Browsing by Subject "Catalyst activity"
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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 niobium-zirconium mixed oxide as a novel catalyst for selective catalytic reduction of NO x(2009) Cayirtepe, I.; Naydenov, A.; Ivanov, G.; Kantcheva, M.The performance of mixed niobium-zirconium oxide in the SCR of NO x with propene in excess oxygen has been studied. The mixed oxide is prepared by impregnation of hydrated zirconia with acidic solution (pH 0.5) of peroxoniobium(V) complex, [Nb2(O2)3] 4+, ensuring ZrO2:Nb2O5 mole ratio of 6:1. The calcined sample (denoted as 25NbZ-P) has the structure of Zr 6Nb2O17. According to the catalytic test, the conversion of NO x over the 25NbZ-P catalyst passes through a maximum at 220 °C. Based on the in situ FT-IR results, a reaction mechanism is proposed with nitroacetone and NCO species as the key reaction intermediates. The results of the investigation show that the catalytic properties of the Zr6Nb2O17 solid solution could be of interest regarding the development of low-temperature catalyst for the SCR of NO x with hydrocarbons. © 2009 Springer Science+Business Media, LLC.Item Open Access 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.Item Open Access Enhanced photocatalytic activity of homoassembled ZnO nanostructures on electrospun polymeric nanofibers: a combination of atomic layer deposition and hydrothermal growth(Elsevier, 2014) Kayaci, F.; Vempati S.; Ozgit Akgun, C.; Bıyıklı, Necmi; Uyar, TamerWe report on the synthesis and photocatalytic activity (PCA) of electrospun poly(acrylonitrile) (PAN) nanofibrous mat decorated with nanoneedles of zinc oxide (ZnO). Apart from a detailed morphological and structural characterization, the PCA has been carefully monitored and the results are discussed elaborately when juxtaposed with the photoluminescence. The present hierarchal homoassembled nanostructures are a combination of two types of ZnO with diverse optical qualities, i.e. (a) controlled deposition of ZnO coating on nanofibers with dominant oxygen vacancies and significant grain boundaries by atomic layer deposition (ALD), and (b) growth of single crystalline ZnO nanoneedles with high optical quality on the ALD seeds via hydrothermal process. The needle structure (~25. nm in diameter with an aspect ratio of ~24) also supports the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. Furthermore, it is shown that enhanced PCA is because of the catalytic activity at surface defects (on ALD seed), valence band, and conduction band (of ZnO nanoneedles). PCA and durability of the PAN/ZnO nanofibrous mat have also been tested with aqueous solution of methylene blue and the results showed almost no decay in the catalytic activity of this material when reused.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 FT-IR spectroscopic investigation of the surface reaction of CH4 with NOx species adsorbed on Pd/WO3–ZrO2 catalyst(2007) Kantcheva, M.; Cayirtepe, I.The interaction of methane at various temperatures with NO x species formed by room temperature adsorption of NO + O2 mixture on tungstated zirconia (18.6 wt.% WO3) and palladium(II)-promoted tungstated zirconia (0.1 wt.% Pd) has been investigated using in situ FT-IR spectroscopy. A mechanism for the reduction of NO over the Pd-promoted tungstated zirconia is proposed, which involves a step consisting of thermal decomposition of the nitromethane to adsorbed NO and formates through the intermediacy of cis-methyl nitrite. The HCOO- formed acts as a reductant of the adsorbed NO producing nitrogen. © Springer Science+Business Media, LLC 2007.Item Open Access FTIR spectroscopic study on nickel(II)-exchanged sulfated alumina: nature of the active sites in the catalytic oligomerization of ethene(Springer, 2002) Davydov, A. A.; Kantcheva, M.; Chepotko, M. L.The nature of the active sites in nickel(II)-exchanged sulfated alumina in the reaction of ethene oligomerization has been studied by means of FTIR spectroscopy of adsorbed CO. It has been established that isolated nickel(I) species are the active sites in this process. These sites are formed by a reduction process, in which protonic centers are involved. The latter are due to the presence of covalently-bonded sulfate ions on the catalyst surface.Item Open Access Gold catalysts supported on ceria doped by rare earth metals for water gas shift reaction: influence of the preparation method(2009) Andreeva, D.; Ivanov, I.; Ilieva, L.; Abrashev, M. V.; Zanella, R.; Sobczak, J. W.; Lisowski, W.; Kantcheva, M.; Avdeev, G.; Petrov, K.Gold catalysts based on ceria, doped by various RE metals (La, Sm, Gd, Yb, Y) were studied. The influence of the preparation methods on structure, properties and catalytic activity in the WGS reaction was investigated. The catalysts' supports were prepared using two different methods: co-precipitation (CP) and mechanochemical activation (MA). The catalysts were tested in a wide temperature interval without and after reactivation. All samples were characterized using a combination of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS) and TPR. It was found