Scopus İndeksli Yayınlar Koleksiyonu / Scopus Indexed Publications Collection
Permanent URI for this collectionhttps://hdl.handle.net/11147/7148
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Article Citation - WoS: 1Citation - Scopus: 1Synthesis of Acetonitrile From Nh<sub>3</Sub> Mixtures on Molybdenum Nitride: Insights Into the Reaction Mechanism(Elsevier, 2024) Kizilkaya, Ali Can; Martinez-Monje, Maria Elena; Prieto, GonzaloOwing to their metallic-like surface electronic properties and their capacity to act as reservoirs and solid transfer agents for active nitrogen, transition metal nitrides are interesting as solid catalysts for C-C and C-N coupling reactions for the bottom-up production of higher (C2+) nitrogenated chemicals from unconventional carbon resources. The catalytically active state and reaction mechanism for the direct synthesis of acetonitrile from syngas/ammonia mixtures are studied on an unsupported Mo catalyst from complementary experimental and computational approaches. Temperature resolved X-ray diffraction and X-ray photoemission spectroscopy verify that an oxidic MoO(3 )catalyst precursor undergoes in situ (near-surface) nitridation, upon exposure to reaction conditions at 723 K, rendering Mo2N the actual working catalyst. Density Functional Theory mechanistic investigations on a gamma- Mo 2 N(100) model surface point to a hydrogen-assisted CO dissociation on the nitride surface. Moreover, surface oxygen, evolved from CO dissociation, is predicted to play a central role as hydrogen acceptor, to enable the dehydrogenative NH3 dissociation. Direct condensation of CH and N adspecies proceeds with a low energy barrier of 33 kJ mol(-1), which makes C-N coupling preferred over full hydrogenation of CHx species, in agreement with the experimental modest selectivity to methane (ca. 10 %). Both experimental and computational results indicate that HCN is a major intermediate product along the reaction pathway to acetonitrile. No energetically feasible associative reaction pathways could be identified for C-C coupling from HCN. The dissociation of the latter intermediate product is predicted to precede the reaction of CN adspecies to CHx. Similarly to NH3 dissociation, dehydrogenative HCN activation on the Mo2N 2 N surface is predicted to be facilitated through hydrogen abstraction by surface oxygen species, yet subjected to a comparatively higher energy barrier (>120 kJ mol(-1)), therefore likely to control the overall kinetics. These findings suggest that the enhancement of HCN dissociation is a central design objective towards Mo2N-based 2 N-based catalysts with advanced performance.Article Citation - WoS: 3Citation - Scopus: 4Enhancing Biogas Production From Chicken Manure Through Vacuum Stripping of Digestate(Springer Heidelberg, 2023) Sengur, Ozlem; Akgul, Deniz; Bayrakdar, Alper; Calli, BarisThe vacuum stripping's combined ammonia removal and disintegration effect on chicken manure digestate was evaluated for the first time at different pH values (8.5, 9.5, and 10.5) and temperatures (30, 50, and 70 degrees C). In this way, the potential increase in biogas production by recirculating the vacuum-stripped digestate to the anaerobic digester was determined. Experimental results showed that increasing pH and temperature significantly increase TAN removal, but pH is more effective. A significant portion of the ammonia was removed in the first 30 min. Therefore, a second set of stripping tests was performed for 30 min and at 70 degrees C and pH 10.5. After 30-min tests, a biomethane potential (BMP) assay was performed using the vacuum-stripped digestate to determine how vacuum stripping affects biomethane production. Despite having the lowest disintegration efficiency, the highest biomethane potential (56.2 +/- 29.7 mL CH4/gVS) was obtained with the digestate, which was subjected to vacuum stripping at 70 celcius without pH adjustment, and 48.7% more methane was produced than the control set. The lower residual biomethane potential in vacuum-stripped digestate at pH 9.5 and 10.5 was attributed to Na+ inhibition resulting from high NaOH consumption for pH adjustment.Article Citation - WoS: 3Citation - Scopus: 3Amperometric Detection of Nh3 by Aromatic Sam-Modified Graphene(IEEE, 2023) Yağmurcukardeş, Nesli; Bayram, Abdullah; Aydın, Hasan; Can, Mustafa; Demiç, Şerafettin; Açıkbaş, Yaşar; Çelebi, CemAmmonia (NH3) is a toxic substance resulting in various acute and chronic effects on individuals. NH3 detection, monitoring methods, and detection tools are desperately needed. In this work, we improved the NH3 sensing capabilities of grapheme (GP) films deposited by chemical vapor deposition (CVD) by modifying aromatic self-assembled monolayer (SAM) molecules such as 5-[(3-methylphenyl) (phenyl) amino] isophthalic acid (MeIPA) and 5-(diphenyl)amino] isophthalic acid (PhIPA) on amperometric detection method. Morphological investigations of the films were carried out by optical and scanning electron microscopy (SEM). Surface potential was characterized with Kelvin probe force microscopy (KPFM), and vibrational properties were characterized with Raman spectroscopy. MeIPA modification increased NH3 uptake by two times compared to unmodified GP. The results indicated that the SAM modification enhanced NH3 molecule adsorption and improved its periodic reversible and reproducible response using the amperometric detection system, indicating that SAM molecules might be a feasible probe for NH3. © 2001-2012 IEEE.Article Citation - WoS: 7Citation - Scopus: 6Anisotropic Etching of Cvd Grown Graphene for Ammonia Sensing(Institute of Electrical and Electronics Engineers Inc., 2022) Yağmurcukardeş, Nesli; Bayram, Abdullah; Aydın, Hasan; Yağmurcukardeş, Mehmet; Açıkbaş, Yaser; Peeters, François M.; Çelebi, CemBare chemical vapor deposition (CVD) grown graphene (GRP) was anisotropically etched with various etching parameters. The morphological and structural characterizations were carried out by optical microscopy and the vibrational properties substrates were obtained by Raman spectroscopy. The ammonia adsorption and desorption behavior of graphene-based sensors were recorded via quartz crystal microbalance (QCM) measurements at room temperature. The etched samples for ambient NH3 exhibited nearly 35% improvement and showed high resistance to humidity molecules when compared to bare graphene. Besides exhibiting promising sensitivity to NH3 molecules, the etched graphene-based sensors were less affected by humidity. The experimental results were collaborated by Density Functional Theory (DFT) calculations and it was shown that while water molecules fragmented into H and O, NH3 interacts weakly with EGPR2 sample which reveals the enhanced sensing ability of EGPR2. Apparently, it would be more suitable to use EGRP2 in sensing applications due to its sensitivity to NH3 molecules, its stability, and its resistance to H2O molecules in humid ambient.Article Citation - WoS: 6Citation - Scopus: 6Effect of Ammonia on Cobalt Fischer-Tropsch Synthesis Catalysts: a Surface Science Approach(Royal Society of Chemistry, 2019) Kızılkaya, Ali Can; Niemantsverdriet, J. W.; Weststrate, C. J.Ammonia adsorption and decomposition on defect-rich hcp-Co(0001) surfaces were investigated under ultra-high vacuum conditions in order to provide a fundamental explanation for industrially observed ammonia poisoning of cobalt based Fischer-Tropsch synthesis (FTS) catalysts. Temperature-programmed desorption, infrared spectroscopy and work function measurements indicate that undercoordinated sites bind ammonia stronger than sites on flat Co(0001), and they also induce its dehydrogenation. Density functional theory calculations were employed to explore the reactivity of defective Co surfaces using the fcc-Co(211) as a model. The results indicate that the decomposition products (NH x ) adsorb strongly on or around the step site on fcc-Co(211). We find that NH (+2H ad ), adsorbed in the threefold site on the upper terrace, is equally stable as NH 2 (+H ad ), adsorbed in the bridge position at the step edge, both being significantly more stable than the equivalent species adsorbed on the flat Co(0001). The calculated activation barriers for NH 3,ad dehydrogenation steps are in reasonable agreement with the barriers obtained by fitting experimental data. Based on these fundamental insights, poisoning of cobalt nanoparticles during FTS by NH 3 contaminants can be linked mainly to the blocking of undercoordinated sites by strongly adsorbed NH 2 species.Article Citation - WoS: 2Citation - Scopus: 3The Amido and Bisalkoxo-Complexes of [tri(3,5-Dimethylpyrazolyl)borato]molydenum Nitrosyl(TÜBİTAK, 1998) Topaloğlu, IşılIn this study, the amido nitrosyl molybdenum complex, [Mo{HM(3,5-Me2C3HN2)3}(NO)Cl(NH 2)], was prepared. This compound reacts with alocohols, yielding the bisalkoxo complexes, [Mo{HM(3,5-Me2C3HN2)3}(NO)(OR) 2] (R = Me, Et, Prn, Bun). The new complexes were analyzed by IR and 1H-NMR spectroscopy.Article Citation - WoS: 1Citation - Scopus: 2Synthesis and Characterization of Amido and Amido(monoalkylamido)nitrosyl-[tris(3,5 Complexes(Marcel Dekker Inc., 1997) Topaloğlu, Işıl; McCleverty, Jon A.The chloro-amido complex [Mo{HB(3,5-Me2C3HN2)3}(NO)Cl(NH 2)] was prepared by treating [Mo{HB(3,5-Me2C3HN2)3}(NO)Cl 2] with an excess of ammonia. The monoalkylamido complexes [Mo{HB(3,5-Me2C3HN2)3}-(NO)(NH 2)(NHR)] (R = Me, Et, Pr-n and Bu-n) were obtained by the reaction of [Mo{HB(3,5-Me2C3HN2)3}(NO)Cl(NH 2)] with the appropriate primary amines. The IR and 1H NMR spectra of the new complexes were investigated.