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Article Citation - WoS: 9Citation - Scopus: 10Chromium 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, MehmetPalladium 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.Article Citation - WoS: 13Citation - Scopus: 13Ruthenium Nanoparticles Supported on Reduced Graphene Oxide: Efficient Catalyst for the Catalytic Reduction of Cr(vi) in the Presence of Amine-Boranes(Wiley-v C H verlag Gmbh, 2020) Yurderi, Mehmet; Bulut, Ahmet; Kanberoglu, Gulsah Saydan; Kaya, Murat; Kanbur, Yasin; Zahmakiran, MehmetHexavalent chromium (Cr(VI)) is a toxic, mutagen and carcinogen contaminant exist in surface and groundwater, while its reduced form trivalent chromium (Cr(III)) is known as an essential element to normal carbohydrate, lipid and protein metabolism in nature. Addressed herein, for the first time, ruthenium nanoparticles supported on reduced graphene oxide (Ru@rGO) catalyze the reduction of aqueous Cr(VI) to Cr(III) in the presence of amine-boranes; ammonia-borane (AB; NH3BH3), methylamine-borane (MeAB; CH3NH2BH3), dimethylamine-borane (DMAB; (CH3)(2)NHBH3) as reducing agents under mild conditions (at room temperature and under air). Ru@rGO catalyst was reproducibly fabricated through a double-solvent method followed by wet-chemical reduction and characterized by using various spectroscopic and visualization techniques, which showed that the formation of well-dispersed and highly crystalline ruthenium(0) nanoparticles with a mean particle size of 2.7 +/- 0.9 nm on the surface of rGO. The catalytic performance of Ru@rGO was investigated in terms of activity and stability in the ammonia-borane assisted reduction of Cr(VI) to Cr(III), and the sum of the results gained from these catalytic tests revealed that Ru@rGO acts as both active (TOF=7.6 mol Cr2O72-/mol Ru.min) and stable (80% of its initial activity at 90% conversion at 5(th)reuse) heterogeneous catalyst in this significant catalytic transformation. This study also reports kinetic studies for Ru@rGO catalyzed Cr(VI) reduction in the presence of ammonia-borane depending on ruthenium ([Ru]), ammonia-borane ([AB]) concentrations and temperature to shed some light on the nature of the catalytic reaction and activation parameters.Article Citation - WoS: 29Amine-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, MehmetFormic 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.
