Browsing by Subject "Platinum"
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Item Open Access 97 percent light absorption in an ultrabroadband frequency range utilizing an ultrathin metal layer: randomly oriented, densely packed dielectric nanowires as an excellent light trapping scaffold(Royal Society of Chemistry, 2017) Ghobadi, A.; Dereshgi, S. A.; Hajian, H.; Birant, G.; Butun, B.; Bek, A.; Özbay, EkmelIn this paper, we propose a facile and large scale compatible design to obtain perfect ultrabroadband light absorption using metal-dielectric core-shell nanowires. The design consists of atomic layer deposited (ALD) Pt metal uniformly wrapped around hydrothermally grown titanium dioxide (TiO2) nanowires. It is found that the randomly oriented dense TiO2 nanowires can impose excellent light trapping properties where the existence of an ultrathin Pt layer (with a thickness of 10 nm) can absorb the light in an ultrabroadband frequency range with an amount near unity. Throughout this study, we first investigate the formation of resonant modes in the metallic nanowires. Our findings prove that a nanowire structure can support multiple longitudinal localized surface plasmons (LSPs) along its axis together with transverse resonance modes. Our investigations showed that the spectral position of these resonance peaks can be tuned with the length, radius, and orientation of the nanowire. Therefore, TiO2 random nanowires can contain all of these features simultaneously in which the superposition of responses for these different geometries leads to a flat perfect light absorption. The obtained results demonstrate that taking unique advantages of the ALD method, together with excellent light trapping of chemically synthesized nanowires, a perfect, bifacial, wide angle, and large scale compatible absorber can be made where an excellent performance is achieved while using less materials.Item Open Access Analysis of the oxidation state of platinum particles in supported catalysts by double differentiation of XPS lines(M A I K Nauka - Interperiodica, 2016) Smirnov, M. Y.; Kalinkin, A. V.; Vovk, E. I.; Bukhtiyarov, V. I.In the work the double differentiation of functions describing the Pt4f7/2 band in the XPS spectra of model supported Pt/SiO2 catalysts is performed in order to determine the number of different chemical states of platinum particles. The functions for the differentiation are obtained by the deconvolution of the experimental spectral contour into two spin-orbit components. As a result of the performed analysis of the number and position of the minima of the second derivative of the function of Pt437/2 the conditions of the oxidation of platinum particles in the Pt/SiO2 sample on treating in a NO + O2 mixture and the reduction of platinum oxide particles on interacting of the PtOx/SiO2 sample with hydrogen are determined.Item Open Access Carbon supported nano-sized Pt-Pd and Pt-Co electrocatalysts for proton exchange membrane fuel cells(2009) Kadirgan, F.; Kannan, A. M.; Atilan, T.; Beyhan, S.; Ozenler, S. S.; Süzer, Şefik; Yörür, A.Nano-sized Pt-Pd/C and Pt-Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt-Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H2, CO and H2-CO mixtures, the Pt-Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt-Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt-Pd/C and Pt-Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3-4 nm. It was found that while the Pt-Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt-Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H2 and O2 gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt-Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt-Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.Item Open Access Characterization of platinum nitride from first-principles calculations(Institute of Physics Publishing, 2009) Yıldız, A.; Akıncı, Ü.; Gülseren, O.; Sökmen, İ.We have performed a systematic study of the ground state properties of the zinc-blende, rock-salt, tetragonal, cuprite, fluorite and pyrite phases of platinum nitride by using the plane wave pseudopotential calculations within the density functional theory. The equilibrium structural parameters and bulk moduli are computed within both the local density approximation (LDA) and generalized gradient approximation (GGA). The comparison of the equation of state (EOS) calculated within the LDA for the pyrite structure with the experimental results demonstrates an excellent agreement, hence the use of the LDA rather than the GGA is essential. Complete sets of elastic moduli are presented for cubic forms. The analysis of the results reveal that the pyrite phase with PtN2 stoichiometry leads to the formation of a hard material with the shear modulus G = 206 GPa. The electronic structure of pyrite PtN2 is given, which shows a narrow indirect gap. The vibrational properties of platinum nitride are investigated in detail from lattice dynamical calculations. The calculations show that fluorite and pyrite structures are dynamically stable as well. However, the calculated vibrational modes of pyrite PtN2 do not show complete agreement with experimental Raman frequencies.Item Open Access Conducting polymer composites of polypyrrole and a poly(arylene ether ketone)(1998) Selampinar F.; Akbulut, U.; Toppare L.Electrically conducting composites of polypyrrole and a poly(arylene ether ketone) were synthesized by electroinitiated polymerization of pyrrole on a poly(arylene ether ketone)-coated platinum electrode. The electrolysis medium was water and p-toluene sulfonic acid. The conductivities of the composites were in the range 1-10 S/cm. The composites were characterized by scanning electron microscopy, Fourier transform infrared, and thermal analyses. The composites were found to be composed of bilayers which can be peeled into two free-standing polymer films. The solution side of the polypyrrole layer of the alloy film contains globular structures, whereas the other side is smoother.Item Open Access Direct evidence for the instability and deactivation of mixed-oxide systems: influence of surface segregation and subsurface diffusion(2011) Emmez, E.; Vovk, E. I.; Bukhtiyarov V. I.; Ozensoy, E.In the current contribution, we provide a direct demonstration of the thermally induced surface structural transformations of an alkaline-earth oxide/transition metal oxide interface that is detrimental to the essential catalytic functionality of such mixed-oxide systems toward particular reactants. The BaOx/TiO2/Pt(111) surface was chosen as a model interfacial system where the enrichment of the surface elemental composition with Ti atoms and the facile diffusion of Ba atoms into the underlying TiO2 matrix within 523 873 K leads to the formation of perovskite type surface species (BaTiO3/Ba2TiO4/BaxTiyOz). At elevated temperatures (T > 973 K), excessive surface segregation of Ti atoms results in an exclusively TiO2/TiOx-terminated surface which is almost free of Ba species. Although the freshly prepared BaOx/TiO2/Pt(111) surface can strongly adsorb ubiquitous catalytic adsorbates such as NO2 and CO2, a thermally deactivated surface at T > 973 K practically loses all of its NO2/CO2 adsorption capacity due to the deficiency of surface BaOx domains.Item Open Access Dynamic relationship between precious metals(2013) Sensoy, A.We use a relatively new approach to endogenously detect the volatility shifts in the returns of four major precious metals (gold, silver, platinum and palladium) from 1999 to 2013. We reveal that the turbulent year of 2008 has no significant effect on volatility levels of gold and silver however causes an upward shift in the volatility levels of palladium and platinum. Using the consistent dynamic conditional correlations, we show that precious metals get strongly correlated with each other in the last decade which reduces the diversification benefits across them and indicates a convergence to a single asset class. We endogenously detect the shifts in these dynamic correlation levels and reveal uni-directional volatility shift contagions among precious metals. The results show that gold has a uni-directional volatility shift contagion effect on all other precious metals and silver has a similar effect on platinum and palladium. However, the latter two do not matter in terms of volatility shift contagion. Thus, investors that hedge with precious metals should, in particular, monitor the volatility levels of gold and silver. © 2013 Elsevier Ltd.Item Open Access Electronic properties of polypyrrole/polyindene composite/metal junctions(Elsevier, 1997) Bozkurt, A.; Ercelebi, C.; Toppare, L.Junction properties between conducting polymer composites of polypyrrole/polyindene (PPy/PIn) with