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Article Citation - WoS: 34Citation - Scopus: 37Hydroxyapatite-Nanosphere Supported Ruthenium(0) Nanoparticle Catalyst for Hydrogen Generation From Ammonia-Borane Solution: Kinetic Studies for Nanoparticle Formation and Hydrogen Evolution(Royal Soc Chemistry, 2014) Durak, Halil; Gulcan, Mehmet; Zahmakiran, Mehmet; Ozkar, Saim; Kaya, MuratThe development of readily prepared effective heterogeneous catalysts for hydrogen generation from ammonia-borane (AB; NH3BH3) solution under mild conditions still remains a challenge in the field of "hydrogen economy". In this study, we report our finding of an in situ generated, highly active ruthenium nanocatalyst for the dehydrogenation of ammonia-borane in water at room temperature. The new catalyst system consists of ruthenium(0) nanoparticles supported on nanohydroxyapatite (RuNPs@nano-HAp), and can be reproducibly prepared under in situ conditions from the ammonia-borane reduction of Ru3+ ions exchanged into nanohydroxyapatite (Ru3+@nano-HAp) during the hydrolytic dehydrogenation of ammonia-borane at 25 +/- 0.1 degrees C. Nanohydroxyapatite-supported ruthenium(0) nanoparticles were characterized by a combination of advanced analytical techniques. The sum of their results shows the formation of well-dispersed ruthenium(0) nanoparticles with a mean diameter of 2.6 +/- 0.6 nm on the surface of the nanospheres of hydroxyapatite by keeping the host matrix intact. The resulting RuNPs@nano-HAp are highly active catalyst in the hydrolytic dehydrogenation of ammonia-borane with an initial TOF value of 205 min(-1) by generating 3.0 equiv. of H-2 per mole of ammonia-borane at 25 +/- 0.1 degrees C. Moreover, they are sufficiently stable to be isolated and bottled as solid materials, which can be reused as active catalyst under the identical conditions of first run. The work reported here also includes the following results: (i) monitoring the formation kinetics of the in situ generated RuNPs@nano-HAp by hydrogen generation from the hydrolytic dehydrogenation of ammonia-borane as the reporter reaction. The sigmoidal kinetics of catalyst formation and concomitant dehydrogenation fits well to the two-step, slow nucleation, followed by autocatalytic surface growth mechanism, P -> Q (rate constant k(1)) and P + Q -> 2Q (rate constant k(2)), in which P is Ru3+@nano-HAp and Q is the growing, catalytically active RuNPs@nano-HAp; (ii) the compilation of kinetic data for the RuNPs@nano-HAp catalyzed hydrolytic dehydrogenation of ammonia-borane depending on the temperature and catalyst concentration to determine the dependency of reaction rate on catalyst concentration and activation parameters (E-a, Delta H-#, and Delta S-#) of the reaction.Article Citation - WoS: 102Citation - Scopus: 107Copper(0) Nanoparticles Supported on Silica-Coated Cobalt Ferrite Magnetic Particles: Cost Effective Catalyst in the Hydrolysis of Ammonia-Borane With an Exceptional Reusability Performance(Amer Chemical Soc, 2012) Kaya, Murat; Zahmakiran, Mehmet; Ozkar, Saim; Volkan, MurvetHerein we report the development of a new and cost-effective nanocomposite catalyst for the hydrolysis of ammonia-borane (NH3BH3), which is considered to be one of the most promising solid hydrogen carriers because of its high gravimetric hydrogen storage capacity (19.6% wt) and low molecular weight. The new catalyst system consisting of copper nanoparticles supported on magnetic SiO2/CoFe2O4 particles was reproducibly prepared by wet-impregnation of Cu(II) ions on SiO2/CoFe2O4 followed by in situ reduction of the Cu(II) ions on the surface of magnetic support during the hydrolysis of NH3BH3 and characterized by ICP-MS, XRD, XPS, TEM, HR-TEM and N-2 adsorption-desorption technique. Copper nanoparticles supported on silica coated cobalt(II) ferrite SiO2/CoFe2O4 (CuNPs@SCF) act as highly active catalyst in the hydrolysis of ammonia-borane, providing an initial turnover frequency of TOF = 2400 h(-1) at room temperature, which is not only higher than all the non-noble metal catalysts but also higher than the majority of the noble metal based homogeneous and heterogeneous catalysts employed in the same reaction.. More importantly, they were easily recovered by using a permanent magnet in the reactor wall and reused for up, to 10 recycles without losing their inherent catalytic activity significantly, which demonstrates the exceptional reusability of the CuNPs@SCF catalyst.Article Citation - WoS: 16Citation - Scopus: 16Keggin Type-Polyoxometalate Decorated Ruthenium Nanoparticles: Highly Active and