Browsing by Subject "Nickel"
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Item Open Access Atomic layer deposition of NiOOH/Ni(OH) 2 on PIM-1-based N-Doped carbon nanofibers for electrochemical water splitting in alkaline medium(Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim, 2019) Patil, Bhushan; Satılmış, Bekir; Khalily, Mohammad Aref; Uyar, TamerPortable and flexible energy devices demand lightweight and highly efficient catalytic materials for use in energy devices. An efficient water splitting electrocatalyst is considered an ideal future energy source. Well‐aligned high‐surface‐area electrospun polymers of intrinsic microporosity (PIM‐1)‐based nitrogen‐doped carbon nanofibers were prepared as a free‐standing flexible electrode. A non‐noble‐metal catalyst NiOOH/Ni(OH)2 was precisely deposited over flexible free‐standing carbon nanofibers by using atomic layer deposition (ALD). The morphology, high surface area, nitrogen doping, and Ni states synergistically showed a low onset potential (ηHER=−40 and ηOER=290 mV vs. reversible hydrogen electrode), small overpotential at η10 [oxygen evolution reaction (OER)=390.5 mV and hydrogen evolution reaction (HER)=−147 mV], excellent kinetics (Tafel slopes for OER=50 mV dec−1 and HER=41 mV dec−1), and high stability (>16 h) towards water splitting in an alkaline medium (0.1 m KOH). The performance was comparable with that of state‐of‐the‐art noble‐metal catalysts (e.g., Ir/C, Ru/C for OER, and Pt/C for HER). Post‐catalytic characterization with X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy further proved the durability of the electrode. This study provides insight into the design of 1D‐aligned N‐doped PIM‐1 electrospun carbon nanofibers as a flexible and free‐standing NiOOH/Ni(OH)2 decorated electrode as a highly stable nanocatalyst for water splitting in an alkaline medium.Item Open Access Covalent organic framework constructed by clicking azido porphyrin with perpropargyloxy-cucurbit[6]uril for electrocatalytic hydrogen generation from water splitting(American Chemical Society, 2021-04-26) Khaligh, Aisan; Sheidaei, Yasaman; Tuncel, DönüşIn the present study, we describe the synthesis and characterization of a new covalent organic framework (COF-TPP-CB[6]) which was assembled together by clicking perpropargyloxy cucurbit[6]uril (CB[6]) to the azido-functionalized tetraphenylporphyrin (TPP-4N3) through a copper-catalyzed azide–alkyne cycloaddition reaction (CuAAC). Perpropargyloxy CB[6] was synthesized through the direct oxidation of CB[6] to afford perhydroxy CB[6] followed by subsequent O-propargylation using NaH. We also demonstrated that the resulting framework (COF-TPP-CB[6]) can be employed as an efficient and stable electrocatalyst for hydrogen evolution reaction (HER) in alkaline medium upon loading it with a nickel cocatalyst. The effect of TiO2 and different loadings of Ni on the HER performance of TPP-CB[6] was also studied. Herein, 12%Ni@TPP-CB[6] as the optimum catalyst showed an impressive H2 production rate of 18.7 mmol h–1 g–1 with a low onset potential of −250 mV.Item Open Access Design, synthesis and application of electrospun heterostructured nanofibers for electrocatalytic hydrogen evolution reactions from water splitting(Bilkent University, 2021-11) Yılmaz, Elif BegümEnvironmental problems and climate changes have increased the importance of studies on the development of sustainable and clean energy methods that can be an alternative to energy production technologies using fossil fuels in recent years. Green hydrogen is environmentally friendly and a high-capacity energy carrier, as it does not cause any toxic by-products during its production. For this reason, attempts are being made to increase the efficiency of green hydrogen produced from water splitting. Development of the catalytic activities and stability of electrocatalysts has gained great importance in order to increase the performance of the hydrogen evolution reaction (HER). This study examines the effect of Ni/NiO-reduced graphene oxide catalysts fabricated in the form of heterostructured fibers by electrospinning on their intrinsic and extrinsic activities and their performance for HER. In order to examine the stability, activity and kinetics of the synthesized electrocatalyst, studies such as linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), chronoamperometry (CA), were carried out and Tafel curves were interpreted. It has been observed that the optimal electrocatalyst exhibits outstanding electrocatalytic performance with an over potential of -212 mV at 10 mA cm-2, and a Tafel slope of 90.6 mV dec-1 in alkaline electrolyte. Morphological and structural characterizations of electrocatalysts were investigated using X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM) methods.Item Open Access Differences in the accumulation and distribution profile of heavy metals and metalloid between male and female crayfish (Astacus leptodactylus)(2013) Tunca, E.; Ucuncu, E.; Ozkan, A.D.; Ulger, Z.E.; Cansizoǧlu, A.E.; Tekinay, T.Concentrations of selected heavy metals