Browsing by Author "Bulut, Ahmet"

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Ald Preparation of Sio2 Protected Pd-Mnox Nanoparticles Supported on Tio2: Highly Efficient Nanocatalyst for the Dehydrogenation of Formic Acid
(Amer Chemical Soc, 2017) Caner, Nurdan; Yurderi, Mehmet; Bulut, Ahmet; Zahmakiran, Mehmet
Amine Grafted Silica Supported Craupd Alloy Nanoparticles: Superb Heterogeneous Catalysts for the Room Temperature Dehydrogenation of Formic Acid
(Royal Soc Chemistry, 2015) Yurderi, Mehmet; Bulut, Ahmet; Caner, Nurdan; Celebi, Metin; Kaya, Murat; Zahmakiran, Mehmet
Herein we show that a previously unappreciated combination of CrAuPd alloy nanoparticles and amine-grafted silica support facilitates the liberation of CO-free H-2 from dehydrogenation of formic acid with record activity in the absence of any additives at room temperature. Furthermore, their excellent catalytic stability makes them isolable and reusable heterogeneous catalysts in the formic acid dehydrogenation.
Amine-Functionalized Graphene Nanosheet-Supported Pdauni Alloy Nanoparticles: Efficient Nanocatalyst for Formic Acid Dehydrogenation
(Royal Soc Chemistry, 2018) Bulut, Ahmet; Yurderi, Mehmet; Kaya, Murat; Aydemir, Murat; Baysal, Akin; Durap, Feyyaz; Zahmakiran, Mehmet
Formic acid (HCOOH), a major by-product of biomass processing with high energy density, stability and non-toxicity, has a great potential as a safe and a convenient liquid hydrogen (H-2) storage material for combustion engines and fuel cell applications. However, high-purity hydrogen release from the catalytic decomposition of aqueous formic acid solution at desirable rates under mild conditions stands as a major challenge that needs to be solved for the practical use of formic acid in on-demand hydrogen generation systems. Described herein is a new nanocatalyst system comprised of 3-aminopropyltriethoxysilane-functionalized graphene nanosheet-supported PdAuNi alloy nanoparticles (PdAuNi/f-GNS), which can reproducibly be prepared by following double solvent method combined with liquid-phase chemical reduction, all at room temperature. PdAuNi/f-GNS selectively catalyzes the decomposition of aqueous formic acid through the dehydrogenation pathway (similar to 100% H-2 selectivity), in the absence of any promoting additives (alkali formates, Bronsted bases, Lewis bases, etc.). PdAuNi/f-GNS nanocatalyst provides CO-free H-2 generation with a turnover frequency of 1090 mol H-2 mol metal(-1) h(-1) in the additive-free dehydrogenation of formic acid at almost complete conversion (>= 92%) even at room temperature. The catalytic activity provided by PdAuNi/f-GNS nanocatalyst is higher than those obtained with the heterogeneous catalysts reported to date for the additive-free dehydrogenation of formic acid. Moreover, PdAuNi/f-GNS nanoparticles show high durability against sintering, clumping and leaching throughout the catalytic runs, so that the PdAuNi/f-GNS nanocatalyst retains almost its inherent catalytic activity and selectivity at the end of the 10th recycle.
Atomic Layer Deposition of Ruthenium Nanoparticles on Electrospun Carbon Nanofibers: a Highly Efficient Nanocatalyst for the Hydrolytic Dehydrogenation of Methylamine Borane
(Amer Chemical Soc, 2018) Khalily, Mohammad Aref; Yurderi, Mehmet; Haider, Ali; Bulut, Ahmet; Patil, Bhushan; Zahmakiran, Mehmet; Uyar, Tamer
We report the fabrication of a novel and highly active nanocatalyst system comprising electrospun carbon nanofiber (CNF)-supported ruthenium nanoparticles (NPs) (Ru@CNF), which can reproducibly be prepared by the ozone-assisted atomic layer deposition (ALD) of Ru NPs on electrospun CNFs. Polyacrylonitrile (PAN) was electropsun into bead-free one-dimensional (1D) nanofibers by electrospinning. The electrospun PAN nanofibers were converted into well-defined 1D CNFs by a two-step carbonization process. We took advantage of an ozone-assisted ALD technique to uniformly decorate the CNF support by highly monodisperse Ru NPs of 3.4 +/- 0.4 nm size. The Ru@CNF nanocatalyst system catalyzes the hydrolytic dehydrogenation of methylamine borane (CH3NH2BH3), which has been considered as one of the attractive materials for the efficient chemical hydrogen storage, with a record turnover frequency of 563 mol H-2/mol Ru x min and an excellent conversion (>99%) under air at room temperature with the activation energy (E-a) of 30.1 kJ/mol. Moreover, Ru@CNF demonstrated remarkable reusability performance and conserved 72% of its inherent catalytic activity even at the fifth recycle.