different conductivities and metals like Pt, Au, Al and In have been investigated. Rectifying junctions were observed for low work function metals, In and Al; however, high work function metals, Pt and Au, were observed to form ohmic contacts to PPy/PIn composite in the sandwich geometry. The rectifying behavior of the metal/composite/Pt junctions improved when the conductivity of the composite was decreased from 1 to 0.01 S/cm. Using the ideal Schottky theory various junction parameters have been determined. All planar junctions were ohmic regardless of the conductivities of the samples.Item Embargo Facile synthesis of bimetallic nanoparticles with diverse nanostructures using metal acetylacetonates(Bilkent University, 2024-01) Sayma, Dalya M. F.Bimetallic nanoparticles (NPs) have become a fundamental subject in the field of nanoscience and inorganic chemistry. Owing to the fascinating optical and catalytic properties that rise from their synergetic effect, plasmonic-catalytic bimetallic NPs, in particular, are employed in a myriad of applications such as catalysis, sensing and photocatalysis. Optical properties of plasmonic NPs such as gold or silver NPs are based on the localized surface plasmon resonance (LSPR) in the visible spectral range. Plasmonic NPs enhance the localization of electromagnetic fields, converting light to hot carriers or heat that can be used to drive chemical reactions. On the other hand, catalytic metals, which have d-bands close to the Fermi-level, make strong binding to reactants and lower the activation energy of chemical reactions. The properties of plasmonic-catalytic bimetallic NPs such as efficiency or product selectivity in the chemical reaction do not only rely on factors like size and composition of metal NPs, but more importantly, on the types of nanostructures formed. Herein, several nanostructures were synthesized by developing a facile approach using metal acetylacetonates. The synthesized NPs include bare silver NPs, bare palladium NPs, Pd@Ag core-shell NPs, Pd@Ag nanowires, Ag-Pd alloyed core-satellite NPs, Ag-Pt alloyed nano-stars and concave nano-cubes, and trimetallic AgPdPt NPs. In this study, it was found that the temperature, composition of metal components, and amount of capping and reducing agents play a key role in the synthesis of different types of bimetallic NPs. This study is important in the field of nanochemistry as it provides a novel synthesis method for generating plasmonic-catalytic bimetallic NPs.Item Open Access Facile Synthesis of Three-Dimensional Pt-TiO2Nano-networks: A Highly Active Catalyst for the Hydrolytic Dehydrogenation of Ammonia–Borane(Wiley, 2016) Khalily, M. A.; Eren, H.; Akbayrak, S.; Susapto, H. H.; Bıyıklı, Necmi; Özkar, S.; Güler, Mustafa O.Three‐dimensional (3D) porous metal and metal oxide nanostructures have received considerable interest because organization of inorganic materials into 3D nanomaterials holds extraordinary properties such as low density, high porosity, and high surface area. Supramolecular self‐assembled peptide nanostructures were exploited as an organic template for catalytic 3D Pt‐TiO2 nano‐network fabrication. A 3D peptide nanofiber aerogel was conformally coated with TiO2 by atomic layer deposition (ALD) with angstrom‐level thickness precision. The 3D peptide‐TiO2 nano‐network was further decorated with highly monodisperse Pt nanoparticles by using ozone‐assisted ALD. The 3D TiO2 nano‐network decorated with Pt nanoparticles shows superior catalytic activity in hydrolysis of ammonia–borane, generating three equivalents of H2.Item Open Access Forward tunneling current in Pt/p-InGaN and Pt/n-InGaN Schottky barriers in a wide temperature range(Elsevier, 2012-07-27) Arslan, E.; Çakmak, H.; Özbay, EkmelThe current-transport mechanisms of the Pt contacts on p-InGaN and n-InGaN were investigated in a wide temperature range (80-360 K) and in the forward bias regime. It was found that the ideality factor (n) values and Schottky barrier heights (SBHs), as determined by thermionic emission (TE), were a strong function of temperature and Φb0 show the unusual behavior of increasing linearly with an increase in temperature from 80 to 360 K for both Schottky contacts. The tunneling saturation ( JTU(0)) and tunneling parameters (E 0) were calculated for both Schottky contacts. We observed a weak temperature dependence of