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    Crosslinked polyethyleneimine-based structures in different morphologies as promising CO2 adsorption systems: A comprehensive study
    (Wiley, 2024) Demirci, Şahin; Inger, Erk; Bhethanabotla, Venkat; Şahiner, Nurettin
    Although there are many studies on CO2 adsorption via PEI-modified carbon particles, metal-organic frameworks, zeolitic imidazolate frameworks, and silica-based porous structures, only a limited number of studies on solely cross-linked PEI-based structures. Here, the CO2 adsorption capacities of PEI-based microgels and cryogels were investigated. The effects of various parameters influencing the CO2 adsorption capacity of PEI-based structures, for example, crosslinker types, PEI types (branched [bPEI] or linear [lPEI]), adsorbent types (microgel or cryogel), chemical-modification including their complexes were examined. NaOH-treated glycerol diglycidyl ether (GDE) crosslinked lPEI microgels exhibited higher CO2 adsorption capacity among other microgels with 0.094 +/- 0.006 mmol CO2/g at 900 mm Hg, 25 degrees C with 2- and 7.5-fold increase upon pentaethylenehexamine (PEHA) modification and Ba(II) metal ion complexing, respectively. The CO2 adsorption capacity of bPEI and lPEI-based cryogels were compared and found that lPEI-GDE cryogels had higher adsorption capacity than bPEI-GDE cryogels with 0.188 +/- 0.01 mmol CO2/g at 900 mm Hg and 25 degrees C. The reuse studies revealed that NaOH-treated GDE crosslinked bPEI and lPEI microgels and cryogels showed promising potential, for example, after 10-times repeated use >50% CO2 adsorption capacity was retained. The results affirmed that PEI-based microgels and cryogels are encouraging materials for CO2 capture and reuse applications.
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    Hydrogen production from ammonia borane via hydrogel template synthesized Cu, Ni, Co composites
    (Pergamon-Elsevier Science Ltd, 2011) Özay, Özgür; Inger, Erk; Aktaş, Nahit; Şahiner, Nurettin
    In situ Co, Cu and Ni nanoparticles were synthesized by chemical reduction of the absorbed Co (II), Cu (II) and Ni (II) ions inside hydrogel networks prepared from 2-acryl-amido-2-methyl-1-propansulfonic acid (AMPS) and were used as a catalyst system in the generation of hydrogen in hydrolysis of ammonia borane (AB). Several parameters affecting the hydrolysis reaction such as the type of the metal, the amount of catalyst, the initial concentration of AB, and temperature, were investigated. The activation energy values in the hydrolysis reaction of AB solution in the presence p(AMPS)-Co, p(AMPS)-Cu and p(AMPS)-Ni catalyst systems were calculated as E-a = 47.7 kJ mol(-1), 48.8 kJ mol(-1) and 52.8 kJ mol(-1), respectively. Thus, the catalytic activity of the metal nanoparticles prepared inside the same hydrogel matrix was found to be Ni < Cu < Co. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
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    PEI modified natural sands of Florida as catalysts for hydrogen production from sodium borohydride dehydrogenation in methanol
    (John Wiley and Sons Ltd, 2021) Inger, Erk; Demirci, Şahin; Can, Mehmet; Sunol, Aydin K.; Philippidis, George; Şahiner, Nurettin
    Sand samples from Tampa (T) and Panama (P) City beaches in Florida were used as catalysts for dehydrogenation of NaBH4 in methanol. T and P sand samples were sieved to [removed]500 μm sizes, and the smallest fractions resulted in faster hydrogen generation rates (HGR), 565 ± 18 and 482 ± 24 mL H2 (min.g of catalyst)−1, respectively. After various base/acid treatments, HGR values of 705 ± 51 and 690 ± 47 mL H2 (min g of catalyst)−1 for HCl-treated T and P sand samples were attained, respectively. Next, T and P sand samples were modified with polyethyleneimine (PEI) that doubled the HGR values, 1344 ± 103, and 1190 ± 87 mL H2 (min.g of catalyst)−1 and increased ~8-fold, 4408 ± 187, and 3879 ± 169 mL H2 (min g of catalyst)−1, correspondingly after protonation (PEI+). The Ea values of T and P sand samples were calculated as 24.6 and 25.9 kJ/mol, and increased to 36.1, and 36.6 kJ/mol for T-PEI+ and P-PEI+ samples, respectively.
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    The on demand generation of hydrogen from Co-Ni bimetallic nano catalyst prepared by dual use of hydrogel: As template and as reactor
    (Pergamon-Elsevier Science Ltd, 2011) Şahiner, Nurettin; Özay, Özgür; Aktaş, Nahit; Inger, Erk; He, Jibao
    We report the preparation of metal nanoparticles in various formulations inside p(2-acrylamido-2-methyl-1-propansulfonic acid; p(AMPS)) hydrogels and their utilization as a catalyst in hydrolysis of NaBH4. The swollen, flexible p(AMPS) network was used for metal ion loading and reduction in situ for the preparation of Co:Ni nanoparticles as bimetallic clusters in various formulation, and Co and Ni bimetallic catalysts as Co + Co, Co + Ni, Ni + Co and Ni + Ni. In addition to utilization of hydrogels as support materials, the p(AMPS)-metal nanoparticle system was used as catalyst to generate hydrogen in the hydrolysis of NaBH4 with very high yield. Various parameters for the hydrolysis reaction were determined and the activation parameters were calculated. For the first time, inclusion of ferrite magnetic particles to control hydrogen generation on demand by using an externally applied magnetic field to remove the hydrogel-catalyst system from the hydrolysis medium is reported. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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