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Article Citation - WoS: 79Citation - Scopus: 84Methylene Blue Photocatalytic Degradation Under Visible Light Irradiation on Copper Phthalocyanine-Sensitized Tio2 Nanopowders(Elsevier Science Bv, 2017) Cabir, Beyza; Yurderi, Mehmet; Caner, Nurdan; Agirtas, Mehmet Salih; Zahmakiran, Mehmet; Kaya, MuratDescribed herein is a new photocatalytic material that shows remarkable catalytic performance in terms of activity and reusability in the photocatalytic degradation of methylene blue (MB) in water. The new catalyst system comprised of copper phthalocyanine modified titanium(IV) oxide (TiO2) nanopowders (CuPc-TiO2\) was prepared by the wet chemical impregnation method to improve the photocatalytic activity of TiO2 and characterized by the combination of various spectroscopic tools including ICP-OES, P-XRD, DR/UV-Vis, FTIR, FE-SEM, SEM-EDX, BFTEM, HRTEM and N-2-adsorption-desorption techniques. The photocatalytic performance of the resulting CuPc-TiO2 in terms of activity and stability was evaluated by the photocatalytic degradation of MB in aqueous solution under mild conditions. Our results revealed that CuPc-TiO2 photocatalyst displayed remarkable activity (TOF = 3.73 mol MB/(mol CuPc + mol TiO2) x h) in the complete (100%) photocatalytic degradation of MB under visible light irradiation (150 W). Moreover, CuPc-TiO2 photocatalyst showed excellent stability against to sintering and clumping throughout the reusability experiments and it retained >80% of its initial activity even at 5th reuse, which makes it reusable photocatalyst in the photocatalytic degradation of MB. (C) 2017 Elsevier B.V. All rights reserved.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: 128Mnox< 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, MehmetFormic 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.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.Article Citation - WoS: 13Citation - Scopus: 14Thermally Highly Stable Polyhedral Oligomeric Silsesquioxane (poss)-Sulfur Based Hybrid Inorganic/Organic Polymers: Synthesis, Characterization and Removal of Mercury Ion(Royal Soc Chemistry, 2022) Berk, Hasan; Kaya, Murat; Cihaner, AtillaElemental sulfur was copolymerized with octavinyl polyhedral oligomeric silsesquioxane (OV-POSS) cages in diglyme solution via the inverse vulcanization method and characterized using NMR and FTIR spectroscopic techniques. The polysulfur copolymer called poly(sulfur-random-octavinyl polyhedral oligomeric silsesquioxane) (poly(S-r-OV-POSS)) was cured successfully sequentially at 170, 200 and 230 degrees C without changing the structure of the POSS cages in the polymer backbone. Highly crosslinked poly(S-r-OV-POSS) polymer cured at 200 and 230 degrees C exhibited high thermal stability at high temperatures; the loss of the samples was only 10% weight at 400 degrees C and 27% at 800 degrees C. Finally, the feasibility of poly(S-r-OV-POSS) as an adsorbent for the removal of Hg(ii) ions, as an example of a toxic heavy metal, from an aqueous solution was investigated. Optimization of the pH of the solution and contact time was performed and almost all Hg(ii) ions were collected from the aqueous solution at pH = 7 in 1 h (99% adsorption).Article Citation - WoS: 1Citation - Scopus: 1Silver Nanoparticles Added Polymer Film Prepared by Electrochemical Route for Surface Enhanced Raman Scattering Applications(Electrochemical Soc inc, 2019) Khadim, Raisan; Uzun, Ceren; Cihaner, Atilla; Kaya, MuratA simplemethod for the fabrication of stable and highly active surface enhanced Raman scattering (SERS) substrate by exploiting the optical properties of the silver nanoparticles (AgNPs) and organizational characteristics of the polymer is presented. Homogeneous distribution ofAgNPs is achieved with the usage of poly (4,7-di-2,3-dihydrothieno [3,4-b] [1,4] dioxin-5-yl-2,1,3 benzoselena diazole) (PESeE) film coated on the indium tin oxide glass (ITO) surface. The obtained structure ensured the emergence of a large number of hot spots where the localization of electromagnetic energy can result in enhancement of the Raman signal. The effect of the PESeE film thickness, the density of AgNPs added to the polymer film, and the concentration of silver ion solution on the morphology of the substrate and the enhancement of the SERS signal was revealed by using field emission scanning electron microscopy (FE-SEM) and SERS measurements. Enhancement power, homogeneity, and stability of the PESeE-AgNPs substrate were also investigated with measurement of the Raman probe. Spot-to-spot and batch-to-batch reproducibilities of the prepared substrate were calculated as 8.4%, and 10.2% (RSD %) respectively. Due to these properties, PESeE-AgNPs SERS substrate can be a good candidate for the detection and sensor application of various biological and chemical analytes. (C) 2019 The Electrochemical Society.Article Citation - WoS: 148Citation - Scopus: 152Carbon 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, MuratTrimetallic 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.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: 24Citation - Scopus: 27The Pimpled Gold Nanosphere: a Superior Candidate for Plasmonic Photothermal Therapy(Dove Medical Press Ltd, 2020) Nasseri, Behzad; Turk, Mustafa; Kosemehmetoglu, Kemal; Kaya, Murat; Piskin, Erhan; Rabiee, Navid; Webster, Thomas J.Background: The development of highly efficient nanoparticles to convert light to heat for anti-cancer applications is quite a challenging field of research. Methods: In this study, we synthesized unique pimpled gold nanospheres (PGNSs) for plasmonic photothermal therapy (PPTT). The light-to-heat conversion capability of PGNSs and PPTT damage at the cellular level were investigated using a tissue phantom model. The ability of PGNSs to induce robust cellular damage was studied during cytotoxicity tests on colorectal adenocarcinoma (DLD-1) and fibroblast cell lines. Further, a numerical model of plasmonic (COMSOL Multiphysics) properties was used with the PPTT experimental assays. Results: A low cytotoxic effect of thiolated polyethylene glycol (SH-PEG400-SH-) was observed which improved the biocompatibility of PGNSs to maintain 89.4% cell viability during cytometry assays (in terms of fibroblast cells for 24 hrs at a concentration of 300 mu g/mL). The heat generated from the nanoparticle-mediated phantom models resulted in Delta T=30 degrees C, Delta T=23.1 degrees C and Delta T=21 degrees C for the PGNSs, AuNRs, and AuNPs, respectively (at a 300 mu g/mL concentration and for 325 sec). For the in vitro assays of PPTT on cancer cells, the PGNS group induced a 68.78% lethality (apoptosis) on DLD-1 cells. Fluorescence microscopy results showed the destruction of cell membranes and nuclei for the PPTT group. Experiments further revealed a penetration depth of sufficient PPTT damage in a physical tumor model after hematoxylin and eosin (H&E) staining through pathological studies (at depths of 2, 3 and 4 cm). Severe structural damages were observed in the tissue model through an 808-nm laser exposed to the PGNSs. Conclusion: Collectively, such results show much promise for the use of the present PGNSs and photothermal therapy for numerous anti-cancer applications.
