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Browsing by Subject "Palladium"

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    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.
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    Continuous mesoporous pd films by electrochemical deposition in nonionic micellar solution
    (American Chemical Society, 2017) Iqbal, M.; Li C.; Wood, K.; Jiang B.; Takei, T.; Dag, Ö.; Baba, D.; Nugraha, A. S.; Asahi, T.; Whitten, A. E.; Hossain, M. S. A.; Malgras, V.; Yamauchi, Y.
    Mesoporous metals that combine catalytic activity and high surface area can provide more opportunities for electrochemical applications. Various synthetic methods, including hard and soft templating, have been developed to prepare mesoporous/nanoporous metals. Micelle assembly, typically involved in soft-templates, is flexible and convenient for such purposes. It is, however, difficult to control, and the ordering is significantly destroyed during the metal deposition process, which is detrimental when it comes to designing precisely mesostructured materials. In the present work, mesoporous Pd films were uniformly electrodeposited using a nonionic surfactant, triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), as a pore-directing agent. The interaction between micelles and metal precursors greatly influences the metal growth and determines the final structure. The water-coordinated species interact with the ethylene oxide moiety of the micelles to effectively drive the Pd(II) species toward the working electrode surface. From small-angle neutron scattering data, it is found that spherical P123 micelles, with an average diameter of ∼14 nm, are formed in the electrolyte, and the addition of Pd ions does not significantly modify their structure, which is the essence of the micelle assembly approach. The uniformly sized mesopores are formed over the entire mesoporous Pd film and have an average pore diameter of 10.9 nm. Cross-sectional observation of the film also shows mesopores spanning continuously from the bottom to the top of the film. The crystallinity, crystal phase, and electronic coordination state of the Pd film are also confirmed. Through this study, it is found that the optimized surfactant concentration and applied deposition potential are the key factors to govern the formation of homogeneous and well-distributed pores over the entire film. Interestingly, the as-prepared mesoporous Pd films exhibit superior electrocatalytic activity toward the ethanol oxidation reaction by fully utilizing the accessible active surface area. Our approach combines electrochemistry with colloidal and coordination chemistry and is widely applicable to other promising metals and alloy electrocatalysts.
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    Cyclodextrin functionalized nanofibers via electrospinning
    (2014) Çelebioğlu, Aslı
    Electrospinning is a commonly studied and widely applied technique for generating nanofibers, with a diameter ranging from several tens of nanometers to a few micrometers. The low-cost, simple set-up, relatively high production rate and reproducibility increase the interests on this method in both academia and industry. Electrospun nanofibers are produced from a broad range of materials with extremely high surface area, very light-weight, nano-porous features and distinct physical/mechanical properties. The general talk in this technique focuses on the production of nanofibers from polymer base materials. However, very recent studies demonstrated that, it is also possible to obtain nanofibers from non-polymeric systems. For this novel development in electrospinning researches, we have achieved to generate nanofibers from cyclodextrins (CD) without using a polymeric template. CD are cyclic oligosaccharides consisting of α-(1,4)-linked glucopyranose units. The truncated cone shape structure of CD provides a favorable place for various kinds of organic molecules to form non-covalent host-guest inclusion complexes (IC). The enhancements and progressing at the guest molecules property and situation, creating with the inclusion complexation, make CD applicable in variety of areas including filtration, pharmaceuticals, cosmetics, functional foods, textiles, analytic chemistry etc. In this thesis, we report on the electrospinning of CD nanofibers, represent their functionalization and potential applications. Firstly, we produced CD nanofibers from three different chemically modified CD types (hydroxypropyl-β-cyclodextrin (HPβCD), hydroxypropyl-γ-cyclodextrin (HPγCD) and methyl-β-cyclodextrin (MβCD)). Afterwards, the electrospinning of native CD (α-CD, β-CD and γ-CD) nanofibers was achieved. The molecular entrapment capability of CD nanofibers was shown by capturing toxic volatile organic compounds (VOCs) from the surrounding. As the next step, the polymer-free nanofibers were obtained from the cyclodextrin inclusion complexes (CD-IC) with antibacterial agent, vanillin and essential oils. Here, we have also indicated applicability of CD-IC nanofibers as a result of antibacterial test. The functionalization of the CD nanofibers was continued with the green and one-step synthesis of metal nanoparticles (Ag-NP, Au-NP and Pd-NP) incorporated nanofibers, in which CD were used as reducing, stabilizing agent and fiber template. Even, the antibacterial, SERS and catalyst potential of these CD based nanofibers were demonstrated for the related nanoparticles. Our research is expanded to a new stage by the production of insoluble poly-CD nanofibers. We have worked on different crosslinking agents to attain insoluble poly-CD nanofibers with uniform morphology. After the optimization of poly-CD nanofibers, the most durable polyCD nanowebs were selected for further analysis and evaluation of the filtration performance in liquid environment. Within poly-CD nanofibers, we have eliminated the solubility challenge of CD nanofibers that restrict their usage. So, we assume that, poly-CD nanofibers will lead-up to generation of new advances for practices of CD nanofibers. All studies showed that, the self-assembly and self-aggregation property of CD are the prior requirements for the electrospinnability of these small molecules. To conclude, very intriguing materials were obtained by integrating large surface area of nanofibers with specific host-guest inclusion complexation capability and non-toxic, biocompatible nature of the CD. Moreover, CD molecules, which are generally used in the powder form, were rendered into more applicable nanofibers form that will represent ease during their usage.
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    Electroless synthesis of 3nm wide alloy nanowires inside Tobacco mosaic virus
    (2012) Balci, S.; Hahn, K.; Kopold P.; Kadri, A.; Wege, C.; Kern, K.; Bittner, A.M.
    We show that 3nm wide cobaltiron alloy nanowires can be synthesized by simple wet chemical electroless deposition inside tubular Tobacco mosaic virus particles. The method is based on adsorption of Pd(II) ions, formation of a Pd catalyst, and autocatalytic deposition of the alloy from dissolved metal salts, reduced by a borane compound. Extensive energy-filtering TEM investigations at the nanoscale revealed that the synthesized wires are alloys of Co, Fe, and Ni. We confirmed by high-resolution TEM that our alloy nanowires are at least partially crystalline, which is compatible with typical Co-rich alloys. Ni traces bestow higher stability, presumably against corrosion, as also known from bulk CoFe. Alloy nanowires, as small as the ones presented here, might be used for a variety of applications including high density data storage, imaging, sensing, and even drug delivery. © 2012 IOP Publishing Ltd.
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    Facile synthesis of bimetallic nanoparticles with diverse nanostructures using metal acetylacetonates
    (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.
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    First-principles calculations of Pd-terminated symmetrical armchair graphene nanoribbons
    (Elsevier, 2013) Kuloglu, A. F.; Sarikavak-Lisesivdin, B.; Lisesivdin, S. B.; Özbay, Ekmel
    The effects of Palladium (Pd) termination on the electronic properties of armchair graphene nanoribbons (AGNRs) were calculated by using ab initio calculations. After a geometric optimization process, the electronic band structures, density of states, and binding energies of AGNRs with Na = 5-15 were calculated. Pd-termination was found to significantly influence the electronic properties of AGNRs. In DOS, many Q0D and Q1D type states were observed. Binding energy (BE) for single-side or both-side Pd-terminated structures represents characteristic drops with the increasing GNR width. With the increasing GNR width, the BEs of these structures become similar to hydrogenated structures. Because of the GNR width, dependent BE also gave information on the possible stiffness information, in which all of this information can be used in studies where controlled binding to graphene is required.