and a metalloid were measured by ICP-MS in crayfish (Astacus leptodactylus) collected from Lake Hirfanli, Turkey. Aluminum (Al), chromium (52Cr, 53Cr), copper ( 63Cu, 65Cu), manganese (Mn), nickel (Ni) and arsenic (As) were measured in the exoskeleton, gills, hepatopancreas and abdominal muscle tissues of 60 crayfish of both genders. With the exception of Al, differences were determined between male and female cohorts for the accumulation trends of the above-mentioned elements in the four tissues. It was also noted that the accumulation rates of Ni and As were significantly lower in gill tissue of females compared to males and no significant difference was observed for Cu isotopes in female crayfish. Cluster Analysis (CA) recovered similar results for both genders, with links between accumulations of Ni and As being notable. Accumulation models were described separately for male and female crayfish using regression analysis, and are presented for models where R2 > 0.85. © 2013 Springer Science+Business Media New York.Item Open Access Effect of milling time on the structure, micro-hardness, and thermal behavior of amorphous/nanocrystalline TiNiCu shape memory alloys developed by mechanical alloying(Elsevier Ltd, 2014) Alijani F.; Amini, R.; Ghaffari, M.; Alizadeh, M.; Okyay, Ali KemalIn the present paper, the effect of milling process on the chemical composition, structure, microhardness, and thermal behavior of Ti-41Ni-9Cu compounds developed by mechanical alloying was evaluated. The structural characteristic of the alloyed powders was evaluated by X-ray diffraction (XRD). The chemical composition homogeneity and the powder morphology and size were studied by scanning electron microscopy coupled with electron dispersive X-ray spectroscopy. Moreover, the Vickers micro-indentation hardness of the powders milled for different milling times was determined. Finally, the thermal behavior of the as-milled powders was studied by differential scanning calorimetery. According to the results, at the initial stages of milling (typically 0-12. h), the structure consisted of a Ni solid solution and amorphous phase, and by the milling evolution, nanocrystalline martensite (B19') and austenite (B2) phases were initially formed from the initial materials and then from the amorphous phase. It was found that by the milling development, the composition uniformity is increased, the inter-layer thickness is reduced, and the powders microhardness is initially increased, then reduced, and afterward re-increased. It was also realized that the thermal behavior of the alloyed powders and the structure of heat treated samples is considerably affected by the milling time.Item Open Access Enhancing oxygen evolution catalytic performance of nickel borate with cobalt dopingand carbon nanotubes(Wiley, 2023-02-16) Enez, S.; Karani Konuksever, V.; Samuei, S.; Karadaş, Ferdi; Ülker, E.Item Open Access Hydrogen recombination on a mixed adsorption layer at saturation on a metal surface: H → (D + H)sat + Ni(100)(2003) Güvenç, Z. B.; Güvenç, D.Interactions of H atom beams with (D+H)-covered Ni(100) surfaces are simulated at saturation level of 0.93 monolayer using quasi-classical microcanonical trajectory method. The Ni substrate is treated as a non-rigid multilayer slab using an embedded-atom method. The model many-body potential energy surface London-Eyring-Polanyi-Sato used to characterize the interactions between H-H and H-Ni(100) systems parameterized by fitting to the results of detailed total-energy calculations based on density functional theory. Since most of the incident H atoms trap to form hot atoms, reactions between the projectile atom and adsorbates are mainly due to the hot atom process. Results of a linear behavior of the total HD and quadratic behavior of the D2 yields with the initial D coverage, in addition, significantly low secondary reactions between the adsorbates are found to be in good agreement with the experiment. In addition distributions of the rotational states of the product molecules, molecular desorption angles, vibrational states of the product molecules, molecular formation and desorption time, total and translational energies of the product molecules are also calculated as functions of different H and D coverages on the surface. © 2003 Elsevier Science B.V. All rights reserved.Item Open Access In situ-Electrochemically reduced graphene oxide integrated with cross-linked supramolecular polymeric network for electrocatalytic hydrogen evaluation reaction(Elsevier, 2021-08-26) Aoudi, Bouthaina; Khaligh, Aisan; Sheidaei, Yasaman; Tuncel, DönüşHerein, we report the synthesis of a new supramolecular polymeric network (PCN) assembled through crosslinking of propyl bromide substituted tetraphenyl porphyrin with perhydroxy-cucurbit [8]uril and its use in the electrocatalytic hydrogen evaluation reaction after loading with nickel and integrating with in situ-electrochemically reduced graphene oxide (ERGO). Electrode was prepared by first coating graphene oxide on the FTO substrate followed by layering the nickel loaded PCN and finally by