• Journal of the Korean Chemical Society
• /
• v.23 no.2
• /
• pp.88-93
• /
• 1979

The adsorption of propylene on copper(II)-exchanged zeolite Y was studied by temperature programmed desorption (TPD) technique and electron spin resonance. The amount of propylene adsorbed increased with increasing copper ion content. Four TPD peaks with desorption temperature maxima at $108^{\circ}C({\alpha})$, $243^{\circ}C({\beta})$, $284^{\circ}C({\gamma})$ and $420^{\circ}C({\delta})$ were observed (heating rate: $6.4^{\circ}C$/min). ${\alpha}$Peak which was also observed in the TPD of propylene from NaY may be assigned to propylene physically adsorbed on the zeolite surface, ${\beta}$ and ${\gamma}$ peaks to the chemisorbed propylene either on copper ion or Bronsted acid site produced by copper ion, and $\delta$ peak to cracking products from the polymeric material formed from propylene adsorbed.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.6
• /
• pp.1980-1984
• /
• 2011

A temperature- and coverage-dependant quasi-reversible change in two-photon photoemission (2PPE) of chemisorbed 1-phenyl-1-propyne (PP) on Cu(111) is reported. For PP on Cu(111) at 300 K probed at a photon energy of 4.13 eV, two broad peaks of comparable intensity show final state energies of 7.25 and 7.75 eV above the Fermi level. The former peak could be assigned to the first image potential state (IS, n = 1) and/or unoccupied molecular orbital (UMO), located at 3.1 eV above the Fermi level. The latter is plausibly attributed to a mix of unoccupied higher-order IS (and/or UMO) and occupied surface state (SS) of Cu(111). With decreasing the temperature, the former 2PPE peak shows a shift in position by about 0.2 eV, and the latter exhibits a dramatic increase in intensity. In the system, intermolecular interactions (and/or order-disorder transition) of PP and substrate lattice temperature may play a significant role in change in photoexcitation lifetime (or excitation cross-section), and the unoccupied molecular orbital (UMO)-metal (IS) charge transfer coupling. Our unique 2PPE results provide a deeper insight for understanding photoexcitation charge transfer with temperature in an organic molecule/metal system.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.4
• /
• pp.1253-1257
• /
• 2011

The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at $50^{\circ}C$ formed well-ordered SAMs with a $(2{\surd}3{\times}{\surd}5)R41^{\circ}$ packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments ($C_5H_9^+$, m/e = 69) generated via C-S bond cleavage and the parent molecular species ($C_5H_9SH^+$, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.3
• /
• pp.875-880
• /
• 2014

Adsorption of 4,4'-bis(mercaptomethyl)biphenyl (44BMBP) on silver nanoparticles has been investigated by surface-enhanced Raman scattering (SERS) spectroscopy. In addition, the Raman spectra of 44BMBP in solid state and in basic condition have been obtained for comparative study to elicit the characteristics of adsorption. The observed Raman and SERS spectra were analyzed comparing with the normal modes and vibrational frequencies from density functional theory (DFT) calculations performed for the feasible structures of 44BMBP molecule. On the basis of excellent agreement between the calculated and the experimental results, the molecule is found to have both the cis- and trans-forms for the mercaptomethyl groups in the solid state as well as in the basic condition. In contrast, the molecule is found to be chemisorbed on the silver surface by forming two Ag-S linkages only in the cis-form but not in the trans-form due to the steric interruption, which indicates the parallel orientation of molecules on the surface. Particularly, the spectral features in the SERS spectra such as the absence of the C-H stretching band and enhancement for the out-of-plane skeletal modes are confirmatory for the parallel geometry through ${\pi}$ interaction between the phenyl rings and the metal surface, based on the electromagnetic surface selection rule.

• Journal of the Microelectronics and Packaging Society
• /
• v.11 no.4 s.33
• /
• pp.87-91
• /
• 2004

We have investigated the effects of W-N/Pt bottom electrode on the ferroelectric degradation of $Sr_{0.8}Bi_{2.4}Ta_2O_9(SBT)/Pt$ due to hydrogen annealing at $350^{\circ}C$ in $N_2$ gas atmosphere containing $5{\%}\;H_2$ gas for 1hr. As a result, inserting the W-N thin films between SBT and Pt, this W-N thin film prevents hydrogen molecules to be chemisorbed at the Pt electrode surface of at the electrode/ferroelectric interface during hydrogen annealing. These hydrogen atoms can diffuse into the SBT and react with the oxide causing the oxygen deficiency in the SBT film, which will result in the ferroelectric degradation. Experimental results show that W-N thin film is a good diffusion barrier during the hydrogen annealing.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2012.02a
• /
• pp.217-217
• /
• 2012

Solution-processed tungsten oxide thin film with thickness of about 30 nm is prepared from ammonium tungstate. This layer is introduced into the interface between the poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) layer and the ITO electrode to be used as an electron blocking layer. The annealed tungsten oxide thin films at $150^{\circ}C$ and $300^{\circ}C$ show amorphous phase, while the $400^{\circ}C$ -annealed tungsten oxide film shows crystalline phase. At $150^{\circ}C$ annealing temperature, the conversion efficiency is significantly improved from 0.71% to 1.42% as the condition is changed from vacuum to air atmosphere, which is related to oxidation state of tungsten in amorphous phase. For the air annealing condition, the conversion efficiency is further increased from 1.42% to 2.01% as the temperature is increased from $150^{\circ}C$ to $300^{\circ}C$, which is mainly due to the removal of the chemisorbed water. However, a slight deterioration in photovoltaic performance is observed when the temperature is increased to $400^{\circ}C$, which is ascribed to poor electron blocking ability due to the formation of crystalline phase. It is concluded that $W^{6+}$ oxidation state and amorphous nature in tungsten oxide interlayer is essential for blocking electron effectively from the active layer to the ITO electrode.