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    Low-pressure deuterium storage on palladium-coated titanium nanofilms: a versatile model system for tritium-based betavoltaic battery applications
    (American Chemical Society, 2023-08-30) Ghobadi, Türkan Gamze Ulusoy; Koçak, Yusuf; Jalal, Ahsan; Altınkaynak, Yağmur; Çelik, Gülşah; Semiz, Tolga; Çakır, Cihan; Bütün, Bayram; Özbay, Ekmel; Karadaş, Ferdi; Özensoy, Emrah
    Deuterium (D2(g)) storage of Pd-coated Ti ultra-thin films at relatively low pressures is fine-tuned by systematically controlling the thicknesses of the catalytic Pd overlayer, underlying Ti ultra-thin film domain, D2(g) pressure (PD2), duration of D2(g) exposure, and the thin film temperature. Structural properties of the Ti/Pd nanofilms are investigated via XRD, XPS, AFM, SEM, and TPD to explore new structure-functionality relationships. Ti/Pd thin film systems are deuterated to obtain a D/Ti ratio of up to 1.53 forming crystallographically ordered titanium deuteride (TiDx) phases with strong Tix+–Dy– electronic interactions and high thermal stability, where >90% of the stored D resides in the Ti component, thermally desorbing at >460 °C in the form of D2(g). Electronic interaction between Pd and D is weak, yielding metallic (Pd0) states where D storage occurs mostly on the Pd film surface (i.e., without forming ordered bulk PdDx phases) leading to the thermal desorption of primarily DOH(g) and D2O(g) at <265 °C. D-storage typically increases with increasing Ti film thickness, PD2, T, and t, whereas D-storage is found to be sensitive to the thickness and the surface roughness of the catalytic Pd overlayer. Optimum Pd film thickness is determined to be 10 nm providing sufficient surface coverage for adequate wetting of the underlying Ti film while offering an appropriate number of surface defects (roughness) for D immobilization and a relatively short transport pathlength for efficient D diffusion from Pd to Ti. The currently used D-storage optimization strategy is also extended to a realistic tritium-based betavoltaic battery (BVB) device producing promising β-particle emission yields of 164 mCi/cm2, an open circuit potential (VOC) of 2.04 V, and a short circuit current (ISC) of 7.2 nA.
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    Mechanochemical activation and patterning of an adhesive surface toward nanoparticle deposition
    (American Chemical Society, 2015) Baytekin, H. T.; Baytekin, B.; Huda, S.; Yavuz, Z.; Grzybowski, B. A.
    Mechanical pulling of adhesive tape creates radicals on the tapes surface. These radicals are capable of reducing metal salts to the corresponding metal nanoparticles. In this way, the mechanically activated tape can be decorated with various types of nanoparticles, including Au, Ag, Pd, or Cu. While retaining their mechanical properties and remaining "sticky, " the tapes can exhibit new properties derived from the presence of metal nanoparticles (e.g., bacteriostaticity, increased electrical conductivity). They can also be patterned with nanoparticles only at selective locations of mechanical activation.
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    Methyldecalin hydrocracking over palladium/zeolite-X
    (Elsevier Science Ltd, Exeter, United Kingdom, 2000) Sayan, S.; Demirel, B.; Paul, J.
