[Show abstract][Hide abstract] ABSTRACT: Although the reaction results of numerous iron-based Fischer–Tropsch synthesis catalysts containing various promoters have been reported, the research on their theoretical foundation is still insufficient. In the present work, highly activated K-doped χ-Fe5C2/charcoal nanocatalysts were designed using calculations based on density functional theory (DFT), and then prepared using a melt-infiltration process and a subsequent incipient-wetness method of K precursors. The catalyst at K/Fe = 0.075 in an atomic ratio that bears small iron carbide nanoparticles of 18 nm showed the highest activity (1.54 × 10−4 molCO gFe−1 s−1) and the best hydrocarbon yield (1.41 × 10−3 gHC gFe−1 s−1), as well as a good selectivity for gasoline-range (C5–C12) hydrocarbon products in the high-temperature Fischer–Tropsch reaction.
[Show abstract][Hide abstract] ABSTRACT: Catalytic decomposition of ammonia (NH3) is a promising chemical reaction in energy and environmental applications. Density functional theory (DFT) calculations were performed to clarify the detailed catalytic mechanism of NH3 decomposition on an Fe(100) surface. Specifically, the elementary steps of the mechanism were calculated for the general dehydrogenation pathway of NH3. The adsorption of two types of ammonia dimers (2NH3), locally adsorbed NH3 and hydrogen-bonded NH3, were then compared, revealing that locally adsorbed NH3 is more stable than hydrogen-bonded NH3. By contrast, the dehydrogenation of dimeric NH3 results in a high energy barrier. Moreover, the catalytic characteristics of NH3 decomposition on a nitrogen (N)-covered Fe surface must be considered because the recombination of nitrogen (N2) and desorption have an extremely high energy barrier. Our results indicate that the catalytic characteristics of the NH3 decomposition reaction are altered by N coverage of the Fe surface. This study primarily focused on energetic and electronic analysis. Finally, we conclude that Fe is an alternative catalyst for the decomposition of NH3 in COx-free hydrogen production.
The Journal of Physical Chemistry C. 03/2014; 118(10):5309–5316.
[Show abstract][Hide abstract] ABSTRACT: The exemption clause for Pb-containing automobile parts in the RoHS (Restriction of Hazardous Substances) legislation will expire in a few years. Therefore, there is an urgent need to develop new Pb-free solder alloys that are suitable for automobiles. To improve the properties of the Pb-free solders used in automobiles that are consistently exposed to high temperatures and vibrations, we investigated the effects of minor alloying additions of chromium, calcium and palladium and examined the various properties of the resulting Sn–0.7Cu solders. We then investigated the new intermetallic compounds observed after the addition of chromium. In addition, we conducted thermal analysis to confirm the stability of the alloys at temperatures of approximately 230 °C. The wettability and interfacial reactions between the solder alloys and the Cu under bump metallurgy are discussed. Furthermore, to evaluate the mechanical properties of the developed solder alloys, tensile tests were conducted. We confirmed that our minor alloying strategy enhances the strength and hardness of solder alloys without decreasing their melting temperatures.
Journal of Alloys and Compounds. 01/2014; 608:126–132.
[Show abstract][Hide abstract] ABSTRACT: Sn whiskers are becoming a serious reliability issue in Pb-free
electronic packaging applications. Among the numerous Sn whisker
mitigation strategies, minor alloying additions to Sn have been proven
effective. In this study, several commercial Sn and Sn-Ag baths of
low-whisker formulations are evaluated to develop optimum mitigation
strategies for electroplated Sn and Sn-Ag. The effects of plating
variables and storage conditions, including plating thickness and
current density, on Sn whisker growth are investigated for matte Sn,
matte Sn-Ag, and bright Sn-Ag electroplated on a Si substrate. Two
different storage conditions are applied: an ambient condition
(30°C, dry air) and a high-temperature/high-humidity condition
(55°C, 85% relative humidity). Scanning electron microscopy is
employed to record the Sn whisker growth history of each sample up to
4000 h. Transmission electron microscopy, x-ray diffraction, and focused
ion beam techniques are used to understand the microstructure, the
formation of intermetallic compounds (IMCs), oxidation, the Sn whisker
growth mechanism, and other features. In this study, it is found that
whiskers are observed only under ambient conditions for both thin and
thick samples regardless of the current density variations for matte Sn.
