Oceanographic and Atmospheric Administration (NOAA) of a newly available analyzer, based on cavity ring-down spectroscopy (CRDS), capable of measuring the concentrations of carbon dioxide (CO₂) and water vapor (H₂O). In addition, we present data from a new analyzer which measures CO₂, methane (CH₄), and H₂O. PACS  07.88.+y     

A novel multiple species ringdown spectrometer for in situ measurements of methane,carbon dioxide,and carbon isotope

We have developed a standalone, user-friendly, multi-species ringdown spectrometer for in situ measurements of methane (CH₄), carbon dioxide (CO₂), and a carbon dioxide isotope (¹³CO₂). The instrument is based on near-infrared continuous-wave cavity ringdown spectroscopy (NIR cw-CRDS) and engineered to be of approximately 16 kg with dimensions of 50 cm × 40 cm × 15 cm. The instrument design, optical configuration, electronic control, and performance are described. CH₄, CO₂, and ¹³CO₂ are measured at different wavelengths that are obtained through multiplexing two distributed feedback laser diodes with central wavelengths at 1597 and 1650 nm. The spectrometer has low power consumption and runs for 4–6 h when powered by a standard car battery. The instrument is operated either locally by interacting with a 7-inch touch screen or remotely via an Internet connection. The 1-σ detection limits for CH₄ and CO₂ are 0.2 and 120 ppmv, respectively. The measurement uncertainty is better than ±4% of full-scale reading for CH₄ and CO₂ and ±1.5‰ for δ¹³C (part per thousand relative to the Pee Dee Belemnite scale). Measurement of each species is near real-time; switching from measuring one species to another takes less than one minute. This work demonstrates a novel multiple-species CRDS-instrumentation platform, which can be adopted for development of an array of ringdown spectrometers for portable, user-friendly, field analysis of a variety of gases in environmental and industrial applications. Discussion of a future version of the spectrometer with better detection sensitivity, higher accuracy, and a smaller geometry is also presented. PACS  42.62.Fi; 42.55.Px; 33.20.Ea; 07.88.+y; 07.57.Ty     

Catalytic ignition of light hydrocarbons over Rh/Al2O3 studied in a stagnation-point flow reactor

The ignition (light-off) temperatures of catalytic oxidation reactions provide very useful information for understanding their surface reaction mechanism. In this study, the ignition behavior of the oxidation of hydrogen (H₂), carbon monoxide (CO), methane (CH₄), ethane (C₂H₆), and propane (C₃H₈) over Rh/alumina catalysts is examined in a stagnation-point flow reactor. The light-off temperatures are identified by means of the sudden increase of the catalyst temperature when linearly heating the catalyst for various fuel/oxygen ratios. For hydrogen and all hydrocarbons studied, the results show a rise of ignition temperature with increasing fuel/oxygen ratio, whereas the opposite trend is observed for the light-off of CO oxidation. Hydrogen oxidation, however, shows an opposite trend compared to previous investigations, performed on platinum [1], [2].     

Study of gas detection based on integrated cavity output spectroscopy

A trace gases detection system based on integrated cavity output spectroscopy (ICOS) was developed, where a NIR tunable diode laser (TDL) was used as light source, an optical cavity composed by two plan-concave mirrors with reflection near 99.7% was used as the absorption cell. Trace water vapour (H₂O), carbon dioxide (CO₂), methane (CH₄), carbon monoxide (CO) and mixture of CO₂ and CO were tested by ICOS based on the characteristics absorption. The wavelength calibration, cavity transmission characteristics, quantitative measurement ability and sensitivity of the TDL-ICOS were also studied, and a evaluated minimum detectable sensitivity of 1.15 × 10^?7 cm^?1 was obtained when the system was used to CH₄ detection. The experiment results show that TDL-ICOS is expected to be a reliable and promising system for the detection of trace gases since it has some advantages such as real-time monitoring, simple device, easy operation, high sensitivity, good stability and quantitative ability.     

