• Korean Chemical Engineering Research
• /
• v.56 no.2
• /
• pp.291-296
• /
• 2018

Direct synthesis of methylchlorosilanes was developed by Rochow with addition of copper on the silicon surface as a catalyst and many research were followed. Most of research were focused on the increase of reaction activity through addition of promoters and concentrated on the increase of selectivity of DMDC. However, there are very few studies about the reaction mechanism. Although formation of DMDC was explained in literature, formation of other silanes were not mentioned at all. This reseach focused on the explanation about formation of all silanes obtained during direct reaction and TPD. Reaction paths were proposed by means of dissociative adsorption of methyl chloride and spillover of surface Cl and H. Surface silicon sites were considered as $=SlCl_2$ and $=Sl(CH_3)Cl$. The synthesis of all methylchlorosilanes were explained by the adsorption of methyl group on the silicon sites and by the surface diffusion of nearby Cl and H. The proposed reaction mechanism explains the formation of all silanes during the reaction and also during the TPD process.

• Journal of Powder Materials
• /
• v.18 no.6
• /
• pp.538-545
• /
• 2011

This study shows that catalytic activity of bimetallic RhPt nanoparticle arrays under CO oxidation can be tuned by varying the size and composition of nanoparticles. The tuning of size of RhPt nanoparticles was achieved by changing concentration of rhodium and platinum precursors in one-step polyol synthesis. Two-dimensional RhPt bimetallic nanoparticle arrays in different size and composition were prepared through Langmuir-Blodgett thin film technique. CO oxidation was carried out on these two-dimensional nanoparticle arrays, revealing higher activity on the smaller nanoparticles compared to the bigger nanoparticles. X-ray photoelectron spectroscopy (XPS) results indicate the preferential surface segregation of Rh compared to Pt on the smaller nanoparticles, which is consistent with the thermodynamic analysis. Because the catalytic activity is associated with differences in the rates of $O_2$ dissociative adsorption between Pt and Rh, this paper suppose that the surface segregation of Rh on the smaller bimetallic nanoparticles is responsible for the higher catalytic activity in CO oxidation. This result suggests a control mechanism of catalytic activity via synthetic approaches of colloid nanoparticles, with possible application in rational design of nanocatalysts.

• Korean Journal of Metals and Materials
• /
• v.46 no.5
• /
• pp.296-303
• /
• 2008

Hydrogen permeation through dense palladium-based membranes has attracted the attention of many scientists largely due to their unmatched potential as hydrogen-selective membranes for membrane reactor applications. Although it is well known that the permeation mechanism of hydrogen through Pd involves various processes such as dissociative adsorption, transitions to and from the bulk Pd, diffusion within Pd, and recombinative desorption, it is still unclear which process mainly limits hydrogen permeation at a given temperature and hydrogen partial pressure. In this study, we report an all-electron density-functional theory study of hydrogen permeation through Pd membrane (using VASP code). Especially, we focus on the variation of the energy barrier of the penetration process from the surface to the bulk with hydrogen coverage, which means the large reduction of the fracture stress in the brittle crack propagation considering Griffith's criterion. It is also found that the penetration energy barrier from the surface to the bulk largely decreases so that it almost vanishes at the coverage 1.25, which means that the penetration process cannot be the rate determining process.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2012.02a
• /
• pp.265-265
• /
• 2012

The adsorption of molecular $NH_3$ on rutile $TiO_2(110)-1{\times}1$ surfaces was investigated using a temperature-programmed desorption (TPD) technique combined with a molecular beam apparatus. A quantitative investigation into the TPD spectra of $NH_3$ was made for $NH_3$ adsorbed on two kinds of rutile $TiO_2(110)-1{\times}1$ surfaces with the oxygen vacancy ($V_O$) concentration of ~0% (p-$TiO_2(110)$) and ~5% (r-$TiO_2(110)$), respectively. On both surfaces, non-dissociative adsorption of $NH_3$ was inferred from a quantitative analysis on the amount of adsorbed $NH_3$ and those desorbed. With increasing coverage, the monolayer desorption feature shifted from 400 K toward lower temperatures until it saturates at 160 K, suggesting a repulsive nature in the interaction between $NH_3$ molecules. At the very low coverage regime, the desorption features were found to extend up to 430 K and 400 K on p-$TiO_2(110)$ and p-TiO(110), respectively. As a result, the saturation coverage of monolayer of $NH_3$ was higher on the p-$TiO_2(110)$ surface than on the p-TiO(110) by about 10%. The desorption energy ($E_d$) of $NH_3$ obtained by inversion of the Polanyi-Wigner equation indicated that the difference between the $E_d$'s of $NH_3$ (that is, $E_d(on\;p-TiO_2(110)$) - $E_d$(on p-TiO(110)) was 14 kJ/mol at ${\theta}(NH_3)=0$ and decreased to 0 as the coverage approached to a monolayer. The observed adsorption behavior of $NH_3$ was interpreted using an interaction model between $NH_3$ and surface defects on $TiO_2$ such as VO's and $Ti^{3+}$ interstitials.