However, whiskers are not observed on Sn-Ag-plated surfaces due to the
equiaxed grains and fine Ag3Sn IMCs located at grain
boundaries. In addition, Sn whiskers can be suppressed under the
high-temperature/high-humidity conditions due to the random growth of
IMCs and the formation of thick oxide layers.
Journal of Electronic Materials 10/2013; · 1.64 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: To control the optical properties of Cu2O for a variety of application, we synthesized Cu2O in nanoscale without other treatments. Cu2O nanoparticles with an average size of 2.7 nm (sigma < or = 3.7%) were successfully synthesized in this study via a modified thermal decomposition process. Copper (II) acetylacetonate was used as a precursor, and oleylamine was used as a solvent, a surfactant and a reducing agent. The oleylamine-mediated synthesis allowed for the preparation of Cu2O nanoparticles with a narrower size distribution, and the nanoparticles were synthesized in the presence of a borane tert-butylamine (BTB) complex, where BTB was a strong co-reducing agent together with oleylamine. UV-vis spectroscopy analysis suggest that band gap energy of these Cu2O particles is enlarged from 2.1 eV in the bulk to 3.1 eV in the 2.7-nm nanoparticles, which is larger than most other reported value of Cu2O nanoparticles. Therefore, these nanoparticles could be used as a transparent material because of transformed optical property.
Journal of Nanoscience and Nanotechnology 09/2013; 13(9):6027-32. · 1.15 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Intensive research on oxygen reduction reaction (ORR) catalysts has been undertaken to find a Pt substitute or reduce the amount of Pt. Ag nanoparticles are potential Pt substitutes; however, the weak oxygen adsorption energy of Ag prompted investigation of other catalysts. Herein, we prepared AgCu bimetallic nanoparticle (NP) systems to improve the catalytic performance and compared the catalytic performance of Ag, Cu, AgCu (core-shell), and AgCu (alloy) NP systems as new catalyst by investigating the adsorption energy of oxygen and the activation energy of oxygen dissociation, which is known to be the rate-determining step of ORR. By analyzing HOMO-level isosurfaces of metal NPs and oxygen, we found that the adsorption sites and the oxygen adsorption energies varied with different configurations of NPs. We then plotted the oxygen adsorption energies against the energy barrier of oxygen dissociation to determine the catalytic performance. AgCu (alloy) and Cu NPs exhibited strong adsorption energies and low activation-energy barriers. However, the overly strong oxygen adsorption energy of Cu NPs hindered the ORR.
[Show abstract][Hide abstract] ABSTRACT: We report first-principles calculations of adsorption, dissociation, penetration, and diffusion for the complete nitridation mechanism of nitrogen molecules on a pure Fe surface (bcc, ferrite phase). The mechanism of the definite reaction path was calculated by dividing the process into four steps. We investigated various reaction paths for each step including the energy barrier based on the climb image nudged elastic band (CI-NEB) method, and the complete reaction pathway was computed as the minimum energy path (MEP). The adsorption characteristics of nitrogen (N) and molecular nitrogen (N2) indicate that nitrogen atoms and molecules are energetically favorable at the hollow sites on pure Fe(100) and (110). The dissociation of the nitrogen molecule (N2) was theoretically supported by electronic structure calculations. The penetration of nitrogen from the surface to the sub-surface has a large energy barrier compared with the other steps. The activation energy calculated for nitrogen diffusion in pure bcc Fe was in good agreement with the experimental results. Finally, we confirmed the rate-determining step for the full nitridation reaction pathway. This study provides fundamental insight into the nitridation mechanism for nitrogen molecules in pure bcc Fe.