Selective Nanocatalyst for the Oxidation of Veratryl Alcohol as a Lignin Model Compound(Wiley-v C H verlag Gmbh, 2017) Baguc, Ismail Burak; Saglam, Serif; Ertas, Ilknur Efecan; Keles, Muhammed Nuri; Celebi, Metin; Kaya, Murat; Zahmakiran, MehmetDescribed herein is a new nanocatalyst system that efficiently works in the aerobic oxidation of veratryl alcohol (VA), which is formed by cleavage of beta-O-4 linkages in lignin, to veratraldehyde (VAL) under mild reaction conditions. The new nanocatalyst system comprised of ruthenium(0) nanoparticles supported on the Keggin type polyoxometalate (POM; K-3[PMo12O40]) network (Ru/POM) can simply and reproducibly be prepared by the dimethylamine-borane ((CH3)(2)NHBH3) reduction of ruthenium(III) chloride trihydrate (RuCl3.3H(2)O) in isopropanol solution of K-3[P Mo12O40] at room temperature. The characterization of Ru/POM by the combination of various analytical techniques reveals that the formation of well-dispersed ruthenium(0) nanoparticles with a mean diameter of 4.7 +/- 1.2nm on the surface of POM network structure. This new Ru/POM nanocatalyst displays remarkable activity (TOF=7.5mol VAld/mol Ru x h) at high selectivity (> 98%) and almost complete conversion (98%) in the aerobic oxidation of VA to VAld under mild conditions.Article Citation - WoS: 22Citation - Scopus: 23Complete Dehydrogenation of Hydrazine Borane on Manganese Oxide Nanorod-Supported Ni@ir Core-Shell Nanoparticles(Amer Chemical Soc, 2020) Yurderi, Mehmet; Top, Tuba; Bulut, Ahmet; Kanberoglu, Gulsah Saydan; Kaya, Murat; Zahmakiran, MehmetHydrazine borane (HB; N2H4BH3) has been considered to be one of the most promising solid chemical hydrogen storage materials owing to its high hydrogen capacity and stability under ambient conditions. Despite that, the high purity of hydrogen production from the complete dehydrogenation of HB stands as a major problem that needs to be solved for the convenient use of HB in on-demand hydrogen production systems. In this study, we describe the development of a new catalytic material comprised of bimetallic Ni@Ir core-shell nanoparticles (NPs) supported on OMS-2-type manganese oxide octahedral molecular sieve nanorods (Ni@Ir/OMS-2), which can reproducibly be prepared by following a synthesis protocol including (i) the oleylamine-mediated preparation of colloidal Ni@Ir NPs and (ii) wet impregnation of these ex situ synthesized Ni@Ir NPs onto the OMS-2 surface. The characterization of Ni@Ir/OMS-2 has been done by using various spectroscopic and visualization techniques, and their results have revealed the formation of well-dispersed Ni@Ir core-shell NPs on the surface of OMS-2. The catalytic employment of Ni@Ir/OMS-2 in the dehydrogenation of HB showed that Ni-0.22@Ir-0.78/OMS-2 exhibited high dehydrogenation selectivity (>99%) at complete conversion with a turnover frequency (TOF) value of 2590 h(-1) at 323 K, which is the highest activity value among all reported catalysts for the complete dehydrogenation of HB. Furthermore, the Ni-0.22@Ir-0.78/OMS-2 catalyst enables facile recovery and high stability against agglomeration and leaching, which make it a reusable catalyst in the complete dehydrogenation of HB. The studies reported herein also include the collection of wealthy kinetic data to determine the activation parameters for Ni-0.22@Ir-0.78/OMS-2-catalyzed dehydrogenation of HB.Article Citation - WoS: 23Citation - Scopus: 27Nanocrystalline Metal Organic Framework (mil-101) Stabilized Copper Nanoparticles: Highly Efficient Nanocatalyst for the Hydrolytic Dehydrogenation of Methylamine Borane(Elsevier Science Sa, 2018) Baguc, Ismail Burak; Ertas, Ilknur Efecan; Yurderi, Mehmet; Bulut, Ahmet; Zahmakiran, Mehmet; Kaya, MuratThe copper nanoparticles stabilized by nanocrystalline MIL-101 framework (Cu/nano-MIL-101) was reproducibly prepared by following double solvent method combined with liquid phase chemical reduction technique. The characterization of the resulting new material was done by using various analytical techniques including ICP-OES, P-XRD, N-2-adsorption-desorption, XPS, FE-SEM, SEM-EDX, BFTEM and HAADF-STEM; the summation of their results reveals that the formation of well-dispersed and very small sized (0.8 nm) copper nanoparticles within nanocrystalline MIL-101 framework. The catalytic performance of Cu/nano-MIL-101 in terms of activity and stability was tested in the hydrolytic dehydrogenation of methylamine borane (CH3NH2BH3), which has been considered as one of the attractive materials for the efficient chemical hydrogen storage. Cu/nano-MIL-101 catalyzes the