    Hydrocracking of methyldecalin over Pd/REX has been studied with surface sensitive techniques in the critical temperature range 325– 3508C. Results from in situ characterization of adsorbed species, and post-reaction analysis of the catalyst surface by infrared and photoemission spectroscopies, were related to product distributions. The results are discussed in light of quantum chemical calculations of free and catalyst bound intermediates, following ring-opening reactions. Liquid and gaseous products were detected by infrared and UV/Vis spectroscopies. Apparent activation energies of product formation hydrogen consumption, over a broader temperature range, were derived from previous autoclave experiments. An increase in temperature, 325–3508C, results in a shift from preferred cracking products to aromatics, an enhanced level of light hydrocarbon off-gases, and a higher coverage of carbonaceous residues. The increased level of carbonaceous residues is accompanied by a lowered coverage of the reactant, at the surface. The altered product distribution can be characterized by apparent single activation energies, valid from 300 to 4508C. Methane and aromatics show a similar rapid increase with temperature, hydrogen consumption a more timid increase, indicating a reaction limited by diffusion, and cycloalkane production a modest inverse temperature dependence. Fully hydrogenated ring-opening products represent valuable fuel components, but hydrogen deficiency can instead lead to chemisorbed precursors to coke. Our calculations show that cyclohexane, 1,2-diethyl, 3-methyl has a lower heat of formation than the corresponding surface intermediates, but a small enthalpy advantage can easily be countered by entropy effects at higher temperatures. This balance is critical to the formation of preferred products, instead of catalyst deactivation and aromatics. The theoretical results further show that surface intermediates, where the terminating hydrogen is replaced by a C–O bond, have distinct vibrations around 1150 cm21. q2000 Elsevier Science Ltd. All rights reserved.
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    MnOx-Promoted pdAg alloy nanoparticles for the additive-free dehydrogenation of formic acid at room temperature
    (American Chemical Society, 2015) Bulut, A.; Yurderi, M.; Karatas, Y.; Say, Z.; Kivrak H.; Kaya, M.; Gulcan, M.; Ozensoy, E.; Zahmakiran, M.
    Formic acid (HCOOH) has a great potential as a safe and a convenient hydrogen carrier for fuel cell applications. However, efficient and CO-free hydrogen production through the decomposition of formic acid at low temperatures (<363 K) in the absence of additives constitutes a major challenge. Herein, we present a new heterogeneous catalyst system composed of bimetallic PdAg alloy and MnOx nanoparticles supported on amine-grafted silica facilitating the liberation of hydrogen at room temperature through the dehydrogenation of formic acid in the absence of any additives with remarkable activity (330 mol H2·mol catalyst-1·h-1) and selectivity (>99%) at complete conversion (>99%). Moreover this new catalytic system enables facile catalyst recovery and very high stability against agglomeration, leaching, and CO poisoning. Through a comprehensive set of structural and functional characterization experiments, mechanistic origins of the unusually high catalytic activity, selectivity, and stability of this unique catalytic system are elucidated. Current heterogeneous catalytic architecture presents itself as an excellent contender for clean hydrogen production via room-temperature additive-free dehydrogenation of formic acid for on-board hydrogen fuel cell applications.
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    Multifunctional electrospun polymeric nanofibrous mats for catalytic reduction, photocatalysis and sensing
    (Royal Society of Chemistry, 2017) Arslan, O.; Uyar, Tamer
    Fabrication and decoration of flexible Nylon 6,6 polymeric nanofibrous mats for production of multifunctional electrospun material was accomplished via visible light-emitting surface-protected silicon quantum dots (Si QD), ZnO nanoparticles (ZnO NP) and Pd nanocubes (Pd NC). UV-range light was utilized for Si QD production and, after hydrolysis/condensation together with nucleation and growth reactions, amine-modified, fluorescent Si QD were obtained. Additionally, available molecular groups on the Si QD coated onto the polymeric nanofibrous mats provided further attachment of metal oxide and metal NP for various catalytic purposes. Analytical investigations showed that visible-light emission could be maintained on the Nylon 6,6 mats for trinitrotoluene (TNT) sensing. Also, due to consecutive NP decoration, multifunctional, polymeric, flexible nanofibrous mats were obtained. Experiments revealed that fabricated multifunctional mats could reduce molecules such as paranitrophenol effectively or decompose waste dyes such as methylene blue via photocatalytic experiments, and sense the pollutant TNT in aqueous solutions as an all-in-one concept.
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    Perfectly absorbing ultra thin interference coatings for hydrogen sensing
    (OSA - The Optical Society, 2016) Serhatlioglu, M.; Ayas S.; Bıyıklı, Necmi; Dana, A.; Solmaz, M. E.