Physical Chemistry Chemical Physics 03/2013; · 3.83 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Acetic acid (AA) has been employed to reduce the surface capping ligands of Ag nanoparticles (NPs) for the fabrication of low-temperature-processable and highly conductive Ag ink. The ligand reduction of the Ag NPs was achieved using a one-step method, in which oleylamine (OA)-capped Ag NPs were immersed in AA for different durations (1, 2, 3, 5 and 10 h). The weight of the total capping ligand was reduced from 12.1 wt% to 2.3 wt% by 10 h AA immersion. According to in situ transmission electron microscopy (TEM) and electrical resistivity, the ligand-reduced Ag NPs were cured at a much lower temperature (approximately 100 °C) and showed better electrical performance than OA-capped NPs under the same conditions. To investigate the reason for this enhancement of the electrical properties, we characterized the surface chemistry of the Ag NPs by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), which revealed that the surface capping ligand was exchanged from the OA to the acetate ion. In addition, the adsorption energy of the ligand was increased by the ligand exchange, which was studied using density functional theory (DFT) calculations. DFT was effective in explaining the adsorption of each ligand on Ag NPs and indicated that the ligand can be exchanged by AA immersion.
[Show abstract][Hide abstract] ABSTRACT: Sn whiskers are becoming a serious reliability problem in microelectronics where Pb-free solder technology is being implemented with pure Sn or Sn-rich alloys. Numerous investigations have been performed to understand the whisker growth mechanisms and thereby to mitigate Sn whisker growth. Among many Sn whisker mitigation strategies, minor alloying additions to Sn have been found to be quite effective. One challenge in evaluating Sn whisker growth is a time-consuming aging test, such as 4000 h testing condition recommended by the JEDEC-JESD201A standard. In this study, several commercial Sn and Sn-Ag baths of low whisker formulations are evaluated. The effects of plating variables and aging conditions on Sn whisker growth are investigated with matte Sn, matte Sn-Ag, and bright Sn-Ag electroplated on a Cu/Ni/Si substrate. The layer thickness and current density are the major plating variables studied. Two different storage conditions are applied; an ambient condition (30°C/dry air), and a high temperature/humidity condition (55°C/85%RH). In addition, the effect of plastic deformation on Sn whisker growth is investigated as an acceleration method for Sn whisker testing. Microhardness indentation technique is applied to electroplated Sn and Sn-Ag samples to plastically deform them before T/H testing. Each sample is examined by SEM at a regular time interval up to 4000 h. Various morphologies of Sn whiskers are observed and their growth statistics are analyzed in terms of plating conditions, plastic deformation and T/H testing conditions. Plastic deformation is found to significantly accelerate Sn whisker growth both in pure Sn and Sn-Ag samples. The method of plastic deformation can be employed to shorten the time-consuming Sn whisker growth testing.
Electronic Components and Technology Conference (ECTC), 2013 IEEE 63rd; 01/2013
[Show abstract][Hide abstract] ABSTRACT: To enhance the reliability of Pb-free solders in high temperature and high humidity conditions, the minor alloying elements of Be and Co are investigated in terms of the growth of Sn whiskers and various properties of Sn-based Pb-free solders. Sn whisker growth is suppressed by adding up to 0.02 wt% Be to Sn-based solders. Adding Be and Co can effectively reduce the undercooling of Sn–1.0Ag–0.5Cu (wt%) solders. And the microstructures of Sn–1.0Ag–0.5Cu–0.02Be solders are similar to those of Sn–1.0Ag–0.5Cu. Furthermore, adding Co to solders increases the microhardness number as a result of the solid solution hardening. Adding Be causes no changes in the morphology or thickness of Cu6Sn5 at the Cu/OSP (organic solderability preservative) under bump metallurgy interface. However, the scallop-like Cu6Sn5 microstructure changes to a flat (Cu,Co)6Sn5 microstructure when 0.05 wt% of Co is added to Sn–1.0Ag–0.5Cu–0.02Be solders.