that the catalytic activity of MA catalysts is higher than CP ones. The gold catalysts based on ceria doped by Yb and Sm exhibited the highest activity. After reactivation in air the MA samples almost kept the WGS activity same, while the CP catalysts increased it. The catalysts of a single- and double-phase structure are formed as a result of CP and MA preparation, respectively. There are no big differences in the gold particles size (2-3 nm) depending on dopants and on the preparation techniques. The RS spectra analysis indicates that most probably the oxygen vacancies are adjacent to Me3+ dopant and the ceria structure seems to be better ordered than in the case of alumina as a dopant. There is no distinct correlation between reducibility and WGS activity. The XPS analysis disclose positively charged gold particles in addition to metallic gold within a surface region of fresh samples and only metallic gold on the samples after catalytic processing. There is no simple correlation between the concentration of Ce3+ in the samples and their WGS activity.Item Open Access Gold supported on ceria doped by Me3+ (Me = Al and Sm) for water gas shift reaction: Influence of dopant and preparation method(2010) Andreeva, D.; Kantcheva, M.; Ivanov, I.; Ilieva, L.; Sobczak, J. W.; Lisowski, W.Gold catalysts supported on ceria doped by Sm and Al were studied. The influence of the preparation method, as well as the nature of dopants on the structure, properties and WGS activity are investigated. The applied methods of preparation cause the modification of ceria in a different extent. In the sample prepared by co-precipitation (CP) and doped by Al, the vacancies are located within the bulk of ceria structure, whereas in the corresponding AuCeSmCP sample the vacancies are located most likely around Sm and the ceria structure seems to be better ordered than the Al doped ceria. There is no distinct correlation between the reducibility and WGS activity of the studied catalysts. The Au 4f XPS spectra of fresh samples reveal higher contribution of dispersed form of Au for Sm doped catalysts than for the corresponding Al doped samples. The Ce 3d XPS spectra disclose also a higher concentration of Ce3+ evaluated before the catalytic operation for Sm doped catalysts as compared with the Al doped fresh samples. The observations by "in situ" FT-IR spectroscopy agree well with the model of active sites and the, mechanism of the WGS reaction proposed recently by some of us. The amount of formate species observed on the AuCeSmCP is higher than that on the AuCeAlCP catalyst and parallels the catalytic activity. The higher concentration of active sites on the surface of the AuCeSmCP catalyst facilitates the dissociation of water.Item Open Access Metal dicyanamides as efficient and robust water-oxidation catalysts(Wiley Blackwell, 2017) Nune, S. V. K.; Basaran, A. T.; Ülker, E.; Mishra, R.; Karadas, F.Non-oxide cobalt-based water-oxidation electrocatalysts have received attention recently for their relative ease of preparation, they are stable both in acidic and basic media, and they have higher turnover frequencies than cobalt oxides. Recent studies show that one of the main bottlenecks in the implementation of non-oxide systems to water splitting is the low number of active metal sites, which is in the order of nmol cm−2. Herein, a new series of non-oxide water-oxidation catalysts has been introduced to the field. Cobalt dicyanamides are observed to have around four times higher surface active sites and better catalytic performances than cyanide-based systems. Long-term catalytic studies (70 h) at an applied potential of 1.2 V and electrochemical studies performed in solutions in pH values of 3.0–12.0 indicate that the compounds are robust and retain their structures even under harsh conditions. Moreover, the addition of Ni impurities to cobalt dicyanamides is a feasible method to improve their catalytic activities.Item Open Access Nickel nanoparticles decorated on electrospun polycaprolactone/chitosan nanofibers as flexible, highly active and reusable nanocatalyst in the reduction of nitrophenols under mild conditions(Elsevier, 2017-04) Karakas, K.; Celebioglu A.; Celebi, M.; Uyar, Tamer; Zahmakiran, M.Today, the reduction of nitro aromatics stands a major challenge because of the pollutant and detrimental nature of these compounds. In the present study, we show that nickel(0) nanoparticles (Ni-NP) decorated on electrospun polymeric (polycaprolactone(PCL)/chitosan) nanofibers (Ni-NP/ENF) effectively catalyze the reduction of various nitrophenols (2-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol) under mild conditions. Ni-NP/ENF nanocatalyst was reproducibly prepared by deposition-reduction technique. The detailed characterization of these Ni-NP/ENF based nanocatalyst have been performed by using various spectroscopic tools including ICP-OES, P-XRD, XPS, SEM, BFTEM, HRTEM and BFTEM-EDX techniques. The results revealed the formation of well-dispersed nickel(0) NP (dmean = 2.71–2.93 nm) on the surface of electrospun polymeric nanofibers. The catalytic activity of the resulting Ni-NP/ENF was