applying an appropriate voltage to reduce the graphene oxide in situ electrochemical reaction. The loading of nickel cocatalyst into PCN together with the integration of ERGO layer substantially improved its HER efficiency. Effect of various concentrations of Ni and GO on the HER activity of the developed electrocatalyst were investigated. Therein, ERGO1/Ni2@PCN catalyst containing 41% Ni and 50% GO (with respect to PCN) with only one layer of each component demonstrated excellent HER activity and stability with low onset and overpotentials of −20 mV, η@10 mA cm−2 of −360 mV, respectively, and remarkable hydrogen generation rate of 27.5 mmol h−1 g−1 in 1 M KOH. This noble-metal-free catalytic system is simple yet highly promising for the efficient hydrogen evolution reaction from water splitting.Item Open Access Isotope Effect and Phonon Softening in Superconducting Borocarbides and Boronitrides(1998) Hakioǧlu, Tuğrul; Ivanov, V. A.The isotope effect in the recently disvovered class o superconductors LuNi2B2C and La3Ni2B2N3 is investigated in the context of electron-squezed phonon interaction renormalizing the Ni-d electron-electron correlations. Squeezed phonon mode originates from the anharmonic character of the tetragonal Ni-B structure and is polarized in the vortical direction to the Ni layers. The isotope effect arises as a result of the zero point motion of the Ni-Ni d-electron hopping amplitude dominantly due to this vertical phonon mode. Within this model the isotope exponent is calculated to be αB ≤ 0.20 as compared to the recently found experimental value αexp B=0.27∓0.10. Finally, the phonon frequency softening predicted by our model eletron-phonon interaction is discussed within the context of recent experiments on the relevant boron A1g softening.Item Open Access Microstructural characterization of medical-grade stainless steel powders prepared by mechanical alloying and subsequent annealing(Elsevier, 2013) Salahinejad, E.; Hadianfard, M. J.; Ghaffari, M.; Amini, R.; Mashhadi, S. B.; Okyay, Ali KemalThe harmful effect of nickel ions released from conventional stainless steel implants has provided a high level of motivation for the further development of nickel-free stainless steels. In this paper, the microstructure of medical-grade nickel-free stainless steel powders, with the chemical composition of ASTM F2581, is studied during mechanical alloying and subsequent annealing. Rietveld X-ray diffraction and transmission electron microscopy evaluations reflect nanocrystallization, austenitization and amorphization of the powders due to mechanical activation. It is also realized that annealing of the as-milled powder can develop a single austenitic structure with nanometric crystallite sizes, implying a considerable inherent resistance to grain growth. This study demonstrates the merit of mechanical alloying and subsequent annealing in the development of nanostructured medical-grade stainless steels.Item Open Access Nickel nanoparticles decorated on electrospun polycaprolactone/chitosan nanofibers as flexible, highly active and reusable nanocatalyst in the reduction of nitrophenols under mild conditions(Elsevier, 2017-04) Karakas, K.; Celebioglu A.; Celebi, M.; Uyar, Tamer; Zahmakiran, M.Today, the reduction of nitro aromatics stands a major challenge because of the pollutant and detrimental nature of these compounds. In the present study, we show that nickel(0) nanoparticles (Ni-NP) decorated on electrospun polymeric (polycaprolactone(PCL)/chitosan) nanofibers (Ni-NP/ENF) effectively catalyze the reduction of various nitrophenols (2-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol) under mild conditions. Ni-NP/ENF nanocatalyst was reproducibly prepared by deposition-reduction technique. The detailed characterization of these Ni-NP/ENF based nanocatalyst have been performed by using various spectroscopic tools including ICP-OES, P-XRD, XPS, SEM, BFTEM, HRTEM and BFTEM-EDX techniques. The results revealed the formation of well-dispersed nickel(0) NP (dmean = 2.71–2.93 nm) on the surface of electrospun polymeric nanofibers. The catalytic activity of the resulting Ni-NP/ENF was evaluated in the catalytic reduction of nitrophenols in aqueous solution in the presence of sodium borohydride (NaBH4) as reducing agent, in which Ni-NP/ENF nanocatalyst has shown high activity (TOF = 46.2 mol 2-nitrophenol/mol Ni min; 48.2 mol 2,4-dinitrophenol/mol Ni min; 65.6 mol 2,4,6-trinitrophenol/mol Ni min). More importantly, due to the nanofibrous polymeric support, Ni-NP/ENF has shown a flexible characteristics along with reusability property. Testing the catalytic stability of Ni-NP/ENF revealed that this new catalytic material provides high reusability performance (at 3rd reuse 86% for 2-nitrophenol, 83% 2,4-dinitrophenol and 82% 2,4,6-trinitrophenol) for the reduction of nitrophenols even at room temperature and under air. The present study reported here also includes the compilation of wealthy kinetic data for Ni-NP/ENF catalyzed the reduction of nitrophenols in aqueous sodium borohydride solution depending on temperature