the saturation current and a fairly small dependence on the temperature of the tunneling parameters in this temperature range. The results indicate that the dominant mechanism of the charge transport across the Pt/p-InGaN and Pt/n-InGaN Schottky contacts are electron tunneling to deep levels in the vicinity of mixed/screw dislocations in the temperature range of 80-360 K.Item Open Access Initial stages of Pt growth on Ge (001) studied by scanning tunneling microscopy and density functional theory(American Physical Society, 2004) Gurlu, O.; Zandvliet, H. J. W.; Poelsema, B.; Dag, S.; Çıracı, SalimWe have studied the initial stages of submonolayer Pt growth on the Ge(001). We have observed several stable and meta-stable adsorption configurations of Pt atoms at various temperatures. Calculations indicate relatively high binding energies of Pt atoms onto the Ge lattice, at different adsorption sites. Our results show that through-the-substrate bonding (concerted bonding) of two Pt atoms is more favored on Ge(001) surface then a direct Pt-Pt bond. Both our experiments and calculations indicate the breaking of Ge-Ge bonds on the surface in the vicinity of Pt adsorbates. We have also observed the spontaneous generation of 2 + 1 dimer vacancy defects at room temperature that cause the ejection of Ge atoms onto the surface. Finally we have studied the diffusion of Pt atoms into the bulk as a result of annealing and found out that they get trapped at subsurface sites.Item Open Access Platinum-palladium loaded polypyrrole film electrodes for the electrooxidation of D-glucose in neutral media(Elsevier Sequoia SA, Lausanne, Switzerland, 1999) Becerik, İ.; Süzer, Ş.; Kadirgan, F.Modified polymer films with metal particles incorporated into the films by electrodeposition are known as possible electrocatalysts for various electrode reactions such as fuel cell applications. This work presents some results concerning the electrooxidation of D-glucose at modified polymer film electrodes prepared on a platinum substrate. This reaction has a great deal of interest in view of its applications to detection systems (glucose sensor), fuel cells (pacemakers) and electroorganic systhesis. The modified polymer film electrodes contain platinum and/or palladium particles dispersed in the polypyrrole film by electrodeposition in neutral media. Addition of palladium to platinum modifies the electrocatalytic behaviour of the electrode drastically. The modification is thought to involve minimization of the poisoning of the catalyst, hence increasing its electrode activity.Item Open Access Preparation of Au and Au-Pt nanoparticles within PMMA matrix using UV and X-ray irradiation(2009) Ozkaraoglu, E.; Tunc, I.; Süzer, ŞefikAu and Au-Pt alloy nanoparticles are prepared and patterned at room temperature within the PMMA polymer matrix by the action of 254 nm UV light or X-rays. The polymer matrix enables us to entangle the kinetics of the photochemical reduction from the nucleation and growth processes, when monitored by UV-vis spectroscopy. Accordingly, increase of the temperature to 50 °C of the reaction medium increases the nucleation and growth rates of the nanoparticle formation by more than one order of magnitude, due to enhanced diffusion and nucleation at the higher temperature, but has no effect on the photochemical reduction process. Presence of Pt ions also increases the same rate, but by a factor two only. Similar photochemical reduction and particle growth take also place within the PMMA matrix, when these metal ions are subjected to prolonged exposure to X-rays, as evidenced by XPS analysis. Both angle-resolved and charge-contrast measurements using XPS reveal that the resultant Au and Pt species are in close proximity to each other, indicating the Au-Pt alloy formation to be the most likely case.Item Open Access Structural superlubricity of platinum on graphite under ambient conditions: the effects of chemistry and geometry(American Institute of Physics Inc., 2017) Özoǧul, A.; Ipek, S.; Durgun, Engin; Baykara, M. Z.An investigation of the frictional behavior of platinum nanoparticles laterally manipulated on graphite has been conducted to answer the question of whether the recent observation of structural superlubricity under ambient conditions [E. Cihan, S. Ipek, E. Durgun, and M. Z. Baykara, Nat. Commun. 