evaluated in the catalytic reduction of nitrophenols in aqueous solution in the presence of sodium borohydride (NaBH4) as reducing agent, in which Ni-NP/ENF nanocatalyst has shown high activity (TOF = 46.2 mol 2-nitrophenol/mol Ni min; 48.2 mol 2,4-dinitrophenol/mol Ni min; 65.6 mol 2,4,6-trinitrophenol/mol Ni min). More importantly, due to the nanofibrous polymeric support, Ni-NP/ENF has shown a flexible characteristics along with reusability property. Testing the catalytic stability of Ni-NP/ENF revealed that this new catalytic material provides high reusability performance (at 3rd reuse 86% for 2-nitrophenol, 83% 2,4-dinitrophenol and 82% 2,4,6-trinitrophenol) for the reduction of nitrophenols even at room temperature and under air. The present study reported here also includes the compilation of wealthy kinetic data for Ni-NP/ENF catalyzed the reduction of nitrophenols in aqueous sodium borohydride solution depending on temperature and type of support material (Al2O3, C, SiO2) to understand the effect of the support material and determine the activation parameters.Item Open Access Oligomerization of ethylene in a slurry reactor using a nickel/sulfated alumina catalyst(American Chemical Society, 1997) Zhang, Q.; Kantcheva, M.; Dalla Lana, I. G.During the oligomerization of ethylene over heterogeneous catalysts, the production of α-olefins may be lowered because of an accompanying deactivation of catalyst resulting from strong adsorption of products, by isomerization or by a tendency to copolymerize into branched products. The oligomerization of ethylene was studied using Ni(II)/sulfated alumina catalysts prepared with a nonporous fumed alumina (ALON) support. The influences of methods of catalyst preparation and activation upon oligomerization activity were screened using a gas - solid microreactor. On the basis of the test results obtained in the microreactor, a modified form of the superior catalyst was prepared and its performance was examined in more detail using a well-agitated gas - liquid - solid slurry reactor. This catalyst exhibited very good oligomerization activity with no apparent deactivation in the slurry reactor at temperatures at or below 298 K and at near-atmospheric pressure. Complete conversion of the ethylene with the production of mainly two oligomers, 1-butene and 1-hexene, was attained. After 34 h in the slurry, formation of a significant amount of two branched C6 isomers was observed.Item Open Access One-dimensional copper (II) coordination polymer as an electrocatalyst for water oxidation(Wiley-VCH Verlag, 2017) Mishra, R.; Ülker, E.; Karadas, F.Although cobalt-based heterogeneous catalysts are the central focus in water oxidation research, interest in copper-based water oxidation catalysts has been growing thanks the great abundance of copper and its biological relevance. Several copper oxides have recently been reported to be active catalysts for water oxidation. In this study, a heterogeneous copper-based water oxidation catalyst that is not an oxide has been reported for the first time. Single-crystal XRD studies indicate that the compound is a one-dimensional coordination compound incorporating copper paddle-wheel units connected through phosphine dioxide ligands. The catalyst exhibits an onset potential of 372 mV at pH 10.2, whereas an overpotential of only 563 mV is required to produce a current density of 1 mA cm−2. In addition to cyclic voltammetric and chronoamperometric studies, an investigation into the effect of pH on the catalytic activity and the robustness of the catalyst using long-term bulk electrolysis (12 h) is presented.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 ZnO nanostructures on electrospun nanofibers by atomic layer deposition/hydrothermal growth and their photocatalytic activity(Materials Research Society, 2014) Kayaci, Fatma; Vempati, Sesha; Ozgit-Akgun, Cagla; Biyikli, Necmi; Uyar, TamerA hierarchy of nanostructured-ZnO was fabricated on the electrospun nanofibers by atomic layer deposition (ALD) and hydrothermal growth, subsequently. Firstly, we produced poly(acrylonitrile) (PAN) nanofibers via electrospinning, then ALD process provided a highly uniform and conformai coating of polycrystalline ZnO with a precise control on the thickness (50 nm). In the last step, this ZnO coating depicting dominant oxygen vacancies and significant grain boundaries was used as a seed on which single crystalline ZnO nanoneedles (average diameter and length of ∼25 nm and ∼600 nm, respectively) with high optical quality were hydrothermally grown. The detailed morphological and structural studies were performed on the resulting nanofibers, and the photocatalytic activity (PCA) was tested with reference to the degradation of methylene blue. The results of PCA were discussed in conjunction with photoluminescence response. The nanoneedle structures supported the vectorial transport of photo-charge carriers, which is crucial for high catalytic activity. The enhanced PCA, structural stability and reusability of the PAN/ZnO nanoneedles indicated that this hierarchical structure is a potential candidate for waste water treatment.