    Here we numerically demonstrate a straightforward method for optical detection of hydrogen gas by means of absorption reduction and colorimetric indication. A perfectly absorbing metal-insulator-metal (MIM) thin film interference structure is constructed using a silver metal back reflector, silicon dioxide insulator, and palladium as the upper metal layer and hydrogen catalyst. The thickness of silicon dioxide allows the maximizing of the electric field intensity at the Air/SiO2 interface at the quarter wavelengths and enabling perfect absorption with the help of highly absorptive palladium thin film (∼7 nm). While the exposure of the MIM structure to H2 moderately increases reflection, the relative intensity contrast due to formation of metal hydride is extensive. By modifying the insulator film thickness and hence the spectral absorption, the color is tuned and eye-visible results are obtained.
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    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.
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    Routes of formation and composition of NOx complexes adsorbed on palladium-promoted tungstated zirconia
    (2006) Kantcheva, M.; Cayirtepe, I.
    Surface species obtained during the adsorption of NO and NO/O2 coadsorption at room temperature on Pd-free (WZ) and Pd-promoted tungstated zirconia (Pd/WZ) are identified by means of in situ FT-IR spectroscopy. The WZ and Pd/WZ samples have a tetragonal structure and contain randomly distributed mesoporous phase. Dispersed palladium(II) species are present in two different environments: (i) Pd2+ ions, which have only Zr4+ ions in their second coordination sphere and (ii) Pd2+ ions, which are linked to both zirconium and tungsten ions via oxygen bridges. On the Pd/WZ sample, NO undergoes oxidation to various NOx species depending on the temperature. The compounds formed at room-temperature oxidation are adsorbed N2O3 and products of its self-ionization, NO+ and NO2-. In this process W(VI) is involved, being reduced to W(IV). At high temperature N2O3 decomposes, restoring the WO species. Under these conditions, NO undergoes oxidation to NO2 by the Pd(II) ions, which are reduced to Pd(I). The nitrosyls of Pd(I) display high thermal stability and do not disappear upon evacuation at 623 K. During NO/O2 coadsorption on the Pd/WZ catalyst at room temperature, the amounts of surface nitrates and NO2/N2O4 formed in the gas phase are significantly lower than those observed under identical conditions in the presence of tungstated zirconia. It is concluded that promotion of tungstated zirconia with palladium(II) suppresses the oxidation of NO by molecular oxygen at room temperature due to the elimination of acidic protons involved in the process. © 2005 Elsevier B.V. All rights reserved.
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    Standing mesochannels: mesoporous PdCu films with vertically aligned mesochannels from nonionic micellar solutions
    (American Chemical Society, 2018) Iqbal, M.; Kim, J.; Yuliarto, B.; Jiang B.; Li C.; Dağ, Ömer; Malgras, V.; Yamauchi, Y.
    Mesoporous bimetallic palladium (Pd) alloy films with mesochannels perpendicularly aligned to the substrate are expected to show superior electrocatalytic activity and stability. The perpendicular mesochannels allow small molecules to efficiently access the active sites located not only at the surface but also within the film because of low diffusion resistance. When compared to pure Pd films, alloying with a secondary metal such as copper (Cu) is cost-effective and promotes resistance against adventitious poisoning through intermediate reactions known to impair the electrocatalytic performance. Here, we report the synthesis of mesoporous PdCu films by electrochemical deposition in nonionic micellar solutions. The mesoporous structures are vertically aligned on the substrate, and the final content of Pd and Cu can be adjusted by tuning the initial precursor molar ratio in the electrolyte solution.
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    Sulfur poisoning and regeneration behavior of perovskite-based NO oxidation catalysts
    (Springer New York LLC, 2017) Kurt M.; Say, Z.; Ercan, K. E.; Vovk, E. I.; Kim, C. H.; Ozensoy, E.