Atomic Layer Deposition-Sio2 Layers Protected Pdconi Nanoparticles Supported on Tio2 Nanopowders: Exceptionally Stable Nanocatalyst for the Dehydrogenation of Formic Acid
(Elsevier Science Bv, 2017) Caner, Nurdan; Bulut, Ahmet; Yurderi, Mehmet; Ertas, Ilknur Efecan; Kivrak, Hilal; Kaya, Murat; Zahmakiran, Mehmet
TiO2 nanopowders supported trimetallic PdCoNi alloy nanoparticles were simply and reproducibly prepared by wet-impregnation followed by simultaneous reduction method, then to enhance their stability against to sintering and leaching atomic layer deposition (ALD) technique was utilized to grow SiO2 layers amongst these surface bound PdCoNi alloy nanoparticles (PdCoNi/TiO2-ALD-SiO2). These new nanomaterials are characterized by the combination of complimentary techniques and sum of their results exhibited that the formation of ALD-SiO2 layers protected well-dispersed and highly crystalline PdCoNi alloy nanoparticles (ca. 3.52 nm) supported on TiO2 nanopowders. The catalytic performance of the resulting PdCoNi/TiO2-ALD-SiO2 in terms of activity, selectivity and stability was investigated in the dehydrogenation of aqueous formic acid (HCOOH), which has recently been suggested as a promising hydrogen storage material with a 4.4 wt% hydrogen capacity, solution under mild conditions. The results collected from our systematic studies revealed that PdCoNi/TiO2-ALD-SiO2 nanomaterial can act as highly active and selective nanocatalyst in the formic acid dehydrogenation at room temperature by providing an initial turnover frequency (TOF) value of 207 mol H-2/mol metal;: h and >99% of dehydrogenation selectivity at almost complete conversion. More importantly, the catalytic reusability experiments separately carried out with PdCoNi/TiO2-ALD-SiO2 and PdCoNi/TiO2 nanocatalysts in the dehydrogenation of formic acid under more forcing conditions pointed out that PdCoNi/TiO2-ALD-SiO2 nanocatalyst displays unprecedented catalytic stability against to leaching and sintering throughout the reusability experiments it retains almost its inherent activity, selectivity and conversion even at 20th reuse, whereas analogous PdCoNi/TiO2 completely lost its catalytic performance. (C) 2017 Elsevier B.V. All rights reserved.
Carbon 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, Mehmet
Herein, 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.
Carbon Supported Trimetallic Pdniag Nanoparticles as Highly Active, Selective and Reusable Catalyst in the Formic Acid Decomposition
(Elsevier Science Bv, 2014) Yurderi, Mehmet; Bulut, Ahmet; Zahmakiran, Mehmet; Kaya, Murat
Trimetallic PdNiAg nanoparticles supported on activated carbon were simply and reproducibly prepared by wet-impregnation followed by simultaneous reduction method without using any stabilizer at room temperature. The characterization of the resulting material was done by the combination of complimentary techniques and the sum of their results shows that the formation of well-dispersed 5.6 +/- 2.2 nm PdNiAg nanoparticles in alloy form on the surface of activated carbon. These carbon supported PdNiAg nanoparticles were employed as heterogeneous catalyst in the catalytic decomposition of formic acid, which has great potential as a safe and convenient hydrogen carrier for fuel cells, under mild conditions. It was found that PdNiAg/C can catalyze the dehydrogenation of formic acid with high selectivity (similar to 100%) and activity (TOF = 85 h(-1)) at 50 degrees C. More importantly, the exceptional stability of PdNiAg nanoparticles against to agglomeration, leaching and CO poisoning make PdNiAg/C reusable catalyst in the formic acid dehydrogenation. PdNiAg/C catalyst retains almost its inherent activity (>94%) even at 5th reuse in the dehydrogenation of formic acid with high selectivity (similar to 100%) at complete conversion. The work reported here also includes the compilation of kinetic data for PdNiAg/C catalyzed dehydrogenation of formic acid depending on catalyst [PdNiAg], substrate [HCOOH], promoter [HCOONa] concentrations and temperature to determine the rate expression and the activation parameters (Ea, Delta H-#, and Delta S-#) of the catalytic reaction. (C) 2014 Elsevier B.V. All rights reserved.