hydrolytic dehydrogenation of methylamine borane with high activity (turnover frequency; TOF = 257 mot H-2/mol Cu x h) and conversion ( > 99%) under air at room temperature. Moreover, these nano-MIL-101 framework stabilized copper nanoparticles show great durability against to sintering and leaching, which make Cu/nano-MIL-101 reusable nanocatalyst in the hydrolytic dehydrogenation of methylamine-borane. Cu/nano-MIL-101 nanocatalyst retains 83% of its inherent activity at complete conversion even at 10th recycle in the hydrolytic dehydrogenation of methylamine borane.Article Citation - WoS: 150Citation - Scopus: 152Pd-mnox< Nanoparticles Dispersed on Amine-Grafted Silica: Highly Efficient Nanocatalyst for Hydrogen Production From Additive-Free Dehydrogenation of Formic Acid Under Mild Conditions(Elsevier Science Bv, 2015) Bulut, Ahmet; Yurderi, Mehmet; Karatas, Yasar; Zahmakiran, Mehmet; Kivrak, Hilal; Gulcan, Mehmet; Kaya, MuratHerein we report the development of a new highly active, selective and reusable nanocatalyst for additive-free dehydrogenation of formic acid (HCOOH), which has great potential as a safe and convenient hydrogen carrier for fuel cells, under mild conditions. The new catalyst system consisting of bimetallic Pd-MnOx nanoparticles supported on aminopropyl functionalized silica (Pd-MnOx/SiO2-NH2) was simply and reproducibly prepared by deposition-reduction technique in water at room temperature. The characterization of Pd-mnO(x)/SiO2-NH2 catalyst was done by the combination of multipronged techniques, which reveals that the existence of highly crystalline individually nucleated Pd(0) and MnOx nanoparticles (d(mean) = 4.6 +/- 1.2 nm) on the surface of aminopropyl functionalized silica. These supported Pd-MnOx nanoparticles can catalyze the additive-free dehydrogenation of formic acid with record activity (TOF = 1300 h(-1)) at high selectivity (>99%) and conversion (>99%) under mild conditions (at 50 degrees C and under air). Moreover, easy recovery plus high durability of these supported Pd-MnOx nanoparticles make them a reusable heterogeneous catalyst in the additive-free dehydrogenation of formic acid. (C) 2014 Elsevier B.V. All rights reserved.Article Citation - WoS: 125Citation - Scopus: 130Pdau-mnox< Nanoparticles Supported on Amine-Functionalized Sio2 for the Room Temperature Dehydrogenation of Formic Acid in the Absence of Additives(Elsevier Science Bv, 2016) Karatas, Yasar; Bulut, Ahmet; Yurderi, Mehmet; Ertas, Ilknur Efecan; Alal, Orhan; Gulcan, Mehmet; Zahmakiran, MehmetFormic acid (HCOOH) has recently been suggested as a promising hydrogen carrier for fuel cell applications. However efficient hydrogen production through the decomposition of formic acid in the absence of additives under mild thermodynamic conditions constitutes a major challenge because of the ease poisoning of active metals with CO formed as intermediate during formic acid decomposition. Recently, we have reported (App. Catal. B: Env. 164 (2015) 324) our discovery that the separately nucleated MnOx nanoparticles act as CO-sponge around catalytically active Pd nanoparticles exist on the same support and enhances both the activity and CO-resistivity of Pd nanoparticles. Using this important finding, herein, we present a new catalyst system consists of the physical mixture of PdAu alloy and MnOx nanoparticles supported on amine-grafted silica (PdAu-MnOx/N-SiO2) for the room temperature dehydrogenation of formic acid in the absence of any additives. PdAu-MnOx/N-SiO2 catalyst was simply prepared by deposition-reduction technique in water at room temperature with high reproducibility and characterized by the combination of various spectroscopic tools including ICP-OES, P-XRD, DR/UV-vis, XPS, BFTEM, STEM-EDX, STEM-line analysis and CO-stripping voltammetry techniques. The sum of their results shows that the formation of physical mixture of PdAu alloy and MnOx (dmean=2.2 nm) nanoparticles on the surface of support material. This new catalytic material facilitates the hydrogen liberation through the additive-free formic acid dehydrogenation at room temperature with previously unprecedented activity (TOF=785 mol H-2 mol catalyst(-1) h(-1)), converging to that of the existing state of the art homogenous catalysts. This new superior catalytic system enables facile catalyst recovery and very high stability against agglomeration, leaching and CO poisoning, which make it highly reusable catalyst (retains >92% activity and 85% conversion at the 5th catalytic reuse) in the additive-free formic acid dehydrogenation at room temperature. (C) 2015 