    SOxuptake and release properties of LaMnO3, Pd/LaMnO3, LaCoO3and Pd/LaCoO3perovskites were investigated via in situ Fourier transform infrared (FTIR) spectroscopy, temperature programmed desorption and X-ray photoelectron spectroscopy. Sulfation of the perovskite leads to the formation of surface sulfite/sulfate and bulk-like sulfate species. Pd addition to LaMnO3and LaCoO3significantly increases the sulfur adsorption capacity. Pd/LaMnO3sample accumulates significantly more sulfur than LaMnO3; however it can also release a larger fraction of the accumulated SOxspecies in a reversible fashion at elevated temperatures in vacuum. This is not the case for Co-based materials, where thermal regeneration of bulk sulfates on poisoned LaCoO3and Pd/LaCoO3is extremely ineffective under similar conditions. However, in the presence of an external reducing agent such as H2(g), Pd/LaMnO3requires much lower temperature (873�K) for complete sulfur regeneration as compared to that of Pd/LaCoO3(973�K). Sequential CO and SOxadsorption experiments performed via in situ FTIR indicate that in the presence of carbonyls and/or carbonates, Pd adsorption sites may have a stronger affinity for SOxas compared to that of the perovskite surface, particularly in the early stages of sulfur poisoning.
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    Trimetalic heterogeneous catalyst for dehydrogenation of formic acid with enhanced CO tolerance
    (2017-09) Perşembe, Elif
    Hydrogen energy is considered to be a promising alternative for the sustainable and environmentally friendly solution of the global energy problem. One of the major obstacles of hydrogen energy applications is to maintain safe and efficient storage of hydrogen which can also be achieved chemically using suitable carrier materials. Formic acid (HCOOH, FA) can be utilized as a hydrogen carrier due to its low molecular weight (46 g/mol) and high hydrogen density (%4.4 weight). FA is a stable, non-flammable, and non-toxic biomass side-product rendering it a perfect candidate for an alternative hydrogen vector. Design of novel heterogeneous catalysts which can substitute the existing homogeneous catalytic systems may allow overcoming catalyst isolation and recovery costs and associated logistical problems hindering their applications in on-board operations. FA can be catalytically decomposed via dehydrogenation and dehydration reactions. Selective dehydrogenation of FA is crucial because, the production of CO from dehydration mechanism can suppress the activity of the catalyst by blocking/poisoning the precious metal sites. Consequently, development of CO-resistant, selective, catalytically active, and reusable heterogeneous catalysts has a great significance. In the current work, a new material that can produce H2(g) from FA under ambient conditions in the absence of additives with high CO-poisoning tolerance will be introduced, which is comprised of Pd-based trimetallic active centers functionalized with Ag and Cr in addition to amine-functionalized MnOx promoters dispersed on a SiO2 support surface. A novel trimetallic FA dehydrogenation catalyst was prepared and studied using analytical, ex-situ and in-situ spectroscopic techniques and compared to the results obtained for monometallic, bimetallic and active site-free counterparts. Trimetallic catalysts were found to reveal superior catalytic activity and stability compared to all of the currently investigated catalysts. Structural and catalytic properties of the trimetallic catalysts were investigated as a function of metal loadings. Structural characterization of the synthesized materials was carried out by Raman spectroscopy, Inductively-Coupled Plasma Optical Emission Spectroscopy (ICP-OES), X-ray Diffraction (XRD), Brunauer, Emmett and Teller (BET) Specific Surface Area Analysis, Transmission Electron Microscopy (TEM), High Resolution TEM (HRTEM), Scanning Transmission Electron Microscopy (STEM), and STEM/Energy Dispersive X-Ray (EDX), High-Angle Annular Dark Field (HAADF)/STEM. In addition, interaction of the catalyst surfaces with reactants and products were also monitored via in-situ FTIR spectroscopy for functional characterization. Detailed in-situ FTIR spectroscopic experiments were also performed using HCOOD, DCOOH and DCOOD in order to understand the nature of the adsorbed species, products and catalytic inhibitors.

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