• Journal of the Korean Vacuum Society
• /
• v.18 no.1
• /
• pp.15-23
• /
• 2009

Saturation-coverage silyl, $-SiH_3(a)$, overlayers were prepared from $Si_2H_6$ adsorption on three comparative surfaces: clean unmodified; D-precovered; and atomically roughened Si(100). Together with its precursor-mediated adsorption behavior, the surface reactivity of $Si_2H_6$ was found to be the highest on the unmodified Si(100)-$2{\times}1$ surface. This was correlated with its dissociative adsorption mechanism, in which both the $H_3Si-SiH_3$ bond scission and the dual surface $Si-SiH_3(a)$ bond formation require a surface dangling bond 'pair'. The unusually high thermal stability of $-SiH_3(a)$ on the unmodified surface was ascribed to a nearly close-packed $-SiH_3(a)$ coverage of ${\sim}0.9$ monolayer and the consequent lack of dangling bonds on the silyl-packed surface.

• Applied Chemistry for Engineering
• /
• v.17 no.2
• /
• pp.125-131
• /
• 2006

Dimethyl ether (DME) is a new clean fuel as an environmentally-benign energy resource. DME can be manufactured from various energy sources including natural gas, coal, biomass and spent plastic. In addition to its environmentally friendly properties, DME has similar characteristics to those of LPG. Therefore, it is considered as an excellent substitute fuel for LPG, fuel cells, power plant, and especially diesel and is expected to be the alternative fuel by 2010. The experimental study of the direct synthesis of DME was investigated under various conditions over a temperature range of $220{\sim}280^{\circ}C$, syngas ratio 1.2~3.0. All experiments were carried out with a hybrid catalyst, composed of a methanol synthesis catalyst ($Cu/ZnO/Al_2O_3$) and a dehydration catalyst (${\gamma}-Al_2O_3$). The observed reaction rate follows qualitatively a Langmiur-Hinshellwood model as the reaction mechanism. Such a mechanism is considered with three reactions; methanol synthesis, methanol dehydration and water gas shift reaction. From a surface reaction with dissociative adsorption of hydrogen, methanol, and water, individual reaction rate was determined.

• 한국신재생에너지학회:학술대회논문집
• /
• 2009.11a
• /
• pp.171-171
• /
• 2009

The electrodes are usually made of a porous mixture of carbon-supported platinum and ionomers. $SnO_2$ particles provide as supports that have been used for DMFCs, and it have high catalytic activities toward methanol oxidation. The main advantage of $SnO_2$ supported electrodes is that it has strong chemical interactions with metallic components. The high activity to a synergistic bifunctional mechanism in which Pt provides the adsorption sites for CO, while oxygen adsorbs dissociative on $SnO_2$. The reaction between the adsorbed species occurs at the Pt/$SnO_2$ boundary. The morphological observations were characterized by FESEM and transmission electron microscopy (TEM). $SnO_2$ particles crystallinity was analyzed by the X-ray diffraction (XRD). The surface bonded state of the $SnO_2$ particles and electrode materials were observed by the X-ray photoelectron spectroscopy (XPS). The electric properties of the Pt/$SnO_2$ catalyst for methanol oxidation have been investigated by the cyclic voltametry (CV) in 0.1M $H_2SO_4$ and 0.1M MeOH aqueous solution. The peak current density of methanol oxidation was increased as the $SnO_2$ content in the anode catalysts increased. Pt/$SnO_2$ catalysts improve the removal of CO ads species formed on the platinum surface during methanol electro-oxidation.