Inner-shell excitation and EXAFS-type phenomena in the chloromethanes

Small angle inelastic scattering of 2.5 keV electrons was used to study the inner-shell excitation of CH₄, CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄ and C₂H₅Cl in the regions of carbon 1s, chlorine 2p and chlorine 2s excitation. Structure observed below the carbon 1s ionization threshold in each molecule is assigned to promotions of a carbon 1s electron to unoccupied valence and Rydberg orbitals. Trends in the distribution of spectral intensities through the series of chloromethane carbon 1s spectra are discussed in terms of the growth of a potential barrier. Broad features are observed in the chlorine 2p continua of CH₂Cl₂, CHCl₃ and CCl₄ and the carbon 1s continuum of CCl₄ which are assigned as the energy loss equivalent of extended X-ray absorption fine structure (EXAFS).     

3D HCCH3-TOCSY for Resonance Assignment of Methyl-Containing Side Chains in C-Labeled Proteins

Two 3D experiments, (H)CCH₃-TOCSY and H(C)CH₃-TOCSY, are proposed for resonance assignment of methyl-containing amino acid side chains. After the initial proton–carbon INEPT step, during which either carbon or proton chemical shift labeling is achieved (t₁), the magnetization is spread along the amino acid side chains by a carbon spin lock. The chemical shifts of methyl carbons are labeled (t₂) during the following constant time interval. Finally the magnetization is transferred, in a reversed INEPT step, to methyl protons for detection (t₃). The proposed experiments are characterized by high digital resolution in the methyl carbon dimension (t_2max = 28.6 ms), optimum sensitivity due to the use of proton decoupling during the long constant time interval, and an optional removal of CH₂, or CH₂ and CH, resonances from the F₂F₃ planes. The building blocks used in these experiments can be implemented in a range of heteronuclear experiments focusing on methyl resonances in proteins. The techniques are illustrated using a ¹⁵N, ¹³C-labeled E93D mutant of Schizosacharomyces pombe phosphoglycerate mutase (23.7 kDa).     

Uniform design and regression analysis of LPCVD boron carbide from BCl3-CH4-H2 system

Boron carbide was prepared by low pressure chemical vapor deposition (LPCVD) from BCl₃-CH₄-H₂ system. The deposition process conditions were optimized through using a uniform design method and regression analysis. The regression model of the deposition rate was established. The influences of deposition temperature (T), deposition time (t), inlet BCl₃/CH₄ gas ratio (δ), and inlet H₂/CH₄ gas ratio (θ) on deposition rate and microstructure of the coatings were investigated. The optimized deposition parameters were obtained theoretically. The morphologies, phases, microstructure and composition of deposits were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman micro-spectroscopy, transmission electron microscopy (TEM), energy dispersive spectra (EDS), and Auger electron spectra (AES), the results showed that different boron carbides were produced by three kinds of deposition mechanisms.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Synthesis and regularities of combustion of acetoxymethylnitroamines. Impact sensitivity of secondary alkylnitroamines

The use of the nitrolysis of cyclic amines and of the direct synthesis from primary nitroamines made it possible to obtain acetates of methylolnitroamines of general formula AcO(CH₂NNO₂) _n R(n = 1–6). A number of high explosives, nitroamines, were synthesized: DNA ((CH₃NNO₂)₂CH₂), DMNA ((CH₃)₂NNO₂), DNA-2 ((CH₃NNO₂CH₂)₂), TRIS ((CH₃NNO₂CH₂)₂NNO₂), and TETRA ((CH₃NNO₂CH₂NNO₂)₂CH₂). The regularities of the combustion of the synthesized compounds were studied, and their characteristics were compared. Stress curve measurements were used to estimate the impact sensitivity of alkylnitroamines. A number of basic macroscopic characteristics of the nitroamines studied and nitroamine-ammonium perchlorate mixtures, including the heat of explosion. For comparison, the characteristics of regular high explosive are given.     

