• Applied Chemistry for Engineering
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• v.23 no.3
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• pp.253-258
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• 2012

The effects of active sites and valence states were investigated over $Pd/TiO_2$ catalyst on simultaneous oxidation of $CH_4$ and CO. The Pd species (PdO) crystallite size increased with increasing Pd loadings, which results in enhancement of the activity of $CH_4$ oxidation. Different results from the activity of $CH_4$ and CO oxidation were shown to be dependent on the Pd valence state on the surface of the catalyst prepared through a thermal treatment. XRD and $H_2-TPR$ analysis confirmed that $Pd^{2+}$species was predominated in the calcination catalyst, while $Pd^0$species was predominated in the reduction catalyst. Additionally, it could be found that the valence state of Pd was a more important factor on the catalytic activity than that of factors as the surface area and pore volume. The reaction mechanism of $CH_4$ and CO followed by the valence state of Pd could be identified using FT-IR analysis.

• Journal of Sensor Science and Technology
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• v.33 no.5
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• pp.259-264
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• 2024

The early detection of hydrogen gas leaks is crucial because of their high explosion risk. Current oxide-semiconductor-based hydrogen sensors are reliant on electrical circuits that may fail during accidents and require high temperatures, thereby raising safety concerns. Thus, there is an urgent need for the development of simpler and more intuitive sensors that can operate at room temperature. This study proposed a hydrogen sensor based on Pd-MoO₃ nanowires. The sensor exhibited a visible color change upon exposure to hydrogen at room temperature. The Pd-MoO₃ nanowires were synthesized by decorating the surface of hydrothermally produced MoO₃ nanowires with 1-5 wt.% Pd. Upon exposure to 5% hydrogen gas at room temperature, all Pd-MoO₃ nanowires exhibited distinct color changes (∆E). In particular, the MoO₃ nanowires with 3 wt.% Pd (3Pd-MoO₃) yielded an exceptionally high ∆E value of over 15 within 10 min. Further, the 3Pd-MoO₃ nanowires exhibited a noticeable color change (∆E > 1.6) within 2 min, demonstrating their potential for highly sensitive and rapid hydrogen detection. The outstanding color change of the 3Pd-MoO₃ nanowires was attributed to valence changes in both Mo (Mo⁶⁺ and Mo⁵⁺) and Pd (Pd²⁺ and Pd⁰) upon exposure to hydrogen.

• Korean Chemical Engineering Research
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• v.46 no.4
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• pp.806-812
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• 2008

The ammonia decomposition reaction has been of increasing interest as a means of treating ammonia in flue gas in the presence of precious metal catalyst. Various catalysts, $Pt-Rh/Al_2O_3$, $Pt-Rh/TiO_2$, $Pt-Rh/ZrO_2$, $Pt-Pd/Al_2O_3$, $Pd-Rh/Al_2O_3$, $Pd-Rh/TiO_2$, $Pd-Rh/ZrO_2$, $Pt-Pd-Rh/Al_2O_3$, $Pd/Ga-Al_2O_3$, $Rh/Ga-Al_2O_3$, and Ru/Ga-$Al_2O_3$, were synthesized by using excess wet impregnation method. Using a homemade 1/4" reactor at $10,000{\sim}50,000hr^{-1}$ of space velocity in the presence of precious metal catalyst ammonia decomposition reactions were carried out to investigate the catalyst activity. The inlet ammonia concentration was maintained at 2,000 ppm, with an air balance. Both $T_{50}$ and $T_{90}$, defined as the temperatures where 50% and 90% of ammonia, respectively, are converted, decreased significantly when alumina-supported catalysts were applied. In terms of catalytic performance on the ammonia conversion in the presence of hydrogen sulfide, $Pt-Rh/Al_2O_3$ catalyst showed no effect on the poisoning caused by hydrogen sulfide. These results indicate that platinum-rhodium bimetallic catalyst is a useful catalyst for ammonia decomposition.

• Journal of IKEEE
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• v.22 no.2
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• pp.356-361
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• 2018

We investigated a hydrogen gas sensor which is available in a high temperature atmosphere. The hydrogen sensors were fabricated into a metal-oxide-semiconductor (MOS) structure made of $Pd/Ta_2O_5/SiC$, and the thin tantalum oxide ($Ta_2O_5$) layer was fabricated by rapid thermal oxidation (RTO). In the experiment, we made three types of sensors with different palladium (Pd) patterns to evaluate the effect of Pd electrode on response characteristics. As the result, the response characteristics in capacitance were improved further when the filled area of the Pd electrode became larger.

• Journal of Surface Science and Engineering
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• v.50 no.5
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• pp.411-420
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• 2017

In this paper, two methods of making the Pd-added $SnO_2$ ($Pd-SnO_2$) powder with pure tetragonal phase by the hydrazine method were suggested and compared in terms of crystal structure, surface morphology, and alcohol gas response. One of the addition methods is to use $PdCl_2$ as a Pd source, the other is to use Pd-based organic with oleylamine (OAM). When Pd concentration was increased from 0 to 5 wt%, the average grain size of $Pd-SnO_2$ made with Pd-OAM were decreased from 32 to 12 nm. In the case of using with $PdCl_2$, grain size of the $PdCl_2$ fell to less than 10 nm. However, agglomerated and extruded surface morphology was observed for the films with Pd addition over 4 wt%. The crack-free $Pd-SnO_2$ thick films were able to successfully fill the $30{\mu}m$ gap of patterned Pt electrodes by optimized ink dropping method. Also, the 2 wt% $Pd-SnO_2$ thick film made with PdCl2 showed gas responses ($R_{air}/R_{gas}$) of 3.7, 5.7 and 9.0 at alcohol concentrations of 10, 50 and 100 ppm, respectively. On the other hand, the prepared 3 wt% $Pd-SnO_2$ thick film with Pd-OAM exhibited very excellent responses of 3.4, 6.8 and 12.2 at the equivalent measurement conditions, respectively. The 3 wt% $Pd-SnO_2$ thick film with Pd-OAM has a specific surface area of $31.39m^2/g$.

