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Article Citation - WoS: 24Citation - Scopus: 28Palladium(0) Nanoparticles Supported on Hydroxyapatite Nanospheres: Active, Long-Lived, and Reusable Nanocatalyst for Hydrogen Generation From the Dehydrogenation of Aqueous Ammonia-Borane Solution(Springer, 2014) Karatas, Yasar; Yurderi, Mehmet; Gulcan, Mehmet; Zahmakiran, Mehmet; Kaya, MuratAmong the solidmaterials considered in the chemical hydrogen storage, ammonia-borane (NH3-BH3) appears to be one of the promising candidates as it can release hydrogen throughout hydrolysis in the presence of suitable catalyst under mild conditions. Herein we report, for the first time, the preparation and characterization of palladium(0) nanoparticles supported on nanohydroxyapatite and their catalytic use in the hydrolysis of ammonia-borane under air at room temperature. These new palladium(0) nanoparticles were generated in situ during the catalytic hydrolysis of ammonia-borane starting with palladium(II) immobilized nanohydroxyapatite. The preliminary characterization of the palladium(0) nanoparticles supported on nanohydroxyapatite was done by the combination of complimentary techniques, which reveals that the formation of well-dispersed Pd(0)NPs nanoparticles (1.41 +/- 0.52 nm) on the surface of hydroxyapatite nanospheres (60-150 nm). The resulting palladium nanocatalyst achieves hydrogen generation from the hydrolysis of ammonia-borane with an initial turnover frequency value (TOF) of 11 mol H-2 mol(-1) Pd x min at room temperature under air. In addition to their high activity, the catalytic lifetime experiment showed that they can also act as a long-lived heterogeneous catalyst for this reaction (TTON = 14,200 mol H-2 mol(-1) Pd) at room temperature under air. More importantly, nanohydroxyapatite- supported palladium(0) nanoparticles were found to be highly stable against to leaching and sintering throughout the catalytic runs that make them isolable, bottleable, and reusable heterogeneous catalyst for the hydrolysis of ammonia-borane.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: 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.