7, 12055 (2016)] is exclusively limited to the gold-graphite interface. Platinum nanoparticles have been prepared by e-beam evaporation of a thin film of platinum on graphite, followed by post-deposition annealing. Morphological and structural characterization of the nanoparticles has been performed via scanning electron microscopy and transmission electron microscopy, revealing a crystalline structure with no evidence of oxidation under ambient conditions. Lateral manipulation experiments have been performed via atomic force microscopy under ambient conditions, whereby results indicate the occurrence of structural superlubricity at mesoscopic interfaces of 4000-75 000 nm2, with a noticeably higher magnitude of friction forces when compared with gold nanoparticles of similar contact areas situated on graphite. Ab initio simulations of sliding involving platinum and gold slabs on graphite confirm the experimental observations, whereby the higher magnitude of friction forces is attributed to stronger energy barriers encountered by platinum atoms sliding on graphite, when compared with gold. On the other hand, as predicted by theory, the scaling power between friction force and contact size is found to be independent of the chemical identity of the sliding atoms, but to be determined by the geometric qualities of the interface, as characterized by an average "sharpness score" assigned to the nanoparticles.Item Open Access Sulfur-tolerant BaO/ZrO2/TiO2/Al2O3 quaternary mixed oxides for deNOX catalysis(Royal Society of Chemistry, 2017) Say, Z.; Mihai, O.; Tohumeken, M.; Ercan, K. E.; Olsson, L.; Ozensoy, E.Advanced quaternary mixed oxide materials in the form of BaO/Al2O3/ZrO2/TiO2 functionalized with Pt active sites (i.e. Pt/BaO/AZT) were synthesized and structurally characterized via XRD and BET in comparison to a conventional Pt/20BaO/Al benchmark NSR/LNT catalyst. The interactions of these catalysts' surfaces with SOx and NOx gases were monitored via in situ FTIR and TPD. There exists a delicate trade-off between NOx storage capacity (NSC) and sulfur uptake/poisoning which is strongly governed by the BaO loading/ dispersion as well as the surface structure and acidity of the support material. Flow reactor measurements performed under realistic catalytic conditions show the high NOx activity for the Pt/20BaO/AZT catalyst at 573 K. After sulfur poisoning and subsequent regeneration at 773 and 973 K, Pt/20BaO/AZT surpassed the NOx catalytic performance at 573 K of all other investigated materials including the conventional Pt/ 20BaO/Al benchmark catalyst.Item Open Access Systematic study of adsorption of single atoms on a carbon nanotube(American Physical Society, 2003) Durgun, Engin; Dag, S.; Bagci, V. M. K.; Gülseren, O.; Yildirim, T.; Çıracı, SalimWe studied the adsorption of single atoms on a semiconducting and metallic single-wall carbon nanotube from first principles for a large number of foreign atoms. The stable adsorption sites, binding energy, and the resulting electronic properties are analyzed. The character of the bonding and associated physical properties exhibit dramatic variations depending on the type of the adsorbed atom. While the atoms of good conducting metals, such as Cu and Au, form very weak bonding, atoms such as Ti, Sc, Nb, and Ta are adsorbed with relatively high binding energy. Most of the adsorbed transition-metal atoms excluding Ni, Pd, and Pt have a magnetic ground state with a significant magnetic moment. Our results suggest that carbon nanotubes can be functionalized in different ways by their coverage with different atoms, showing interesting applications such as one-dimensional nanomagnets or nanoconductors and conducting connects, etc.Item Open Access X-ray induced reduction of Au and Pt ions on silicon substrates(2007) Ozkaraoglu, E.; Tunc, I.; Süzer, ŞefikProlonged exposure to X-rays of HAuCl4, PtCl4 and their mixtures, deposited from an aqueous solution onto a silicon substrate, causes chemical reduction of the metal ions to their metallic states. The corresponding oxidation reaction is the conversion of chloride ions to chlorine. The resultant metal atoms aggregate to form metallic/bimetallic nanoclusters as evidenced from their XPS chemical shifts. Hence, X-rays are usable for in-situ nanoparticle production or for direct-writing applications on silicon substrates. © 2007 Elsevier B.V. All rights reserved.