• Journal of the Korean Vacuum Society
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• v.15 no.4
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• pp.360-366
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• 2006

We have performed density functional theory calculations for the surface structure of O/Pd(100)-p($2{\times}2$), formed by the adsorption of oxygen atoms of 0.25 ML. The oxygen atoms adsorb preferentially at the fourfold hollow site, and the calculated O-Pd bond length is $2,15{\AA}$, The first interlayer spacing ($d_{12}$) of Pd(100) expands by +0.8% due to the oxygen adsorption, which differs from the experimental value of +3.6% reported by a previous LEED study. Assuming that the LEED sample was possibly contaminated by hydrogen atoms, we also examined the effect of hydrogen impurities on the surface structure. Hydrogen atoms adsorbed on O/Pd(100)-p($2{\times}2$) are found to result in large expansions of $d_{12}$ of Pd(100). Our analysis estimates the amount of hydrogen atoms remaining on the LEED sample as -0.3 ML.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.175.2-175.2
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• 2014

Graphene (G) has been modified with palladium, copper, and manganese oxide nanoparticles (NPs), and their catalytic applications have been studied in C-C coupling reactions and methylmercaptan (CH3SH) decomposition reactions. In this research, graphite oxide (GO) sheets were exfoliated and oxidized from graphite powder and impregnated with metal precursors including Pd2+, Cu2+, and Mn2+. The thermal treatments of the metal impregnated GO in preferred gas environments produced Pd NPs on graphene (Pd/G), PdO NPs on GO (PdO/GO), and CuOx and MnOx NPs on graphene (CuOx/MnOx/G). In case of Pd/G and PdO/GO, the TEM images show that, although the mean size of the Pd NPs changed significantly before and after the C-C coupling reaction, that of the PdO NPs didn't, implying that the PdO/GO was superior to Pd/G in terms of the recyclability. Also, we demonstrate that the CuOx/MnOx/G exerts the excellent catalytic efficiency in CH3SH decomposition reaction comparing with conventional catalysts. The chemical and electronic structural changes were investigated using XRD and XPS.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2369-2376
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• 2007

N2O has been found from experimental and theoretical considerations to bind on-top to the Pd(110) surface in a tilted end-on fashion via its terminal N atom. We use a frontier orbital description of the bonding interactions in the Pd-N2O system to obtain molecular insight into the catalytic mechanism of the activation of N2O by the Pd(110) surface giving rise to the formation of N2 and O on the surface. For the tilted end-on N2O binding mode, the LUMO 3π of N2O has good overlap with the Pd dσ and dπ orbitals which can serve as the electron donors. The donor-acceptor orbital overlap is favorable for electron transfer from Pd to N2O and is expected to dominate the surface reaction pathway of N2O decomposition.

• Annals of Hepato-Biliary-Pancreatic Surgery
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• v.27 no.3
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• pp.292-300
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• 2023

Backgrounds/Aims: Current literature presents limited data regarding outcomes following conversion at the time of minimally invasive pancreaticoduodenectomy (MI-PD). Methods: The National Cancer Database was queried for patients who underwent pancreaticoduodenectomy. Patients were stratified into three groups: MI-PD, converted to open pancreaticoduodenectomy (CO-PD), and open pancreaticoduodenectomy (O-PD). Multivariable modeling was applied to compare outcomes of MI-PD and CO-PD to those of O-PD. Results: Of 17,570 patients identified, 12.5%, 4.2%, and 83.4% underwent MI-PD, CO-PD, and O-PD, respectively. Robotic pancreaticoduodenectomy (R-PD) resulted in a higher lymph node yield (n = 23.2 ± 12.2) even when requiring conversion (n = 22.4 ± 13.2, p < 0.001). Margin positivity was higher in the CO-PD group (26.6%) than in the MI-PD group (21.3%) and the O-PD (22.6%) group (p = 0.017). Length of stay was shorter in the MI-PD group (laparoscopic pancreaticoduodenectomy 10.4 ± 8.6, R-PD 10.6 ± 8.8) and the robotic converted to open group (10.7 ± 6.4) than in the laparoscopic converted to open group (11.2 ± 9) and the O-PD group (11.5 ± 8.9) (p < 0.001). After adjusting for patient and tumor characteristics, both MI-PD (odds ratio = 1.40; p < 0.001) and CO-PD (odds ratio = 1.24; p = 0.020) were significantly associated with an increased likelihood of long-term survival. Conclusions: CO-PD does not negatively impact perioperative or oncologic outcomes.

• Bulletin of the Korean Chemical Society
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• v.25 no.1
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• pp.85-89
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• 2004

Geometrical structures of [Pd(L)$Cl_2$] with oxathia macrocycles have been calculated using ab initio secondorder Moller-Plesset (MP2) and Density Functional Theory (DFT) methods with triple zeta plus polarization (TZP) basis set level. In optimized Pd(L)$Cl_2$ complexes, Pd(II) locates at the center surrounded by a square planar array of two sulfurs on an oxathia macrocycle and two chlorides. The endo-Pd(II) complexes with an axial (Pd${\cdots}$O) interaction are more stable than the exo-Pd(II) complexes without the interaction. In the endo-Pd(II) complexes, the atomic charge of the oxygen atom moves to Pd(II) via the axial ($Pd{\cdots}$O) interaction and then, the charge transfer from Pd(II) to the S-atoms occurs stepwise via ${\pi}$-acceptors of the empty d-orbitals.