and type of support material (Al2O3, C, SiO2) to understand the effect of the support material and determine the activation parameters.Item Open Access Oligomerization of ethylene in a slurry reactor using a nickel/sulfated alumina catalyst(American Chemical Society, 1997) Zhang, Q.; Kantcheva, M.; Dalla Lana, I. G.During the oligomerization of ethylene over heterogeneous catalysts, the production of α-olefins may be lowered because of an accompanying deactivation of catalyst resulting from strong adsorption of products, by isomerization or by a tendency to copolymerize into branched products. The oligomerization of ethylene was studied using Ni(II)/sulfated alumina catalysts prepared with a nonporous fumed alumina (ALON) support. The influences of methods of catalyst preparation and activation upon oligomerization activity were screened using a gas - solid microreactor. On the basis of the test results obtained in the microreactor, a modified form of the superior catalyst was prepared and its performance was examined in more detail using a well-agitated gas - liquid - solid slurry reactor. This catalyst exhibited very good oligomerization activity with no apparent deactivation in the slurry reactor at temperatures at or below 298 K and at near-atmospheric pressure. Complete conversion of the ethylene with the production of mainly two oligomers, 1-butene and 1-hexene, was attained. After 34 h in the slurry, formation of a significant amount of two branched C6 isomers was observed.Item Open Access Porous organic polymers for electrochemical and energy storage application(Bilkent University, 2022-08) Yau, Arma MusaThe intrinsic porosity and tunable morphology of Porous Organic Polymers (POPs), materials made from organic building blocks joined by strong covalent bonds, have become appealing in the context of electrochemical applications. In the first section of this thesis, a low-cost thiophene derivative and melamine were assembled into nitrogen and sulfur-enriched microporous organic polymer (MOP) using a pyrolysis-free one-pot Schiff-base type polycondensation reaction. The synthesized polymer is characterized by FT-IR, SEM, TEM, BET, XRD, XPS, TGA and UV-VIS. With 195.731 m2 g–1 surface area and 0.047 cm3 g–1 pore volume, the as-synthesized MOP has a cotton-like morphology and a micropore-dominated pore size distribution. After encapsulating it with a nickel co-catalyst, we showed that the obtained framework (MOP) could be used as an efficient catalyst for hydrogen evolution reaction (HER) in an alkaline electrolyte with the optimum composite (Ni2@MOP) exhibiting a remarkable onset overpotential of -66 mV. Furthermore, the optimum electrocatalyst showed good stability, delivering 90.84% faradaic efficiency (FE) after a 3.5 h chronoamperometry experiment. In the second section, the synthesized porous organic polymer and CB[6]-porphyrin covalent organic framework were investigated for potential use as electrode materials for supercapacitors.Item Open Access Systematic study of adsorption of single atoms on a carbon nanotube(American Physical Society, 2003) Durgun, Engin; Dag, S.; Bagci, V. M. K.; Gülseren, O.; Yildirim, T.; Çıracı, SalimWe studied the adsorption of single atoms on a semiconducting and metallic single-wall carbon nanotube from first principles for a large number of foreign atoms. The stable adsorption sites, binding energy, and the resulting electronic properties are analyzed. The character of the bonding and associated physical properties exhibit dramatic variations depending on the type of the adsorbed atom. While the atoms of good conducting metals, such as Cu and Au, form very weak bonding, atoms such as Ti, Sc, Nb, and Ta are adsorbed with relatively high binding energy. Most of the adsorbed transition-metal atoms excluding Ni, Pd, and Pt have a magnetic ground state with a significant magnetic moment. Our results suggest that carbon nanotubes can be functionalized in different ways by their coverage with different atoms, showing interesting applications such as one-dimensional nanomagnets or nanoconductors and conducting connects, etc.Item Open Access Triazine/thiophene-based microporous organic polymer for electrocatalytic hydrogen evolution reaction(John Wiley and Sons, Ltd, 2022-12-07) Yau, Arma Musa; Khaligh, Aisan; Tuncel, DönüşIn this study, sulfur-enriched microporous organic polymer (MOP) was prepared using one-pot Shiff-base type polycondensation reaction of thiophendicarboxaldehyde with melamine. With 195.731 m2 g−1 surface area and 0.047 cm3 g−1 pore volume, the as-synthesized MOP has a cotton-like morphology and a micropore-dominated pore size distribution. After loading MOP with nickel as a co-catalyst, we demonstrated that the obtained framework could be used as an efficient and robust electrocatalyst for hydrogen evolution reaction (HER) in an alkaline medium with the optimum composite (Ni2@MOP) exhibiting a low onset potential of −66 mV. Furthermore, the optimum electrocatalyst showed good stability, delivering 91% faradaic efficiency (FE) after a 3.5 h chronoamperometry experiment.