Chromium Based Metal-Organic Framework Mil-101 Decorated Palladium Nanoparticles for the Methanolysis of Ammonia-Borane
(Royal Soc Chemistry, 2020) Caner, Nurdan; Yurderi, Mehmet; Bulut, Ahmet; Kanberoglu, Gulsah Saydan; Kaya, Murat; Zahmakiran, Mehmet
Palladium nanoparticles stabilized by an MIL-101 metal-organic framework (Pd@MIL-101) are synthesized by a novel synthesis approach. A Pd@MIL-101 catalyst facilitates H(2)generation from the methanolysis of ammonia-borane with record catalytic activity (TOF = 1080 min(-1)) at room temperature. Moreover, the exceptional stability of Pd@MIL-101 makes it a reusable heterogeneous catalyst in this catalytic transformation.
Cobalt Nanoparticles Supported on Alumina Nanofibers (co/Al2o3): Cost Effective Catalytic System for the Hydrolysis of Methylamine Borane
(Pergamon-elsevier Science Ltd, 2019) Baguc, Ismail Burak; Yurderi, Mehmet; Bulut, Ahmet; Celebi, Metin; Kanberoglu, Gulsah Saydan; Zahmakiran, Mehmet; Baysal, Akin
Amongst different amine-borane derivatives, methylamine-borane (CH3NH2BH3) seems to be one of the capable aspirants in the storing of hydrogen attributable to its high hydrogen capacity, stability and aptitude to generate hydrogen through its catalytic hydrolysis reaction under ambient conditions. In this research paper, we report that cobalt nano-particles supported on alumina nanofibers (Co/Al2O3) are acting as active nanocatalyst for catalytic hydrolysis of methylamine-borane. Co/Al2O3 nanocatalyst was fabricated by double-solvent method followed with wet-chemical reduction, and was characterized by utilizing various spectroscopic methods and imaging techniques. The results gathered from these analyses showed that the formation Al2O3 nanofibers supported cobalt(0) nanoparticles with a mean diameter of 3.9 +/- 1.2 nm. The catalytic feat of these cobalt nanoparticles was scrutinized in the catalytic hydrolysis of methylamine-borane by considering their activity and durability performances. They achieve releasing of 3.0 equivalent of H-2 via methylamine-borane hydrolysis at room temperature (initial TOF = 297 mol H-2/mol metal x h). Along with activity the catalytic durability of Co/Al2O3 was also studied by carrying out recyclability tests and it was found that these supported cobalt nanoparticles have good durability during the course of the catalytic recycles so that Co/Al2O3 preserves almost its innate activity at 5th catalytic recycle. The studies presented here also contains kinetic investigation of Co/Al2O3 catalyzed methylamine borane hydrolysis depending on the temperature, cobalt and methylamine borane concentrations, which were used to define rate expression and the activation energy of the catalytic reaction. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Complete 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, Mehmet
Hydrazine 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.
The Development of Solid-Supported Bimetallic Alloy Nanoclusters, for the High Purity Hydrogen Production From the Catalytic Complete Decomposition of Aqueous Hydrazine Borane
(2021) Bulut, Ahmet; Zahmakıran, Mehmet
Bu tez çalışmasının amacı katı bir hidrojen depolayıcı olarak son yıllarda öne çıkan hidrazin-boranın (N2H4BH3, HB) katalitik tam bozunma tepkimesini katalizleyecek heterojen katalitik sistemlerin geliştirilmesidir. Bu amaçla tez kapsamında mağnezyum oksit (MgO) destekli rodyum (Rh) nanokümeleri (Rh@MgO) ve titanyum(IV) oksit (TiO2) destekli nikel (Ni)-rodyum (Rh) alaşım nanokümeleri (NiRh@TiO2) sentezlenmiş ve ileri analitik/spektroskopik yöntemlerle tanımlanmıştır. Hazırlanan bu heterojen katalizörlerin katalitik performansları, ılımlı koşullar altında (50 °C, açık hava) hidrazin-boranın katalitik tam bozunma tepkimesinde incelenmiştir. Elde edilen sonuçlar Rh@MgO katalizörü için bu tepkime %100 dönüşümle 2005 sa-1 çevrim frekansı (TOFcomplete) ile gerçekleştiğini, Ni0.28Rh0.72@TiO2 katalizörü ile de ve yine %100 dönüşümle 1418 sa-1 çevrim frekansı (TOFcomplete) ile gerçekleştiğini göstermiştir. Bunlara ek olarak her iki katalitik sisteme sızma ve topaklaşmaya karşı dayanıklı bulunmuştur, bu da her iki katalizörü bu önemli tepkime için tekrar kullanılabilir katalizörler yapmaktadır.