Journal of Materials Research 07/2012; 27(14):1877-1886. · 1.82 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Density functional theory (DFT) calculations confirm the structural stability of isomers for 13-atom Ag, Cu, and AgCu nanoparticles. Ag13 and Cu13 nanoparticles have a different stable structure because of the quantum effect and differences in surface energy. We systematically studied the oxygen reduction reaction (ORR) of Ag13, Cu13, Ag12Cu1 (core–shell) and Ag12Cu1 (alloy) nanoparticles by investigating the adsorption property of O2 and the transition state calculations of O2 dissociation, which determine the ORR rate. An Ag alloy with Cu has the high adsorption energy and a low energy barrier. It also exhibits the high structural stability during the reaction.
[Show abstract][Hide abstract] ABSTRACT: We studied the structural evolution of a 270-atom Ag-Au bimetallic nanoparticle (2 nm in size) with varying composition and temperature. The liquid to solid transition region and the solid-state structure were investigated using molecular dynamics simulations. To determine the exact transition temperature region, we applied the mean square displacement and structure deviation methods, as well as the generally used caloric curve of potential energy versus temperature. The results showed that a complete solid-solution phase diagram of the binary Ag-Au system was obtained. Irrespective of the composition, the freezing temperature of a Ag-Au bimetallic nanoparticle was lower than that of the bulk state by a margin of several hundred degrees, and three different solid-state structures are proposed in relation to the Au composition. Our phase diagram offers guidance for the application of Ag-Au nanoparticles.
Physical Chemistry Chemical Physics 02/2012; 14(8):2791-6. · 3.83 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: To steadily apply conductive inks that contain Cu nanoparticles (NPs) to inkjet printing of patterns at temperatures below 150 °C, the size of the Cu NPs must be reduced. Therefore, we obtained Cu NPs in the range of 9-33 nm, and we studied how their size changes. The variation of the chemical reaction rate changed the size of the Cu NPs for two main reasons. First, the fast transition rate of the Cu precursors at high pH values raises the supersaturation level of the Cu precursor above that of a process with a slow transition rate. The high supersaturation level is generally attributed to the small Cu nuclei and the slow growth caused by their density. Second, the high viscosity of the reaction solution, which occurs because polyvinyl pyrrolidone (PVP) causes an increase in the repulsive force, slows the growth of the Cu NPs at high pH values. The recrystallization temperature of the 9 nm Cu NPs was reduced to 108 °C, and a low specific resistivity of 45 μΩ cm was achieved using the conductive ink prepared with 9 nm Cu NPs at 120 °C. This temperature is significantly lower than those reported for other Cu NP inks. Hence, Cu NP conductive ink could considerably reduce costs because of its apparently low temperature, resolving the main bottleneck of inkjet printing on flexible (polymeric) substrates.
[Show abstract][Hide abstract] ABSTRACT: A new yellow-emitting γ-Ca2SiO4:Ce3+,Li+ phosphor was synthesized via a solid-state reaction. The phosphor showed a strong yellow emission with a wide bandwidth of 135.4 nm under blue light excitation. Absorption and photoluminescence measurements and density functional theory calculations suggest that the luminescence of the phosphor can be attributed primarily to the transitions of 5d→4f (2F(7/2) and 2F(5/2)) of Ce3+ ions occupying Ca(1) sites in the host crystal. White light-emitting diodes (LEDs) were fabricated by combining this phosphor with a blue LED, and excellent white light with a high color rendering index of 86 was created owing to the wide emission bandwidth of the phosphor.