Elsevier B.V. All rights reserved.Correction Citation - WoS: 1Citation - Scopus: 2Supported Copper-Copper Oxide Nanoparticles as Active, Stable and Low-Cost Catalyst in the Methanolysis of Ammonia-Borane for Chemical Hydrogen Storage (vol 165, Pg 169, 2015)(Elsevier, 2016) Yurderi, Mehmet; Bulut, Ahmet; Ertas, Ilknur Efecan; Zahmakiran, Mehmet; Kaya, Murat[No Abstract Available]Article Citation - WoS: 141Citation - Scopus: 147Carbon Dispersed Copper-Cobalt Alloy Nanoparticles: a Cost-Effective Heterogeneous Catalyst With Exceptional Performance in the Hydrolytic Dehydrogenation of Ammonia-Borane(Elsevier, 2016) Bulut, Ahmet; Yurderi, Mehmet; Ertas, Ilknur Efecan; Celebi, Metin; Kaya, Murat; Zahmakiran, MehmetHerein, we report the development of a new and cost-effective nanocatalyst for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), which is considered to be one of the most promising solid hydrogen carriers due to its high gravimetric hydrogen storage capacity (19.6 wt%) and low molecular weight. The new catalyst system consisting of bimetallic copper-cobalt alloy nanoparticles supported on activated carbon was simply and reproducibly prepared by surfactant-free deposition-reduction technique at room temperature. The characterization of this new catalytic material was done by the combination of multi-pronged techniques including ICP-MS, XRD, XPS, BFTEM, HR-TEM, STEM and HAADF-STEM-line analysis. The sum of their results revealed that the formation of copper-cobalt alloy nanoparticles (d(mean) =1.8 nm) on the surface of activated carbon (CuCo/C). These new carbon supported copper-cobalt alloy nanoparticles act as highly active catalyst in the hydrolytic dehydrogenation of ammonia-borane, providing an initial turnover frequency of TOF = 2700 h(-1) at 298 K, which is not only higher than all the non-noble metal catalysts but also higher than the majority of the noble metal based homogeneous and heterogeneous catalysts employed in the same reaction. More importantly, easy recovery and high durability of these supported CuCo nanoparticles make CuCo/C recyclable heterogeneous catalyst for the hydrolytic dehydrogenation of ammonia-borane. They retain almost their inherent activity even at 10th catalytic reuse in the hydrolytic dehydrogenation of ammonia-borane at 298K. (C) 2015 Elsevier B.V. All rights reserved.Article Citation - WoS: 203Citation - Scopus: 212Palladium Nanoparticles Supported on Amine-Functionalized Sio2 for the Catalytic Hexavalent Chromium Reduction(Elsevier Science Bv, 2016) Celebi, Metin; Yurderi, Mehmet; Bulut, Ahrnet; Kaya, Murat; Zahmakiran, MehmetHexavalent chromium (Cr(VI)) is commonly identified acutely toxic, a proven mutagen and carcinogen heavy metal pollutant in the aquatic environment, whereas Cr(III) is believed to be an essential element. In the present study, we show that palladium(0) nanoparticles supported on 3-aminopropyltriethoxysilane (APTS) functionalized silica (Pd@SiO2-NH2) effectively catalyze the reduction of Cr(VI) to Cr(III) by using formic acid (HCOOH) as reducing agent under mild conditions (at room temperature under air). Pd@SiO2-NH2 catalyst was reproducibly prepared by deposition-reduction technique and characterized by the combination of various spectroscopic tools including ICP-OES, P-XRD, DR/UV-vis, XPS, BFTEM, HRTEM and TEM-EDX techniques. The sum of their results is indicative of the formation of well-dispersed palladium(0) nanoparticles (d(mean) = 3.7 nm) on the surface of APTS-functionalized SiO2. The catalytic performance of the resulting palladium(0) nanoparticles in terms of activity and stability was evaluated by the catalytic reduction of Cr(VI) to Cr(III) in aqueous solution in the presence of formic acid as a reducing agent. Our results reveal that Pd@SiO2-NH2 catalyst displays unprecedented activity (TOF = 258 mol Cr2O72-/mol Pd min) and reusability (<85% at 5th reuse) for the reduction of Cr(VI) to Cr(III) at room temperature. The present study reported here also includes the compilation of wealthy kinetic data for Pd@SiO2-NH2 catalyzed the reduction of Cr(VI) to Cr(III) in aqueous formic acid (HCOOH)-sodium formate (HCOONa) solution depending on substrate [Cr2O72-], catalyst [Pd@SiO2-NH2], surface grafted amine [APTS], formic acid [HCOOH], sodium formate [HCOONa] concentrations, temperature and type of support material (Al2O3, C, unmodified SiO2) to understand the nature of the catalytic reaction and determine the rate expression and activation parameters. (C) 2015 Elsevier B.V. All rights reserved.
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