The oscillator strengths for C1s and O1s excitation of some saturated and unsaturated organic alcohols,acids and esters

Electron energy loss Spectroscopy (ISEELS) under dipole scattering conditions is used to obtain the carbon and oxygen K-shell oscillator strength spectra of methanol (CH₃OH), propanol (CH₃CH₂CH₂OH), propenol (CH₂=CHCH₂OH), propargyl alcohol (HC≡CCH₂OH), propanoic acid (CH₃CH₂COOH), acrylic acid (CH₂=CHCOOH) and propiolic acid (HC≡CCOOH). A detailed interpretation of these spectra is presented, along with a comparison with the NEXAFS spectra of multilayers of these molecules adsorbed on a Si(111) surface, as recently reported by Outka et al. (Surf. Sci., 185 (1987) 53). Good agreement is found between the multilayer NEXAFS and the gas phase ISEEL spectra, except for the carboxylic acids which differ dramatically in the discrete portion of the O1s spectrum. Possible origins for this difference are discussed. The C1s and O1s spectra of methyl formate (HCOOCH₃) are also reported and interpreted in comparison with the spectra of formic acid and methanol.     

Ester-functionalized soluble single-walled carbon nanotubes

We report the preparation of soluble ester- functionalized single-wall carbon nanotubes (sSWNT-COO(CH₂)₁₇CH₃). By use of solution phase IR spectroscopy we are able to compare the ratio of the carbon atoms in the SWNT backbone to the carbon atoms in the ester and amide functionalities of s-SWNTs. Received: 16 July 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Substituent effect on electron affinity,gas‐phase basicity,and structure of monosubstituted propargyl radicals and their anions: a theoretical study

The substituent effect of electron‐withdrawing groups on electron affinity and gas‐phase basicity has been investigated for substituted propargyl radicals and their corresponding anions. It is shown that when a hydrogen of the α‐CH₂ group or acetylenic CH in the propargyl system is substituted by an electron‐withdrawing substituent, electron affinity increases, whereas gas‐phase basicity decreases. The calculated electron affinities are 0.95 eV (CH?C? CH₂?), 1.15 eV (CH?C? CHF?), 1.38 eV (CH?C? CHCl?), 1.48 eV (CH?C? CHBr?) for the isomers with terminal CH and 1.66 eV (CF?C? CH₂?), 1.70 eV (CCl?C? CH₂?), 1.86 eV (CBr?C? CH₂?) for the isomers with terminal CX at B3LYP level. The calculated gas‐phase basicities for their anions are 378.4 kcal/mol (CH?C? CH₂:^?), 371.6 kcal/mol (CH?C? CHF:^?), 365.1 kcal/mol (CH?C? CHCl:^?), 363.5 kcal/mol (CH?C? CHBr:^?) for the isomers with terminal CH and 362.6 kcal/mol (CF?C? CH₂:^?), 360.4 kcal/mol (CCl?C? CH₂:^?), 356.3 kcal/mol (CBr?C? CH₂:^?) for the isomers with terminal CX at B3LYP level. It is concluded that the larger the magnitude of electron‐withdrawing, the greater is the electron affinity of radical and the smaller is the gas‐phase basicity of its anion. This tendency of the electron affinities and gas‐phase bacisities is greater in isomers with the terminal CX than isomers with the terminal CH. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical study on the reactions of CH3NHNH2 with ground state O(3P) atom and excited state O(1D) atom

The reaction mechanisms of methylhydrazine (CH₃NHNH₂) with O(³P) and O(¹D) atoms have been explored theoretically at the MPW1K/6-311+G(d,p), MP2/6-311+G(d,p), MCG3-MPWPW91 (single-point), and CCSD(T)/cc-pVTZ (single-point) levels. The triplet potential energy surface for the reaction of CH₃NHNH₂ with O(³P) includes seven stable isomers and eight transition states. When the O(³P) atom approaches CH₃NHNH₂, the heavy atoms, namely N and C atoms, are the favourable combining points. O(³P) atom attacking the middle-N atom in CH₃NHNH₂ results in the formation of an energy-rich isomer (CH₃NHONH₂) followed by migration of O(³P) atom from middle-N atom to middle-H atom leading to the product P6 (CH₃NNH₂+OH), which is one of the most favourable routes. The estimated major product CH₃NNH₂ is consistent with the experimental measurements. Reaction of O(¹D) + CH₃NHNH₂ presents different features as compared with O(³P) + CH₃NHNH₂. O(¹D) atom will first insert into C–H2, N1–H4, and N2–H5 bonds barrierlessly to form the three adducts, respectively. There are two most favourable paths for O(¹D) + CH₃NHNH₂. One is that the C–N bond cleavage accompanied by a concerted H shift from O atom to N atom (mid-N) leads to the product P_I (CH₂O + NH₂NH₂), and the other is that the N–N bond rupture along with a concerted H shift from O to N (end-N) forms P_IV (CH₃NH₂ + HNO). The similarities and discrepancies between two reactions are discussed.     