[Show abstract][Hide abstract] ABSTRACT: Density functional theory was used to study the CO oxidation catalytic activity of CeO(2)-supported Au nanoparticles (NPs). Experimental observations on CeO(2) show that the surface of CeO(2) is enriched with oxygen vacancies. We compare CO oxidation by a Au(13) NP supported on stoichiometric CeO(2) (Au(13)@CeO(2)-STO) and partially reduced CeO(2) with three vacancies (Au(13)@CeO(2)-3VAC). The structure of the Au(13) NP was chosen to minimize structural rearrangement during CO oxidation. We suggest three CO oxidation mechanisms by Au(13)@CeO(2): CO oxidation by coadsorbed O(2), CO oxidation by a lattice oxygen in CeO(2), and CO oxidation by O(2) bound to a Au-Ce(3+) anchoring site. Oxygen vacancies are shown to open a new CO oxidation pathway by O(2) bound to a Au-Ce(3+) anchoring site. Our results provide a design strategy for CO oxidation on supported Au catalysts. We suggest lowering the vacancy formation energy of the supporting oxide, and using an easily reducible oxide to increase the concentration of reduced metal ions, which act as anchoring sites for O(2) molecules.
Journal of the American Chemical Society 12/2011; 134(3):1560-70. · 10.68 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Utilizing density functional theory calculations and a modified kinetic model, we report the CO oxidation reactivity of negatively and positively charged isolated cuboctahedron (COh) and icosahedron (Ih) Ag13 nanoparticles. Charging the nanoparticles modifies the electron distribution in the core and shell atoms as well as the structural stability of the Ag nanoparticles. During the reaction, Ih Ag13 nanoparticles can be easily deformed into an amorphous or COh structure, which is more stable than the Ih structure. However, it does not function well as a renewable catalyst. Although a neutral COh Ag13 nanoparticle exhibits relatively poor reactivity, the reactivity is enhanced significantly by excess electrons. This study provides fundamental insight into how the electronic and structural interaction between an oxide support and the supported nanoparticle affects the catalytic activity of the general nanocatalyst.
The Journal of Physical Chemistry C. 11/2011; 115(50):24771–24777.
[Show abstract][Hide abstract] ABSTRACT: We report the geometric and electronic effects of amine (with one lone pair electron) and thiol (with two lone pair electrons) ligands on the structural transformation of Pt(55) nanoparticles (NPs) by first-principles calculation. Although a cuboctahedral (COh) structure is less stable than an icosahedral (Ih) structure by 1.36 eV for a bare Pt(55) NP, the activation barrier from the COh to the Ih structure is very high, by 1.97 eV, indicating that it would be difficult to observe the structural evolution of a COh structure to an Ih structure for a bare Pt(55) NP at ambient temperature. However, with the help of the adsorption of methylamine, the structural evolution from a COh structure to an Ih structure is accomplished by the Mackay transformation. This transformation is driven by a combination of both the external forces resulting from the adsorption of the ligand, which pull out the Pt atoms on the face sites of NPs in a radial direction, and the contraction forces in a tangential direction. As more methylamine is added, the Ih structure is observed to return to the original COh structure owing to the directional orbital hybridization that occurs between the Pt NPs and the methylamine. In contrast, such structural evolutions are not observed in the case of methylthiol because the sulfur (S) in the ligand has two lone pair electrons, leading to two Pt-S bonds. As a result, the radial-directed external force that the NPs experience because of the adsorption of methylthiols is much lower than that found in methylamine-ligated NPs. Furthermore, the adsorption of methylthiol leads to an expansion (not contraction) in the tangential direction, which does not qualify as a Mackay transformation. Thus, the Pt NPs ligated with methylthiol do not have a driving force strong enough to cause structural change. The methylthiol-stabilized Pt NPs retain their initial COh structure despite an abundance of ligand adsorption. From these results, we suggest that the NP structure can be controlled by varying the amount and species of ligands.
[Show abstract][Hide abstract] ABSTRACT: We report a new and highly versatile approach to artificial layered materials synthesis which borrows concepts of molecular beam epitaxy, self-assembly, and graphite intercalation compounds. It readily yields stacks of graphene (or other two-dimensional sheets) separated by virtually any kind of "guest" species. The new material can be "sandwich like", for which the guest species are relatively closely spaced and form a near-continuous inner layer of the sandwich, or "veil like", where the guest species are widely separated, with each guest individually draped within a close-fitting, protective yet atomically thin graphene net or veil. The veils and sandwiches can be intermixed and used as a two-dimensional platform to control the movements and chemical interactions of guest species.