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121.
Ab initio molecular orbital and hybrid density functional theory calculations have been performed to study the adsorption, isomerization, and decomposition of HCN on Si(100)-2×1 using the Si9H12 cluster model of the surface. The results of our calculations indicate that the HCN can adsorb molecularly without a barrier onto the surface with both end-on (LM1) and side-on (LM2) positions. LM1 can isomerize to LM2 with a small barrier of 8 kcal/mol. The isomerization of LM2 by H-migration from C to the N atom, requires 76 kcal/mol activation energy (c.f. 47.5 kcal/mol in the gas phase) because of surface stabilization. Both HCN(a) and HNC(a) end-on adsorbates were found to dissociate readily, as concluded in our earlier experiment, to produce H and CN adspecies. The computed vibrational frequencies of HCN, CN, and also HCNH adspecies agree reasonably well with those observed experimentally. HCNH was found to be stable, with either the C or the N attaching to the surface. 相似文献
122.
The effects of temperature on the stability of a soil humic acid were studied in the present work. Solid samples of Gohy-573 humic acid (HA) and dissolved ones in aqueous solution (pH 6.0, 0.1 mol L−1 NaClO4) were investigated in order to understand the impact of temperature on the chemical properties of the material. The methods applied to solid samples in the present investigation were thermogravimetric analysis (TGA), temperature-programmed desorption coupled with mass spectrometry (TPD-MS), and in situ diffuse reflectance infrared Fourier transformed spectroscopy (in situ DRIFTS). Humic acid samples were studied in the 25-800 °C range, with focus on thermal/chemical processes up to 250 °C. The reversibility of the changes observed was investigated by cyclic changes to specified temperature ranges (40-110 °C). All measurements were conducted under inert-gas atmosphere in order to avoid samples combustion at increased temperatures. Aqueous solutions were analyzed by UV-vis absorption spectroscopy after storage at temperatures up to 95 °C, and storage times up to 1 week. For temperatures below 100 °C experiments on solid and aqueous samples have shown results which were consistent to each other. The amount of water desorbed is temperature dependent and up to 70 °C this process was totally reversible. Above 70 °C an irreversible loss of water was also observed, which according to UV-vis spectroscopy corresponds to water produced by condensation leading to more condensed polyaromatic structures. The water released up to 110 °C was about 7 wt% of the total mass of the dried humic acid, where less than 50% corresponded to reversibly adsorbed water. At higher temperatures (>110 °C), gradual decomposition resulting in the formation of carbon dioxide (110-240 °C), and carbon monoxide (140-240 °C) takes place. Hence, thermal treatment of Gohy-573 humic acid above 70 °C results in irreversible structural changes, that could affect chemical properties (e.g., complex formation) of the material. 相似文献
123.
M. Jasiński M. Dors J. Mizeraczyk 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2009,54(2):179-183
In this paper, results of hydrogen production via methane pyrolysis in the atmospheric pressure microwave plasma with CH4 swirl are presented. A waveguide-based nozzleless cylinder-type microwave plasma source (MPS) was used to convert methane
into hydrogen. The plasma generation was stabilized by a CH4 swirl having a flow rate of 87.5 L min-1. The absorbed microwave power was 1.5–5 kW. The hydrogen production rate and the corresponding energy efficiency were 866 g
(H2) h-1 and 577 g (H2) kWh-1 of microwave energy absorbed by the plasma, respectively. These parameters are better than our previous results when nitrogen
was used as a swirl gas and much better than those typical for other plasma methods of hydrogen production (electron beam,
gliding arc, plasmatron). 相似文献
124.
Wenhua Chen Alan L. Stottlemyer Payam Kaghazchi Theodore E. Madey Robert A. Bartynski 《Surface science》2009,603(20):3136-16391
We report on the adsorption and decomposition of NO on O-covered planar Ir(2 1 0) and nanofaceted Ir(2 1 0) with variable facet sizes investigated using temperature programmed desorption (TPD), high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT). When pre-covered with up to 0.5 ML O, both planar and faceted Ir(2 1 0) exhibit unexpectedly high reactivity for NO decomposition. Upon increasing the oxygen coverage to 0.7 ML O, planar Ir(2 1 0) has little activity while faceted Ir(2 1 0) still remains active toward NO decomposition, although NO decomposition is completely inhibited when both surfaces are pre-covered by 1 ML O. NO molecularly adsorbs on O-covered Ir at 300 K. At low NO and oxygen coverage, NO adsorbs on the atop sites of planar Ir(2 1 0) while on the bridge and atop sites of faceted Ir(2 1 0) composed of (1 1 0) and {3 1 1} faces. No evidence for size effects in the decomposition of NO on O-covered faceted Ir(2 1 0) is observed for average facet size in the range 5-14 nm. Our findings should be of importance for development of Ir-based catalysts for NO decomposition under oxygen-rich conditions. 相似文献
125.
The reaction of formamide over the (0 1 1) faceted TiO2(0 0 1) surface has been studied by Temperature Programmed Desorption (TPD) and X-ray Photoelectron Spectroscopy (XPS). Two main reactions were observed: dehydration to HCN and H2O and decomposition to NH3 and CO. The dehydration reaction was found to be three to four times larger than the decomposition at all coverages. Each of these reactions is found to occur in two temperature domains which are dependent upon surface coverage. The low temperature pathway (at about 400 K) is largely insensitive to surface coverage while the high temperature pathway (at about 500 K) shifts to lower temperatures with increasing surface coverage. These two temperature pathways may indicate two adsorption modes of formamide: molecular (via an η1(O) mode of adsorption) and dissociative (via an η2(O,N) mode of adsorption). C1s and N1s XPS scans indicated the presence of multiple species after formamide absorption at 300 K. These occurred at ca. 288.5 eV (-CONH-) and 285 eV (sp3/sp2 C) for the C1s and 400 eV-(NH2), 398 eV (-NH) and 396 eV (N) for the N1s and result from further reaction of formamide with the surface. 相似文献
126.