• Korean Chemical Engineering Research
• /
• v.46 no.6
• /
• pp.1069-1074
• /
• 2008

In this work, we made a study for the 3D SAM formation of octanethiol, decanethiol, and dodecanethiol on copper nanoparticles and we verified stability of the copper particle depending on the ratio of dodecanethiol to copper. The reaction was performed in a one-phase system under nitrogen atmosphere and the thiolated copper particles could be obtained by centrifugation. We could confirm that the nanoparticles consisted of a spherical shape of 3~6 nm from TEM images. FT-IR, XPS and TGA results showed that alkanethiols were chemisorbed via thiol group and the packing density of the alkanethiols on copper surface increased with the alkyl chain lengths. XRD patterns gave us useful information about superlattice formations. Finally, $Cu_2O$ was formed when the molar ratio of dodecanethiol to copper is less than unity and copper nanoparticles formed more compact 3D SAMs when the molar ratio of dodecanethiol to copper was 1.25.

• Transactions of the Korean Society of Automotive Engineers
• /
• v.14 no.3
• /
• pp.125-132
• /
• 2006

Transient kinetics of $NH_3$ adsorption/desorption and of SCR(selective catalytic reduction) of NO with $NH_3$ were studied over vanadium based catalysts, such as $V_2O_5/TiO_2$ and $V_2O_5-WO_3/TiO_2$. In the present catalytic reaction process, NO adsorption is neglected while $NH_3$ is strongly chemisorbed on the catalytic surface. Accordingly, it is ruled out the possibility of a reaction between strongly adsorbed $NH_3$ and NO species in line with the hypothesis of an Eley-Rideal mechanism. The present kinetic model assumes; (1) non-activated $NH_3$ adsorption, (2) Temkin-type $NH_3$ coverage dependence of the desorption energy, (3) non-linear dependence of the SCR reaction rate on the $NH_3$ surface coverage. Thus, the surface heterogeneity for adsorption/desorption of $NH_3$ is taken into account in this model. The present study extends the pure chemical kinetic model based on a powdered-phase catalytic system to the chemico-physical one applicable to a realistic monolith reactor.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2007.11a
• /
• pp.145-146
• /
• 2007

Dye-Sensitized Solar Cell Solar cells(DSSC) were appeared for overcoming global environmental problems and lack of fossil fuel problems. And it is one of study field that is getting into the spotlight lately because manufacturing method is more simple and inexpensive than existing silicon solar cells. Oxide semiconductor is used for adsorption of dye and electron transfer in DSSC study, and $TiO_2$ is used most usually. Overall light conversion efficiency is changed by several elements such as $TiO_2$ particle size and structure, pore size and shape. In this study, we report the solar cell performance of titania$(TiO_2)$ film electrodes with various particle sizes. $TiO_2$ particle size was 16 nm, 25 nm, and mixture of 16nm and 25 nm, and manufactured using Doctor blade method. When applied each $TiO_2$ film to DSSC, the best efficiency was found at 16nm of $TiO_2$ particle. 16nm of $TiO_2$ particle has the highest efficiency compared to the others, because particles with smaller diameters would adsorb more dye due to larger surface area. And in case of the mixture of 16nm and 25 nm, the surface area was smaller than expected. It is estimated that double layer is adsorbed a large amount of chemisorbed dye and improved light scattering leading due to efficiency concentration light than mono layer.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.9
• /
• pp.934-942
• /
• 1998

$^13CO$ chemisorbed on platinum particles in L-zeolite has been investigated by static and magic angle spinning NMR spectroscopy. The representative spectra are composed of a broad asymmetric peak with a center of gravity at 230±30 ppm and a sharp symmetric peak at 124±2 ppm which is tentatively assigned to physisorbed $CO_2$, on inner walls of L-zeolite. Overall, the broad resonance component is similar to our previous results of highly dispersed (80-96%) CO/Pt/silica or CO/Pt/alumina samples, still showing metallic characters. The principal difference is in the first moment value. The broad peak in the spectra is assigned to CO linearly bound to Pt particles in the L-zeolites, and indicates a distribution of isotropic shifts from bonding site to bonding site. The NMR results reported here manifest that the Pt particles inside of the L-zeolites channels are not collectively the same with the ones supported on silica or alumina with similar dispersion in terms of Pt particle shape and/or ordering of Pt atoms in a particle. As a result, Pt particles of CO/Pt/L-zeolite were agglomerated accompanying CO desorption upon annealing. There were no definite changes in the NMR spectra due to differences of exchanged cations. Comparison of our observation on CO/Pt/L-zeolite with Sharma et al.'s reveals that even when the first moment, the linewidtb, and the relaxation times of the static spectra and the dispersion measured by chemisorption are similar, the properties of Pt particles can be dramatically different. Therefore, it is essential to take advantage of the strengths of several techniques together in order to interpret data reliably, especially for the highly dispersed samples.