Characterization of methylidyne on Pt(1 1 1) with infrared spectroscopy

Methylidyne (CH) was prepared on Pt(1 1 1) by three methods: thermal decomposition of diiodomethane (CH₂I₂), ethylene decomposition at temperatures above 450 K, and surface carbon hydrogenation. Methylidyne and its precursors are characterized by reflection absorption infrared spectroscopy (RAIRS). The C-I bond of diiodomethane breaks upon adsorption to produce methylene (CH₂), which decomposes to methylidyne at temperatures above 130 K. Above 200 K, methylidyne is the only hydrocarbon species observed with RAIRS, although reaction channels for the formation of methane (CH₄) and ethylene (C₂H₄) are indicated by temperature programmed desorption (TPD). As is well known from numerous previous studies, ethylene decomposes to ethylidyne (CCH₃) upon exposure to Pt(1 1 1) at 410 K. Upon annealing to 450 K, ethylidyne dissociates through two reaction pathways, dehydrogenation to ethynyl (CCH) and C-C bond scission to methylidyne. Ethylene dehydrogenation on the surface at 750 K and under low ethylene exposures produces surface carbon that can be hydrogenated to methylidyne with C-H and C-D stretch frequencies of 2956 and 2206 cm⁻¹, respectively. Hydrogen co-adsorption on the surface causes these frequencies to shift to higher values. Methylidyne is stable on Pt(1 1 1) to temperatures up to 500 K.     

甲醛在金红石型TiO2(100)-(1×1)表面的光解离

We have investigated the photoinduced decomposition of formaldehyde (CH₂O) on a rutile TiO₂(100)-(1×1) surface at 355 nm using temperature-programmed desorption. Products, formate (HCOO^-), methyl radical (CH₃·), ethylene (C₂H₄), and methanol (CH₃OH) have been detected. The initial step in the decomposition of CH₂O on the rutile TiO₂(100)-(1×1) surface is the formation of a dioxymethylene intermediate in which the carbonyl O atom of CH₂O is bound to a Ti atom at the five-fold-coordinated Ti⁴⁺ (Ti_5c) site and its carbonyl C atom bound to a nearby bridge-bonded oxygen (O_b) atom, respectively. During 355 nm irradiation, the dioxymethylene intermediate can transfer an H atom to the O_b atom, thus forming HCOO^- directly, which is considered as the main reaction channel. In addition, the dioxymethylene intermediate can also transfer methylene to the O_b row and break the C-O bond, thus leaving the original carbonyl O atom at the Ti_5c site. After the transfer of methylene, several pathways to products are available. Thus, we have found that O_b atoms are intimately involved in the photoinduced decomposition of CH₂O on the rutile TiO₂(100)-(1×1) surface.     

Theoretical study on the reaction of CH3CHCl + NO2

The detailed reaction mechanism of 1-chloroethyl radical with NO₂ is investigated theoretically. The results show that the title reaction is more favourable on the singlet potential energy surface than on the triplet one. For the singlet PES of CH₃CHCl?+?NO₂, it is shown that the CH₃CHCl radical can react with NO₂ to barrierlessly generate adduct a (H₃CHClCNO₂), b₁ (H₃CHClCONO-trans), and b₂ (H₃CHClCONO-cis), respectively. A total of six energetically reaction pathways and ten products are found. However, the most competitive path way is P₁ (CH₃CHO?+?ClNO), which can further dissociate to give P₆ (CH₃CHO?+?Cl?+?NO) and P₂ (CH₃CClO?+?HNO). The present results can lead to a deep understanding of the mechanism of the title reaction and may be helpful for understanding the halogenated ethyl chemistry.