Electrochemical Sensing of Hydrogen Peroxide Using Pd@ag Bimetallic Nanoparticles Decorated Functionalized Reduced Graphene Oxide
(Pergamon-elsevier Science Ltd, 2018) Guler, Muhammet; Turkoglu, Vedat; Bulut, Ahmet; Zahmakiran, Mehmet
In this study, an excellent sensitive, selective, and stable electrochemical sensor was fabricated for the determination of hydrogen peroxide (H2O2) using nafion (Nf) and Pd@Ag bimetallic nanoparticles supported on (3-aminopropyl) triethoxysilane (APTES) functionalized reduced graphene oxide (rGO-NH2) modified glassy carbon (GC) electrode. The synthesized nanocomposites were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray powder diffractometer (XRD), and High-resolution transmission electron microscopy (HRTEM). The electrochemical properties of the nanocomposites were investigated by means of electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Under optimized conditions, the electrochemical detection of H2O2 was carried out using amperometric method as well as CV. The linear range for H2O2 determination was 0.002-19.500 mM with a detection limit of 0.7 mu A and sensitivity of 1307.46 mu A mM(-1) cm(-2) due to the strong synergistic effect between Pd and Ag nanoparticles. The fabricated sensor was used for the determination of H2O2 in milk samples. The obtained results showed that the novel Nf/Pd@Ag/rGO-NH2/GC sensor can be used for the determination of H2O2 in real samples. (C) 2018 Elsevier Ltd. All rights reserved.
Electrochemical Sensing of Hydrogen Peroxide Using Pd@ag Bimetallic Nanoparticles Decorated Functionalized Reduced Graphene Oxide (Vol 263, Pg 118, 2018)
(Pergamon-elsevier Science Ltd, 2018) Guler, Muhammet; Turkoglu, Vedat; Bulut, Ahmet; Zahmakiran, Mehmet
Hydrotalcite Framework Stabilized Ruthenium Nanoparticles (ru/Htal): Efficient Heterogeneous Catalyst for the Methanolysis of Ammonia-Borane
(Tubitak Scientific & Technological Research Council Turkey, 2020) Baguc, Ismail Burak; Yurderi, Mehmet; Kanberoglu, Gulsah Saydan; Bulut, Ahmet
Ruthenium nanoparticles stabilized by a hydrotalcite framework (Ru/HTaL) were prepared by following a 2-step procedure comprising a wet-impregnation of ruthenium(III) chloride precatalyst on the surface of HTaL followed by an ammonia-borane (NH3BH3) reduction of precatalyst on the HTaL surface all at room temperature. The characterization of Ru/HTaL was done by using various spectroscopic and visualization methods including ICP-OES, P-XRD, FTIR, B-11 NMR, XPS, BFTEM, and HRTEM. The sum of the results gained from these analyses has revealed the formation of well-dispersed and highly crystalline ruthenium nanoparticles with a mean diameter of 1.27 +/- 0.8 nm on HTaL surface. The catalytic performance of Ru/HTaL in terms of activity, selectivity, and stability was investigated in the methanolysis of ammonia-borane (NH3BH3, AB), which has been considered as one of the most promising chemical hydrogen storage materials. It was found that Ru/HTaL can catalyse methanolysis of AB effectively with an initial turnover frequency (TOF) value of 392.77 min(-1) at conversion (>95%) even at room temperature. Moreover, the catalytic stability tests of Ru/HTaL in AB methanolysis showed that Ru/HTaL acts as a highly stable and reusable heterogeneous catalyst in this reaction by preserving more than 95% of its initial activity even at the 5th recycle.
