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Article Citation - WoS: 1Outperformance of CaO-Incorporated Alumina-Supported Pd Catalysts in Methanol Decomposition(Springer, 2025) Eryildirim, Busra; Oktar, Nuray; Dogu, DorukThis study aimed to investigate the impact of CaO incorporation to alumina-supported Pd catalysts on the methanol decomposition reaction. For this purpose, mayenite, alumina and/or calcium oxide-supported Pd catalysts were synthesized. The synthesized catalysts were characterized by XRD, FTIR, Laser Raman spectroscopy, N2 adsorption-desorption, pyridine adsorbed DRIFTS, CO2-TPD, XPS, SEM-EDS, and ICP-OES techniques. Catalytic activity tests were carried out over a 6 h reaction period in the range of 100-400 degrees C. The results of the characterization and activity tests showed that the addition of CaO had significant effects on the physicochemical properties of the catalyst as well as on the catalytic activity. By adding CaO to the alumina support material, the acidity was reduced, thus reducing the selectivity for dimethyl ether (DME) formation, which is significantly high for the 1Pd@Al2O3 catalyst, and increasing the H2 and CO selectivity. The mayenite-supported catalyst (1Pd@SGM), which contains alumina and calcium oxide in its unique crystal structure, showed an excellent catalytic performance close to complete methanol conversion with DME selectivity below 1% at 400 degrees C. In the stability test carried out at 350 degrees C for 6 h with 1Pd@Al2O3, 1Pd@SGM, and 1Pd@48CaO@Al2O3 catalysts used in the temperature scan, it was concluded that all catalysts were stable and 1Pd@SGM catalyst showed higher catalytic activity than the others.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: 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.Conference Object Citation - WoS: 85Citation - Scopus: 92Enhancement of Pem Fuel Cell Performance at Higher Temperatures and Lower Humidities by High Performance Membrane Electrode Assembly Based on Nafion/Zeolite Membrane(Pergamon-elsevier Science Ltd, 2015) Devrim, Yilser; Albostan, AyhanThis work reports the preparation of Nafion/zeolite composite membranes with different zeolite loading. The structure of the Nafion/zeolite composite membranes are investigated by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD) and by thermogravimetric analysis (TGA). The introduction of zeolite particles into the Nafion matrix helps to improve the water uptake, proton conductivity and thermal stability of the nanocomposite membranes compared to the virgin Nafion membrane. The SEM analyses have proved the uniform and homogeneous distribution of zeolite in composite membranes. The composite membranes are tested in a single PEMFC with a 5 cm(2) active area operating at the temperature range of 75-120 degrees C and in humidified under 50% relative humidity (RH) and fully humidified conditions. Single PEMFC tests show that Nafion/zeolite composite membrane is more stable and also performed better than virgin Nafion membrane at low humidity condition. The results indicate the Nafion/zeolite composite membranes could be utilized as the proton exchange membranes for PEMFC. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.Conference Object Citation - WoS: 98Citation - Scopus: 101Experimental Investigation of Co Tolerance in High Temperature Pem Fuel Cells(Pergamon-elsevier Science Ltd, 2018) Devrim, Yilser; Albostan, Ayhan; Devrim, HuseyinIn the present work, the effect of operating a high temperature proton exchange membrane fuel cell (HT-PEMFC) with different reactant gases has been investigated throughout performance tests. Also, the effects of temperature on the performance of a HT-PEMFC were analyzed at varying temperatures, ranging from 140 degrees C to 200 degrees C. Increasing the operating temperature of the cell increases the performance of the HT-PEMFC. The optimum operating temperature was determined to be 160 degrees C due to the deformations occurring in the cell components at high working temperatures. To investigate the effects of CO on the performance of HT-PEMFC, the CO concentration ranged from 1 to 5 vol %. The current density at 0.6 V decreases from 0.33 A/cm(2) for H-2 to 0.31 A/cm(2) for H-2 containing 1 vol % CO, to 0.29 A/cm(2) for 3 vol % CO, and 0.25 A/cm(2) for 5 vol % CO, respectively. The experimental results show that the presence of 25 vol % CO2 or N-2 has only a dilution effect and therefore, there is a minor impact on the HT-PEMFC performance. However, the addition of CO to H-2/N-2 or H-2/CO2 mixtures increased the performance loss. After longterm performance test for 500 h, the observed voltage drop at constant current density was obtained as similar to 14.8% for H-2/CO2/CO (75/22/3) mixture. The overall results suggest that the anode side gas mixture with up to 5 vol % CO can be supplied to the HT-PEMFC stack directly from the reformer. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.Review Citation - WoS: 83Citation - Scopus: 92A Review on the Development of the Electrochemical Hydrogen Compressors(Elsevier, 2021) Durmus, Gizem Nur Bulanik; Colpan, C. Ozgur; Devrim, YilserHydrogen should be stored at high pressure and high purity, especially when utilized in fuel cells. Conventionally, mechanical compressors are used for pressurization of hydrogen; however, this technology has disadvantages such as noise and vibration during operation due to their moving parts. Electrochemical hydrogen compressors (ECHC) have emerged as an alternative solution, as these devices can purify and compress hydrogen electrochemically in a single device. This review provides a comprehensive overview of key components and management strategies of the ECHC systems. This review will also provide an overview of different hydrogen compression technologies and provides a comprehensive overview of the latest developments and current issues and future of ECHCs. For this purpose, firstly, the advantages and disadvantages of ECHC compared to mechanical compressors are explained. Then, recent studies on hydrogen purification methods are given. The working principle of ECHC, material development studies and mathematical modeling of ECHCs are also discussed.Article Citation - WoS: 18Citation - Scopus: 20Cobalt 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, AkinAmongst 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.Article Citation - WoS: 19Citation - Scopus: 20Synthesis, Characterization, and Enhanced Formic Acid Electrooxidation Activity of Carbon Supported Mnox Promoted Pd Nanoparticles(Elsevier, 2018) Bulut, Ahmet; Yurderi, Mehmet; Alal, Orhan; Kivrak, Hilal; Kaya, Murat; Zahmakiran, MehmetFormic acid (HCOOH) is one of the promising fuels for direct liquid fed fuel cells. However, CO poisoning is a major challenge for the development of effective catalytic system for formic acid electrooxidation (FAEO). Herein, a novel CO-resistive activated carbon supported Pd-MnOx bimetallic catalyst (Pd-MnOx/C) was presented for FAEO. Pd-MnOx/C catalyst was prepared via simple and reproducible surfactant-free deposition-reduction technique. The characterization of this novel Pd-MnOx/C catalyst was performed by inductively coupled plasma-optical emission spectroscopy (ICP-OES), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), bright field transmission electron microscopy (BFTEM), high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and scanning transmission electron microscope-energy dispersive X-ray spectroscopy (STEM-EDX). The characterization results revealed that Pd and MnOx nanoparticles (NPs) were well dispersed and separately nucleated with a mean diameter of 2.9 nm on the surface of active carbon. FAEO studies were performed on both Pd-MnOx/C and Pd/C catalysts to comprehend the effect of separately formed MnOx on the electrocatalytic activity of Pd NPs. The electrochemical measurements were carried out by using Cyclic Voltammetry (CV) and Chronoamperometry (CA), CO-Strriping Voltammetry, Lineer Sweep Voltammetry (LSV), Electrochemical impedance spectroscopy (EIS) techniques. Electrochemical results revealed that FAEO was activated by the addition of MnOx. Pd-0.6-Mn-0.4 exhibited the optimum catalytic activity with 1.05 A/mg Pd current density. The sum of their results clearly points that the existence of MnOx NPs enhances the electrocatalytic activity of Pd NPs by increasing their CO-resistivity and durability throughout the FAEO. (C) 2018 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