Tetsu Hanmura Masahiko Ichihashi Ryuji Okawa Tamotsu Kondow 《International journal of mass spectrometry》2009,280(1-3):184
Reactions of NO molecules on cobalt cluster ions were studied in a beam-gas geometry by using a tandem mass spectrometer. Single-particle collision reactions of ComNO+ (m = 3–10) with NO were found to proceed in such a manner that NO decomposition dominates at m = 4–6 with the maximum reaction cross section at m = 5 and chemisorption dominates in m ≥ 7. On the other hand, in two-particle collision reactions of Con+ (n = 2–10) with NO, NO decomposition at n ≥ 5 and chemisorption of two NO molecules with Co atoms loss at n ≥ 8 were found to proceed. These results indicate that the size-dependency of the multiple collision reactions originates from secondary attacking of an NO molecule to primary products of the initial single collision reactions. The DFT calculation supports the scheme that both the decomposition and chemisorption of two-particle collision reactions proceed via a common intermediate, ComN2O2+, in which the two NO molecules are dissociatively chemisorbed on the cobalt cluster ion, and the size-dependency of the two-particle collision reactions is explained in terms of the structure of this reaction intermediate. 相似文献
127.
C. J. Lin S. Lucidi L. Palagi A. Risi M. Sciandrone 《Journal of Optimization Theory and Applications》2009,141(1):107-126
Many real applications can be formulated as nonlinear minimization problems with a single linear equality constraint and box
constraints. We are interested in solving problems where the number of variables is so huge that basic operations, such as
the evaluation of the objective function or the updating of its gradient, are very time consuming. Thus, for the considered
class of problems (including dense quadratic programs), traditional optimization methods cannot be applied directly. In this
paper, we define a decomposition algorithm model which employs, at each iteration, a descent search direction selected among
a suitable set of sparse feasible directions. The algorithm is characterized by an acceptance rule of the updated point which
on the one hand permits to choose the variables to be modified with a certain degree of freedom and on the other hand does
not require the exact solution of any subproblem. The global convergence of the algorithm model is proved by assuming that
the objective function is continuously differentiable and that the points of the level set have at least one component strictly
between the lower and upper bounds. Numerical results on large-scale quadratic problems arising in the training of support
vector machines show the effectiveness of an implemented decomposition scheme derived from the general algorithm model. 相似文献
128.
In this work we consider the problem of minimizing a continuously differentiable function over a feasible set defined by box
constraints. We present a decomposition method based on the solution of a sequence of subproblems. In particular, we state
conditions on the rule for selecting the subproblem variables sufficient to ensure the global convergence of the generated
sequence without convexity assumptions. The conditions require to select suitable variables (related to the violation of the
optimality conditions) to guarantee theoretical convergence properties, and leave the degree of freedom of selecting any other
group of variables to accelerate the convergence. 相似文献
129.
利用高里德堡态氢原子飞行时间探测技术, 在224~248 nm激发波长研究了间-吡啶基紫外光化学中的氢原子解离通道的动力学过程.氢原子光解碎片产率谱显示在234 nm附近有较宽的吸收.产物的平动能释放较小;在224~248 nm激发波长区间平均〈 fT〉是0.12~0.19.产物的平动能分布显示产物是H+HC≡C-CH=CH-C≡N,H 3,4-吡啶和H 2,3-吡啶,以H HC≡C-CH=CH-C≡N为主要的氢原子生成通道.氢原子碎片具有各向同性的角度分布.研究结果表明,在紫外电子态激发以后,间-吡啶基经过内转换到电子基态,再经由单分子解离到H HC≡C-CH=CH-C≡N,H 3,4-吡啶和H 2,3-吡啶产物.间-吡啶基的紫外光解机理和以前报道过的邻-吡啶基的紫外光解机理相似. 相似文献
130.
P. Giangiacomo V. Michelassi 《International Journal of Computational Fluid Dynamics》2013,27(1):15-26
The paper describes a domain decomposition strategy which allows high efficiency parallel simulations of turbomachinery flows. The implicit ADI parallel solver is based on the scalar approximate factorisation. The Navier-Stokes (NS) and turbulence model equations are discretised by centred finite differences. The results prove that the parallel calculations with domain decomposition, in which each sub-domain explicitly communicates with the adjacent ones at the end of each implicit iteration, may suffer from a considerable deterioration of the convergence rate. A simple sub-iterative domain recoupling strategy allows recovering the convergence rate of a single processor computation. The strategy is carefully analysed and optimised in terms of inter-processor data communication rate and algorithm memory requirements. The span-wise domain decomposition is particularly suited for turbomachinery flows and is applied to a radial impeller and to an axial turbine stator and stage to prove the validity and the accuracy of the proposed approach. The results indicate that the parallel recoupled algorithm usually reach efficiencies of 0.8, with peaks over 0.9 with up to 16 processors, thereby allowing a considerable speed-up of design and verification calculations. 相似文献