Metal-Organic Framework (mil-101) Stabilized Ruthenium Nanoparticles: Highly Efficient Catalytic Material in the Phenol Hydrogenation
(Elsevier, 2016) Ertas, Ilknur Efecan; Gulcan, Mehmet; Bulut, Ahmet; Yurderi, Mehmet; Zahmakiran, Mehmet
Ruthenium(0) nanoparticles stabilized by MIL-101 metal-organic framework (Ru/MIL-101) were prepared via gas phase infiltration of Ru(cod) (cot) (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) followed by hydrogenolysis of Ru(cod) (cot)@MIL-101 at 3 bar H-2 and 323 K. The resulting material was characterized by using various analytical tools including ICP-OES, EA, P-XRD, XPS, DR-UV-VIS, SEM, BFTEM, HRTEM, STEM-EDX, CO-chemisorption and N-2-adsorption-desorption technique, which revealed that the formation of ruthenium(0) nanoparticles (4.2 +/- 1.2 nm) mainly exist on the surface of MIL-101 by keeping the host framework intact. The application of Ru/MIL-101 in catalysis by considering their activity, selectivity and reusability was demonstrated in the phenol hydrogenation under mild conditions. Ru/MIL-101 acted as active (lower-limit TOF = 29 mol cyclohexanone/mol Ru x h; corrected TOF = 88 mol cydohexanone/mol Ru x h. at >= 90% conversion) and selective (>= 90%) catalyst in the hydrogenation of phenol to cyclohexanone in water at 323 K and 5 bar initial H-2 pressure. More importantly, the resulting ruthenium(0) nanoparticles in Ru/MIL-101 were found to be highly durable throughout the catalytic reuse in the phenol hydrogenation (retain >= 85% of their inherent activity and selectivity at 5th reuse), which makes Ru/MIL-101 a reusable catalytic material for the liquid phase mediated catalytic transformations. (C) 2015 Elsevier Inc. All rights reserved.
Mnox-Promoted Pdag Alloy Nanoparticles for the Additive-Free Dehydrogenation of Formic Acid at Room Temperature
(Amer Chemical Soc, 2015) Bulut, Ahmet; Yurderi, Mehmet; Karatas, Yasar; Say, Zafer; Kivrak, Hilal; Kaya, Murat; Zahmakiran, Mehmet
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 H-2 center dot mol catalyst(-1)center dot 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.
Nanocrystalline 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, Murat
The 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.
Palladium Nanoparticles Supported on Hydroxyapatite Nanospheres: Highly Active, Reusable and Green Catalyst for Suzuki - Miyaura Cross Coupling Reactions Under Aerobic Conditions
(Wiley-v C H verlag Gmbh, 2018) Bulut, Ahmet; Aydemir, Murat; Durap, Feyyaz; Gulcan, Mehmet; Zahmakiran, Mehmet
The development of simply prepared, highly active and reusable nanocatalysts for Suzuki-Miyaura cross coupling reactions under mild and green conditions remains a challenge in the field of synthetic organic chemistry. Herein, we describe a new nanocatalyst comprising of palladium nanoparticles supported on hydroxyapatite nanospheres, which can reproducibly be formed in-situ during the Suzuki-Miyaura coupling reactions starting with Pd(II)-exchanged nanohydroxyapatite. The characterization of the resulting catalyst by using ICP-OES, P-XRD, XPS, TEM, HRTEM, SEM and N-2-adsorption-desorption analyses revealed that the formation of 3.7 +/- 1.3nm palladium(0) nanoparticles (Pd(0)(similar to 430) nanoclusters) on the surface of nano-sized (similar to 50nm) hydroxyapatite (nano-HAp) support by keeping the host framework intact. This previously unappreciated combination of Pd NPs and nano-HAp (PdNPs@nano-HAp) shows excellent activities (TOF's > 3x10(5) h(-1)) in the Suzuki-Miyaura cross coupling reactions of different arylbromides with phenylboronic acid under mild, green and aerobic conditions. More importanly, these new supported palladium(0) nanoparticles were found to be highly durable nanocatalyst throughout the reusability experiments, they maintain almost their inherent activity after 10(th) catalytic cycle at high conversion (> 98%).
Pd-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, Murat
Herein 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.
Pdau-Mnox Nanoparticles Supported on Amine-Functionalized Sio2 for the Room Temperature Dehydrogenation of Formic Acid in the Absence of Additives
(Elsevier, 2016) Karatas, Yasar; Bulut, Ahmet; Yurderi, Mehmet; Ertas, Ilknur Efecan; Alal, Orhan; Gulcan, Mehmet; Zahmakiran, Mehmet
Formic 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.